WO2019189792A1 - Mixed composition - Google Patents

Mixed composition Download PDF

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Publication number
WO2019189792A1
WO2019189792A1 PCT/JP2019/014074 JP2019014074W WO2019189792A1 WO 2019189792 A1 WO2019189792 A1 WO 2019189792A1 JP 2019014074 W JP2019014074 W JP 2019014074W WO 2019189792 A1 WO2019189792 A1 WO 2019189792A1
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group
film
mass
formula
hydrocarbon group
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PCT/JP2019/014074
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French (fr)
Japanese (ja)
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彩香 櫻井
友宏 伊藤
知典 宮本
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住友化学株式会社
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Priority to KR1020207031032A priority Critical patent/KR20200140841A/en
Priority to CN201980020778.XA priority patent/CN111936583B/en
Publication of WO2019189792A1 publication Critical patent/WO2019189792A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/16—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/16—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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 invention relates to a mixed composition of an organosilicon compound and an organic polysilazane.
  • Patent Documents 1 and 2 disclose coating agents containing polysilazane and silicone oil.
  • the water / oil-repellent film may be exposed to harsh environments such as ultraviolet rays and rain water depending on the use such as outdoors, and it is preferable that good performance can be maintained even after being exposed to harsh environments.
  • harsh environments such as ultraviolet rays and rain water depending on the use such as outdoors
  • the film obtained by using the coating agent disclosed in Patent Documents 1 and 2 still has room for study in terms of wear resistance, sulfuric acid resistance, appearance, and the like.
  • the present invention has been made paying attention to the above-described circumstances, and an object thereof is to provide a composition capable of realizing a film having excellent water and oil repellency and at least excellent sulfuric acid resistance.
  • the film obtained from the composition of the present invention preferably further has at least one of droplet slipperiness, abrasion resistance, appearance, and hot water resistance, preferably droplet slippage, wear resistance, appearance, It is more preferable that all of the hot water resistance is excellent.
  • the present inventors have obtained an organic silicon compound and an organic polysilazane in which a trialkylsilyl group-containing molecular chain and a hydrolyzable group are bonded to a silicon atom.
  • a film excellent in water repellency / oil repellency and sulfuric acid resistance, and preferably excellent in droplet slippage, abrasion resistance, appearance, and warm water resistance was obtained. completed.
  • the present invention is as follows.
  • a mixed composition comprising: The hydrogen atom contained in the trialkylsilyl group may be substituted with a fluorine atom, The mixed composition in which the total concentration of the organosilicon compound (a) and the organic polysilazane (b) is 0.2% by mass or more and less than 2.6% by mass with respect to 100% by mass of the composition.
  • R p21 , R p22 and R p23 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. However, at least one of R p21 and R p22 represents a hydrocarbon group having 1 to 10 carbon atoms.
  • a plurality of R s1 each independently represents a hydrocarbon group or a trialkylsilyloxy group, and the hydrogen atom contained in the hydrocarbon group or trialkylsilyloxy group is a fluorine atom. May be replaced,
  • a plurality of R s2 each independently represents an alkyl group having 1 to 10 carbon atoms; n1 represents an integer of 1 or more, Z s1 represents —O— or a divalent hydrocarbon group, and —CH 2 — contained in the divalent hydrocarbon group may be replaced by —O—.
  • Y s1 represents a single bond or —Si (R s2 ) 2 —L s1 —, the L s1 represents a divalent hydrocarbon group, and —CH 2 — contained in the divalent hydrocarbon group is -O- may be substituted.
  • a ⁇ a1> represents a hydrolysable group each independently, Z a1 represents a trialkylsilyl group-containing molecular chain, a siloxane skeleton-containing group, or a hydrocarbon chain-containing group, The hydrogen atom contained in the trialkylsilyl group in Z a1 may be substituted with a fluorine atom, x is 0 or 1.
  • a composition capable of realizing a film excellent in water repellency / oil repellency and sulfuric acid resistance can be provided by mixing an organosilicon compound and an organic polysilazane at a predetermined concentration. Therefore, the film obtained from the composition of the present invention tends to maintain water and oil repellency for a long period of time even outdoors.
  • the film obtained from the composition of the present invention preferably further has at least one of droplet slipperiness, abrasion resistance, appearance, and hot water resistance, preferably droplet slippage, wear resistance, appearance, It is more preferable that all of the hot water resistance is excellent.
  • composition of the present invention at least one trialkylsilyl group-containing molecular chain and at least one hydrolyzable group are bonded to a silicon atom (hereinafter, this silicon atom may be referred to as “central silicon atom”).
  • this silicon atom may be referred to as “central silicon atom”.
  • the organic silicon compound (a) and the organic polysilazane (b) at a predetermined concentration to form a film with water / oil repellency and sulfuric acid resistance (preferably water / oil repellency and It has been found that in addition to sulfuric acid resistance, droplet slipping, abrasion resistance, appearance and hot water resistance are excellent.
  • the composition of the present invention includes those that have reacted after mixing, for example, during storage.
  • organosilicon compound (a) in the present invention at least one trialkylsilyl group-containing molecular chain and at least one hydrolyzable group are bonded to a central silicon atom.
  • the number of trialkylsilyl group-containing molecular chains bonded to the central silicon atom is 1 or more, preferably 3 or less, more preferably 2 or less, and particularly preferably 1 It is.
  • the hydrolyzable group may be any group that gives a hydroxy group (silanol group) by hydrolysis.
  • examples thereof include an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group; Preferred examples include a group; an acetoxy group; a chlorine atom; an isocyanate group; Among these, an alkoxy group having 1 to 6 carbon atoms is preferable, an alkoxy group having 1 to 4 carbon atoms is more preferable, and an alkoxy group having 1 to 2 carbon atoms is further preferable.
  • the number of hydrolyzable groups bonded to the central silicon atom is 1 or more, preferably 2 or more, and usually 3 or less.
  • the organosilicon compound (a) of the present invention has a large number of silicon atoms, and the hydrolyzable group may be bonded to two or more silicon atoms. It is particularly preferable to bond only to a silicon atom.
  • the central silicon atom of the organosilicon compound (a) includes a siloxane having a number of elements smaller than the number of elements constituting the molecular chain of the trialkylsilyl group-containing molecular chain, in addition to the trialkylsilyl group-containing molecular chain and hydrolyzable group.
  • a skeleton-containing group or a hydrocarbon chain-containing group containing a hydrocarbon chain having a carbon number smaller than the number of elements constituting the molecular chain of the trialkylsilyl group-containing molecular chain may be bonded.
  • composition of the present invention two or more of the above organosilicon compounds (a) may be mixed.
  • the organosilicon compound (a) is preferably a compound represented by the following formula (A1).
  • R a1 represents a trialkylsilyl group-containing molecular chain
  • a a1 each independently represents a hydrolyzable group
  • Z a1 represents a trialkylsilyl group-containing molecular chain or a siloxane skeleton.
  • the hydrogen atom contained in the trialkylsilyl group in R a1 and Z a1 may be substituted with a fluorine atom, and x is 0 or 1;
  • the trialkylsilyl group-containing molecular chain of R a1 is a monovalent group having a structure in which the trialkylsilyl-containing group is bonded to the end of the molecular chain, and the trialkylsilyl-containing group is bonded to the molecular chain.
  • the water repellency and oil repellency of the film formed from the composition of the present invention are improved. Further, the presence of the trialkylsilyl group-containing molecular chain reduces the resistance between the droplet (water droplet, oil droplet, etc.) and the film, and facilitates the movement of the droplet.
  • the alkyl group of the trialkylsilyl-containing group is replaced with a fluoroalkyl group
  • the water / oil repellency of the film interface (surface) can be similarly improved.
  • the trialkylsilyl group is unevenly distributed on the surface of the film, so that sulfuric acid and hot water are prevented from diffusing into the film, and a film having high sulfuric acid resistance is obtained.
  • a film having high hot water resistance is also obtained. It is done.
  • the trialkylsilyl-containing group is a group containing at least one trialkylsilyl group, preferably two or more, more preferably three trialkylsilyl groups.
  • the trialkylsilyl-containing group is preferably a group represented by the formula (s1).
  • each of the plurality of R s1 independently represents a hydrocarbon group or a trialkylsilyloxy group, and the hydrogen atom contained in the hydrocarbon group or trialkylsilyloxy group is substituted with a fluorine atom. It may be. * Represents a bond.
  • R s1 are all alkyl groups.
  • R s1 is a hydrocarbon group
  • the carbon number thereof is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 to 2.
  • R s1 is a hydrocarbon group
  • an aliphatic hydrocarbon group is preferable, and an alkyl group is more preferable.
  • the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.
  • a plurality of R s1 may be the same or different and are preferably the same.
  • the total number of carbon atoms of the three R s1 is preferably 9 or less, more preferably 6 or less, and even more preferably 4 or less. Is preferably at least one of methyl group of the three R s1, more preferably at least two of a methyl group, and particularly preferably all three R s1 is a methyl group.
  • R s1 when R s1 is a trialkylsilyloxy group, at least one of R s1 is preferably a trialkylsilyloxy group.
  • the trialkylsilyloxy group include a group in which an oxygen atom is bonded to a silicon atom of a group (trialkylsilyl group) in which R s1 is a hydrocarbon group (alkyl group).
  • R s1 more preferably 2 or more, and even more preferably 3 R s1 is a trialkylsilyloxy group.
  • R s1 is a trialkylsilyloxy group
  • examples of the group in which at least one of R s1 is a trialkylsilyloxy group include groups represented by the following formulae.
  • the trialkylsilyl-containing group In a trialkylsilyl group-containing molecular chain, the trialkylsilyl-containing group must be bonded to the end (free end side) of the molecular chain, particularly the end of the main chain (longest straight chain) (free end side). Is preferred.
  • the molecular chain to which the trialkylsilyl-containing group is bonded is preferably linear or branched, and is preferably linear.
  • the molecular chain preferably includes a dialkylsiloxane chain, and preferably includes a linear dialkylsiloxane chain.
  • the molecular chain may contain a divalent hydrocarbon group. Even if a part of the molecular chain is a divalent hydrocarbon group, the remainder is a dialkylsiloxane chain, so that the resulting film has good chemical and physical durability.
  • the molecular chain is preferably a group represented by the formula (s2).
  • R s2 each independently represents an alkyl group having 1 to 10 carbon atoms.
  • Z s1 represents —O— or a divalent hydrocarbon group, and —CH 2 — contained in the divalent hydrocarbon group may be replaced by —O—.
  • Y s1 represents a single bond or —Si (R s2 ) 2 —L s1 —.
  • L s1 represents a divalent hydrocarbon group, and —CH 2 — contained in the divalent hydrocarbon group may be replaced by —O—.
  • * On the left side represents a bond with a central silicon atom, and * on the right side represents a bond with a trialkylsilyl-containing group.
  • n1 represents an integer of 1 or more.
  • R s2 preferably has 1 to 4 carbon atoms, more preferably 1 to 3, and still more preferably 1 to 2.
  • N1 is preferably 1 to 100, more preferably 1 to 80, further preferably 1 to 60, even more preferably 1 to 45, and particularly preferably 1 to 30.
  • the number of carbon atoms of the divalent hydrocarbon group in Z s1 and L s1 is preferably 1 to 10, more preferably 1 to 6, and further preferably 1 to 4.
  • the divalent hydrocarbon group is preferably chain-like, and when it is chain-like, it may be either linear or branched.
  • the divalent hydrocarbon group is preferably a divalent aliphatic hydrocarbon group, and preferably an alkanediyl group. Examples of the divalent hydrocarbon group include a methylene group, an ethylene group, a propylene group, and a butylene group.
  • a part of —CH 2 — contained in the divalent hydrocarbon group may be replaced by —O—.
  • two consecutive —CH 2 — are not simultaneously replaced with —O—, and —CH 2 — adjacent to the Si atom is not replaced with —O—.
  • the number of carbon atoms between —O— and —O— is preferably 2 to 4, and more preferably 2 to 3 preferable.
  • Specific examples of the group in which a part of the divalent hydrocarbon group is replaced by —O— include a group having a (poly) ethylene glycol unit, a group having a (poly) propylene glycol unit, and the like. it can.
  • Z s1 is —O— and Y s1 is a single bond, that is, the molecular chain consists only of repeating dialkylsilyloxy groups.
  • the dialkylsiloxane chain consists only of repeating dialkylsilyloxy groups, the resulting film has good chemical and physical durability.
  • Examples of the molecular chain contained in the trialkylsilyl group-containing molecular chain include a molecular chain represented by the following formula.
  • q1 represents an integer of 1 to 60
  • * on the left side represents a bond with a central silicon atom
  • * on the right side represents a bond with a trialkylsilyl-containing group.
  • q1 is preferably an integer of 1 to 45, more preferably an integer of 1 to 30.
  • the total number of elements constituting the trialkylsilyl group-containing molecular chain is preferably 24 or more, more preferably 40 or more, still more preferably 50 or more, and preferably 5000 or less, more preferably 4000. Hereinafter, it is more preferably 2000 or less, even more preferably 1200 or less, even more preferably 700 or less, and particularly preferably 250 or less.
  • the trialkylsilyl group-containing molecular chain is preferably a group represented by the following formula (s3).
  • R s1 , R s2 , Z s1 , Y s1 , and n1 are as defined above. * Represents a bond with the central silicon atom.
  • the trialkylsilyl group-containing molecular chain is preferably a group represented by the following formula (s3-1), and more preferably a group represented by the following formula (s3-1-1).
  • R s2 In formula (s3-1) and formula (s3-1-1), R s2 , Y s1 , Z s1 , and n1 have the same meanings as described above.
  • R s3 each independently represents an alkyl group having 1 to 4 carbon atoms. * Represents a bond with the central silicon atom.
  • the number of carbon atoms of the alkyl group represented by R s3 is preferably 1 to 3, more preferably 1 to 2.
  • the total carbon number of R s3 contained in —Si (R s3 ) 3 is preferably 9 or less, more preferably 6 Hereinafter, it is more preferably 4 or less.
  • at least one R s3 is preferably a methyl group, and two or more R s3 are preferably methyl groups, and three R s3 It is particularly preferred that all are methyl groups.
  • trialkylsilyl group-containing molecular chain is more preferably a group represented by the following formula (s3-2), and particularly preferably a group represented by the following formula (s3-2-1). .
  • R s2 , Y s1 , Z s1 , and n1 have the same meanings as described above.
  • R s4 independently represents an alkyl group having 1 to 4 carbon atoms. * Represents a bond with the central silicon atom.
  • Examples of the alkyl group having 1 to 4 carbon atoms represented by R s4 include the groups described above for R s3 , and the preferred ranges thereof are also the same.
  • Examples of the trialkylsilyl group-containing molecular chain include a group represented by the formula (s3-I).
  • * represents a bond with the central silicon atom.
  • N30 shown in Tables 1 and 2 above is preferably 1 to 30.
  • a a1 in the formula (A1) will be described.
  • a plurality of A a1 are each independently a hydrolyzable group and may be any group that gives a hydroxy group (silanol group) by hydrolysis.
  • carbon such as methoxy group, ethoxy group, propoxy group, butoxy group, etc.
  • Preferred examples include an alkoxy group of 1 to 6; a hydroxy group; an acetoxy group; a chlorine atom; an isocyanate group; Among these, an alkoxy group having 1 to 6 carbon atoms is preferable, an alkoxy group having 1 to 4 carbon atoms is more preferable, and an alkoxy group having 1 to 2 carbon atoms is more preferable.
  • Z a1 in the formula (A1) represents a trialkylsilyl group-containing molecular chain, a siloxane skeleton-containing group, or a hydrocarbon chain-containing group.
  • Z a1 is a trialkylsilyl group-containing molecular chain, the same as the above R a1 can be mentioned.
  • the siloxane skeleton-containing group is a monovalent group containing a siloxane unit (Si—O—), and constitutes a trialkylsilyl group-containing molecular chain of R a1. It is preferable that the number of elements is smaller than the number of elements to be formed. As a result, the siloxane skeleton-containing group is a group having a shorter length than the trialkylsilyl group-containing molecular chain or a small steric spread (bulk height).
  • the siloxane skeleton-containing group may contain a divalent hydrocarbon group.
  • the siloxane skeleton-containing group is preferably a group represented by the following formula (s4).
  • R s2 , Z s1 , and Y s1 have the same meanings as described above.
  • R s5 represents a hydrocarbon group or a hydroxy group, —CH 2 — contained in the hydrocarbon group may be replaced by —O—, and the hydrogen atom contained in the hydrocarbon group is a fluorine atom. May be substituted.
  • n3 represents an integer of 0 to 5. * Represents a bond with the central silicon atom.
  • Examples of the hydrocarbon group represented by R s5 include the same groups as the hydrocarbon group represented by R s1 , preferably an aliphatic hydrocarbon group, and more preferably an alkyl group.
  • the number of carbon atoms is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 to 2.
  • N3 is preferably 1 to 5, and more preferably 1 to 3.
  • the total number of elements of the siloxane skeleton-containing group is preferably 100 or less, more preferably 50 or less, still more preferably 30 or less, and preferably 10 or more.
  • the difference in the number of elements between the molecular chain containing R a1 trialkylsilyl group and the group containing Z a1 siloxane skeleton is preferably 10 or more, more preferably 20 or more, and preferably 1000 or less. More preferably, it is 500 or less, More preferably, it is 200 or less.
  • siloxane skeleton-containing group examples include groups represented by the following formulas.
  • Za1 is a hydrocarbon chain-containing group
  • the hydrocarbon chain portion has a smaller number of carbon atoms than the number of elements constituting the molecular chain of the trialkylsilyl group-containing molecular chain.
  • the number of carbon atoms of the longest straight chain of the hydrocarbon chain is preferably smaller than the number of elements constituting the longest straight chain of the trialkylsilyl group-containing molecular chain.
  • the hydrocarbon chain-containing group is usually composed only of a hydrocarbon group (hydrocarbon chain), but if necessary, a group in which a part of the methylene group (—CH 2 —) of the hydrocarbon chain is replaced with an oxygen atom. It may be.
  • the methylene group (—CH 2 —) adjacent to the Si atom is not replaced with an oxygen atom, and two consecutive methylene groups (—CH 2 —) are not replaced with an oxygen atom at the same time.
  • the carbon number of the hydrocarbon chain portion means the number of carbon atoms constituting the hydrocarbon group (hydrocarbon chain) in the oxygen non-substituted hydrocarbon chain-containing group, and includes the oxygen-substituted hydrocarbon chain. In the group, the number of carbon atoms is assumed assuming that the oxygen atom is a methylene group (—CH 2 —).
  • hydrocarbon chain-containing group will be described by taking an oxygen-nonsubstituted hydrocarbon chain-containing group (that is, a monovalent hydrocarbon group) as an example.
  • an oxygen-nonsubstituted hydrocarbon chain-containing group that is, a monovalent hydrocarbon group
  • the methylene group — Part of CH 2 —
  • oxygen atoms can be replaced with oxygen atoms.
  • the number of carbon atoms is preferably 1 or more and 3 or less, more preferably 1. Further, the hydrocarbon chain-containing group may be branched or linear.
  • the hydrocarbon chain-containing group is preferably a saturated or unsaturated aliphatic hydrocarbon chain-containing group, and more preferably a saturated aliphatic hydrocarbon chain-containing group.
  • the saturated aliphatic hydrocarbon chain-containing group is more preferably a saturated aliphatic hydrocarbon group. Examples of the saturated aliphatic hydrocarbon group include a methyl group, an ethyl group, and a propyl group.
  • X in the formula (A1) is 0 or 1, preferably 0.
  • the organosilicon compound (a) represented by the formula (A1) is preferably a compound represented by the following formula (A2).
  • R s1 , R s2 , Z s1 , Y s1 , n1, A a1 , Z a1 , and x are as defined above.
  • the organosilicon compound (a) represented by the formula (A2) is preferably a compound represented by the following formula (A2-1), and is a compound represented by the formula (A2-1-1) Is more preferable.
  • R s2 , R s3 , Y s1 , Z s1 , n1 and A a1 are as defined above.
  • the organosilicon compound (a) represented by the formula (A2) is more preferably a compound represented by the following formula (A2-2), particularly preferably represented by the formula (A2-2-1). A compound.
  • R s2 , R s4 , Y s1 , Z s1 , n1 and A a1 are as defined above.
  • organosilicon compound (a) represented by the formula (A2) include a compound represented by the formula (AI).
  • N10 shown in the above Table 3-1, Table 3-2, Table 4-1, and Table 4-2 is preferably 1-30.
  • n is 1 to 60, preferably 1 to 30.
  • the amount of the organosilicon compound (a) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and further preferably 0.3% by mass or more in 100% by mass of the composition. It is. Moreover, as an upper limit, it is preferable that it is less than 2.6 mass%, More preferably, it is 2.0 mass% or less, More preferably, it is 1.5 mass% or less, Most preferably, it is 1.0 mass% or less. As for the amount of the above-mentioned organosilicon compound (a), it is preferable that either the blending amount at the time of preparing the composition or the value calculated from the analysis result of the composition satisfies the above range.
  • the amount (concentration) or mass ratio range of each component when the amount (concentration) or mass ratio range of each component is described, the value calculated from the blending amount at the time of preparing the composition and the analysis result of the composition, as described above. It is preferable that either satisfies the range.
  • Examples of the method for synthesizing the organosilicon compound (a) include the method described in JP-A-2017-201109.
  • the organic polysilazane (b) in the present invention preferably has a structural unit represented by the following formula (B2).
  • R p21 , R p22 and R p23 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. However, at least one of R p21 and R p22 represents a hydrocarbon group having 1 to 10 carbon atoms.
  • R p21 , R p22 and R p23 are hydrocarbon groups, the carbon number thereof is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 to 2.
  • the hydrocarbon group is preferably an aliphatic hydrocarbon group, and more preferably an alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group, and among them, a methyl group is preferable.
  • R p23 is more preferably a hydrogen atom.
  • the organic polysilazane (b) preferably further has a structural unit represented by the following formula (B1).
  • R p10 and R p11 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
  • Y represents a divalent hydrocarbon group having 1 to 10 carbon atoms
  • X represents a hydrolysable group each independently.
  • the hydrocarbon group in R p10 and R p11 preferably has 1 to 4 carbon atoms, more preferably 1 to 3, and still more preferably 1 to 2.
  • the hydrocarbon group for R p10 and R p11 is preferably an aliphatic hydrocarbon group, more preferably an alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group, and among them, a methyl group is preferable.
  • the divalent hydrocarbon group for Y preferably has 1 to 4 carbon atoms, more preferably 1 to 3, and still more preferably 1 to 2.
  • the divalent hydrocarbon group is preferably chain-like, and when it is chain-like, it may be either linear or branched.
  • the divalent hydrocarbon group is preferably a divalent aliphatic hydrocarbon group, and preferably an alkanediyl group. Examples of the divalent hydrocarbon group include a methylene group, an ethylene group, a propylene group, and a butylene group.
  • a part of —CH 2 — contained in the divalent hydrocarbon group may be replaced by —O—.
  • two consecutive —CH 2 — are not simultaneously replaced with —O—, and —CH 2 — adjacent to the Si atom is not replaced with —O—.
  • the number of carbon atoms between —O— and —O— is preferably 2 to 4, and more preferably 2 to 3 preferable.
  • Specific examples of the group in which a part of the divalent hydrocarbon group is replaced by —O— include a group having a (poly) ethylene glycol unit, a group having a (poly) propylene glycol unit, and the like. it can.
  • the hydrolyzable group of X may be any group that gives a hydroxy group (silanol group) by hydrolysis, and examples thereof include an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group; Preferred examples include hydroxy group; acetoxy group; chlorine atom; isocyanate group; Among these, an alkoxy group having 1 to 4 carbon atoms is preferable, and an alkoxy group having 1 to 2 carbon atoms is more preferable.
  • a plurality of X may be the same or different and are preferably the same.
  • composition of the present invention two or more organic polysilazanes (b) may be mixed.
  • the organic polysilazane (b) preferably contains 2% by mass or more of the SiX 3 group of the formula (B1) with respect to 100% by mass of the organic polysilazane (b), more preferably 5% by mass or more. Preferably it is 8 mass% or more. Although an upper limit is not limited, 50 mass% or less may be sufficient, 40 mass% or less may be sufficient, and 30 mass% or less may be sufficient.
  • the total concentration of the organosilicon compound (a) and the organic polysilazane (b) is 0.2% by mass or more and less than 2.6% by mass with respect to 100% by mass of the composition of the present invention.
  • the lower limit is preferably 0.3% by mass or more, and more preferably 0.5% by mass or more.
  • the upper limit is preferably 2.0% by mass or less, more preferably 1.8% by mass or less, further preferably 1.3% by mass or less, and particularly preferably 1.0% by mass or less.
  • the mass ratio (a / b) between the organosilicon compound (a) and the organopolysilazane (b) is preferably 0.2 or more, more preferably 0.4 or more. More preferably, it is 0.5 or more.
  • the upper limit is preferably 100 or less, more preferably 50 or less, still more preferably 10 or less, and particularly preferably 8 or less.
  • the content ratio of the Si—H hydrogen atom in the organic polysilazane (b) and the hydrocarbon group having 1 to 10 carbon atoms bonded to Si can be appropriately selected.
  • the molar ratio of hydrocarbon group / hydrogen atom is 0.00. 1 to 50, preferably 0.2 to 10. These molar ratios can be calculated from NMR measurements and the like.
  • composition of the present invention is mixed with the solvent (c).
  • Examples of the solvent (c) include alcohol solvents, ether solvents, ketone solvents, ester solvents, amide solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, and the like.
  • Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, 1-propoxy 2-propanol, and the ether solvent includes dimethoxyethane, tetrahydrofuran, dioxane, dibutyl ether.
  • Examples of ketone solvents include acetone and methyl ethyl ketone (2-butanone)
  • examples of ester solvents include ethyl acetate and butyl acetate
  • examples of amide solvents include dimethylformamide and the like.
  • aliphatic hydrocarbon solvents examples include pentane, hexane, heptane, octane, isooctane, cyclopentane, cyclohexane, cycloheptane, methylcyclohexane, mineral spirits. .
  • aromatic hydrocarbon solvents examples include pentane, hexane, heptane, octane, isooctane, cyclopentane, cyclohexane, cycloheptane, methylcyclohexane, mineral spirits.
  • aromatic hydrocarbon solvents examples include pentane, hexane, heptane, octane, isooctane, cyclopentane, cyclohexane, cycloheptane, methylcyclohexane, mineral spirits.
  • aromatic hydrocarbon solvents examples include pentane, hexane, hept
  • the concentration of the solvent (c) with respect to 100% by mass of the composition is preferably 50% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and particularly preferably 95% by mass or more.
  • the upper limit is set according to the amount of the organic silicon compound (a), the organic polysilazane (b), and other additive components (hereinafter referred to as the third component (d)), and the organic silicon compound (a) and the organic polysilazane.
  • the solvent (c) may be other than (b) and the third component (d).
  • the composition of the present invention may coexist with a catalyst.
  • the catalyst is not particularly limited as long as it is a catalyst capable of curing organic polysilazane.
  • Products such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, butylamine, dibutylamine, tributylamine, pentylamine, dipentylamine, tripentylamine, hexylamine, Amines such as dihexylamine, trihexylamine, heptylamine, diheptylamine, octylamine, dioctylamine, trioctylamine, phenylamine, diphenylamine, triphenylamine, such as 1,8-diazabicyclo [5,4,0 ] 7-Undecene (DBU), 1,5-diazabicyclo [4,3,0] 5-nonene (DBN), 1,5,9-triazacyclododecane, 1,4,7-triazacyclo Nan and the like.
  • DBU 1,8-di
  • examples of the catalyst include acidic compounds; basic compounds; organometallic compounds;
  • examples of the acidic compound include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, hydrogen peroxide, chloric acid, and hypochlorous acid; organic acids such as acetic acid, propionic acid, butyric acid, valeric acid, maleic acid, and stearic acid.
  • examples of the basic compound include ammonia.
  • organometallic compound examples include organometallic compounds having a metal element such as Al, Fe, Zn, and Sn as a central metal, and organoaluminum compounds such as aluminum carboxylate, aluminum acetylacetone complex, and aluminum ethylacetoacetate complex; Organic iron compounds such as iron oxide (such as iron octylate); Organic zinc compounds such as zinc acetylacetonate monohydrate, zinc naphthenate and zinc octylate; Organic tin compounds such as dibutyltin diacetate complex; Other organic metals As compounds, metal carboxylates containing Ni, Ti, Pt, Rh, Co, Ru, Os, Pd, Ir, etc .; acetylacetona complexes containing Ni, Pt, Pd, Rh, etc .; Au, Ag, Pd Metal fine particles such as Ni, Zn, Ti; metal peroxides; metal chlorides; Erosen include cyclopentadienyl complexes of metals of
  • composition of the present invention is an antioxidant, a rust inhibitor, a UV absorber, a light stabilizer, a fungicide, an antibacterial agent, an anti-bioadhesive agent, a deodorant, a pigment, a flame retardant, as long as the effect is not impaired
  • additives such as an antistatic agent may coexist.
  • a film that is a cured product of the above composition and a coated body in which the film is coated on a substrate are also included in the present invention.
  • the film obtained from the composition of the present invention is usually formed on a substrate, and examples of the method of contacting the substrate include a method of coating the composition on the substrate, such as a spin coating method, dip coating, and the like. Coating method, spray coating method, roll coating method, bar coating method, hand-painting (a method of soaking a liquid in a cloth, etc., applying to a substrate), pouring (spraying the liquid directly onto the substrate using a dropper, etc. Application method), spraying (method of applying to a substrate using spraying), and the like.
  • the composition brought into contact with the substrate as described above is allowed to stand in the air at room temperature (for example, 1 hour to 48 hours) or heated (for example, 300 ° C.
  • the film thickness can be, for example, about 0.1 to 500 nm.
  • the thickness is preferably 0.2 to 200 nm, more preferably 0.3 to 100 nm.
  • the contact angle of the droplet on the film of the present invention is preferably 90 ° or more, more preferably 98 ° or more, and further preferably 100 ° or more. This contact angle can be determined according to the measurement method of the Example mentioned later.
  • the sliding speed of the droplet on the film of the present invention is preferably 10 mm / second or more, more preferably 25 mm / second or more, further preferably 30 mm / second or more, and particularly preferably 45 mm / second or more. This sliding speed can be determined according to the measurement method of the Example mentioned later.
  • the film of the present invention preferably has a wear resistance of 3000 times or more, more preferably 5000 times or more, and still more preferably 8000 times or more in the measurement of wear resistance of Examples described later.
  • the appearance of the film of the present invention is free from foreign matter, white glaze and the like that can be visually observed after film formation.
  • a foreign object or a white glaze when the liquid droplet is slid down, the liquid droplet is caught and does not slide, or the active ingredient may flow down together with the liquid droplet and the performance may be lost.
  • the film can be used by wiping with a cloth, etc., but the component that contributes to water and oil repellency is removed too much by the wiping work, and the performance deteriorates or the in-plane of the film It is preferable to develop various performances without wiping off.
  • the contact angle of the droplet on the film of the present invention after the hot water test is preferably 90 ° or more, more preferably 97 ° or more, and further preferably 102 ° or more.
  • the contact angle after this hot water test can be determined according to the measurement method of the Example mentioned later.
  • the sliding speed of the droplet on the film of the present invention after the hot water test is preferably 20 mm / second or more, more preferably 25 mm / second or more, and further preferably 27 mm / second or more.
  • the sliding speed after this hot water test can be determined according to the measuring method of the Example mentioned later.
  • the film of the present invention preferably has one or more magic marks wiped off, more preferably two or more points wiped off, and particularly preferably all three points wiped off.
  • the film of the present invention is too thick, the film of the present invention is hygroscopic and curable, so that curing does not proceed sufficiently to the inside, and the film becomes soft, resulting in poor wear resistance. Therefore, it is preferable that the film has an appropriate film thickness.
  • the film surface tends to become cloudy and the appearance tends to deteriorate due to unevenness of the film surface and bleeding components.
  • the density of the film in the vicinity of the substrate is preferably 0.90 g / cm 3 or more, and more preferably 0.95 g / cm 3 or more.
  • the density of the film in the vicinity of the substrate refers to the density of the film on the substrate side in the film in the coated body in which the film of the present invention is coated on the substrate.
  • a method for measuring the density of the film for example, an X-ray reflectivity method can be used.
  • the X-ray reflectivity method is used as a means for measuring the laminated structure, film thickness or density of multilayer thin films whose composition and film structure are unknown.
  • This X-ray reflectivity method is a measurement using interference vibration of X-rays reflected at an interface where layers having different densities are in contact. For example, measurement of a film thickness of an oxide film or the like formed on an electrode or a spin valve It is used to analyze the laminated structure of films.
  • the density of the film on the base material side means a value obtained by fitting treatment.
  • the density of the layer closest to the base material is the density of the film on the base material side. It becomes density.
  • the density is adopted as the density of the film on the substrate side.
  • the fitting is to correct the difference between the theoretical calculated value of the spectrum intensity and the actually measured intensity for the detected X-ray spectrum when X-ray measurement is performed.
  • FIG. 1 shows an example of fitting the XRR measurement result of the film.
  • the density of a thin film having a film thickness of several tens of nanometers from the outermost surface can be calculated from the total reflection critical angle, and the density of other layers can be calculated from the amplitude of interference fringes. .
  • the film thickness of each layer can be calculated from the period of vibration. Further, the roughness can be calculated from the attenuation factor of the entire reflectance measurement data and the attenuation of the interference fringe amplitude on the high angle side, as described in, for example, Japanese Patent Laid-Open No. 2001-349849.
  • measurement data is obtained by X-ray incidence from an angle near the critical angle with respect to the surface of a film sample composed of a single layer film or a multilayer film.
  • Np the number of data measurement points
  • ⁇ (n) the angle of incident X-rays at a measurement point n
  • the reflected X-ray intensity is observed when ⁇ (n) is 0.05 ° to 5 °.
  • R ⁇ (n) ⁇ the X-ray reflectivity at the incident angle ⁇ (n) is obtained.
  • a correlation diagram of ⁇ (n) with respect to R ⁇ (n) ⁇ is referred to as an XRR profile.
  • the appropriate conditions are the measurement range of the angle ⁇ (n) of incident X-rays and the divergence angle [°] of incident X-rays. is there.
  • the measurement start angle needs to satisfy the conditions for total reflection of incident X-rays.
  • the conditions for total reflection of X-rays can be estimated from the element type and density, and the critical angle for total reflection is said to be 0.23 ° for glass substrates, Si substrates, and the like.
  • the measurement end angle is an angle at which the signal intensity is about the same as the background.
  • the divergence angle of incident X-rays it is known that as the film thickness of the film on the substrate increases, the period [°] of X-ray interference decreases.
  • the divergence angle of incident X-rays increases as the film thickness increases. [°] needs to be reduced.
  • the divergence angle needs to be 0.015 ° or less, and when it is 300 nm or more, the divergence angle needs to be 0.003 ° or less.
  • the film thickness, density, and roughness (the interface between the air and the film, the interface between the films, the film and the substrate).
  • the interface parameters are initially set, and at least one of these parameters is changed, which is called a simulation calculation profile obtained by simulation calculation.
  • the density of the film sample is determined by fitting so that the simulation calculation profile is close to the actual measurement profile.
  • the residual sum of squares ( ⁇ 2 ) is the difference between the calculated reflectance (Ical) of the spectral intensity and the experimental reflectance (Iexp), and is expressed by the formula (Y) and is preferably 0.01 or less.
  • Np is the number of data points within the fitting range.
  • ⁇ i is the angle of the incident X-ray.
  • the above-described fitting process can be analyzed by using analysis software (GlobalFit) manufactured by Rigaku Corporation.
  • the substrate to which the composition of the present invention is contacted is not particularly limited, and the shape of the substrate may be a flat surface or a curved surface, or may be a three-dimensional structure in which a large number of surfaces are combined.
  • the material of the base material is not limited and may be composed of either an organic material or an inorganic material.
  • organic material examples include thermoplastic resins such as acrylic resin, polycarbonate resin, polyester resin, styrene resin, acrylic-styrene copolymer resin, cellulose resin, and polyolefin resin; phenol resin, urea resin, melamine resin, epoxy resin,
  • inorganic materials include ceramics; glass; metals such as iron, silicon, copper, zinc, and aluminum; alloys containing the above metals; etc. Is mentioned.
  • the substrate may be subjected to an easy adhesion treatment in advance.
  • the easy adhesion treatment include hydrophilic treatment such as corona treatment, plasma treatment, and ultraviolet treatment.
  • primer treatment with a resin, a silane coupling agent, tetraalkoxysilane, or the like may be performed, or a glass film such as polysilazane may be preliminarily applied to the substrate.
  • the sliding characteristics of water droplets were evaluated based on the sliding speed when water droplets were dropped on the film surface. Specifically, using a contact angle measuring device (DM700) manufactured by Kyowa Interface Science Co., Ltd., 50 ⁇ L of water droplets were dropped on the film on the glass substrate inclined at 20 °, and the water droplets were 15 mm from the initial dropping position. The time until sliding down was measured, and the sliding speed (mm / sec) of water droplets on the film surface was calculated.
  • the sample was immersed in ion-exchanged water at 70 ° C. for 12 hours, and the water contact angle and sliding speed before and after immersion were measured.
  • Example 1 0.03 g of the compound (1) having an average n of 24 in the above formula (A2-26) and 0.03 g of Durazan (registered trademark) 1500 slow cure (manufactured by MERCK) were dissolved in 9.94 g of isooctane, Mixing was performed using a vortex at room temperature for 1 minute to obtain a coating solution.
  • the coating solution is formed on a non-alkali glass (Eagle XG) that has been plasma-treated with a spin coater (manufactured by MIKASA) under the conditions of a rotation speed of 3000 rpm and 20 seconds, and then subjected to a heat treatment at 200 ° C. for 3 hours. A film was obtained on top. Thereafter, the film was evaluated by the measurement method described above.
  • Durazan (registered trademark) 1500 slow cure has a structural unit represented by the following formula (B3).
  • R represents a hydrogen atom or a methyl group.
  • Examples 2-11, Comparative Examples 1-2 A film was prepared in the same manner as in Example 1 except that the types and / or amounts of the organosilicon compound (a), the organic polysilazane (b), and the solvent (c) were changed to the ratios shown in Table 5. Note that Durazan (registered trademark) 1500 rapid cure (manufactured by MERCK) also has the same structural unit as (B3) above.
  • Each of Durazan (registered trademark) 1500 slow cure and Durazan (registered trademark) 1500 rapid cure has 9 to 27% by mass of Si (OC 2 H 5 ) 3 groups, and the structure in (B3) above
  • the molar ratio (methyl group / hydrogen atom) between the hydrogen atom of the SiH group and the methyl group of the Si—CH 3 group was 1.5 to 3.0.
  • the molar ratio of SiH, SiCH 3 , and Si (OCH 2 CH 3 ) 3 in the organic polysilazane was determined from the integrated value, and the molar ratio of hydrogen atoms to methyl groups was calculated. Also, in terms of the respective mass ratio was calculated by mass% of Si (OC 2 H 5) 3 groups contained in the organic polysilazane.
  • the compound (2) used in Comparative Example 1 was a one-end type reactive silicone oil (X-24-9011, manufactured by Shin-Etsu Chemical Co., Ltd.).
  • Table 6 and Table 7 show the evaluation results of the obtained film.
  • Organosilicon compounds have very high stability to light, but on the other hand, since they have a siloxane bond, it is not easy to make the film obtained from the composition containing the organosilicon compound durable against water and warm water. I understand that.
  • a film having high resistance to warm water is required in an actual use environment. It can be said that this is an important performance for maintaining the performance.
  • wear resistance Is also important as a characteristic of the film. Therefore, it is also preferable that the film has hot water resistance and wear resistance.
  • the film obtained from the composition of the present invention has water repellency / oil repellency and sulfuric acid resistance (preferably, in addition to water repellency / oil repellency and sulfuric acid resistance, droplet slipping, abrasion resistance, appearance and warm water resistance. ). Therefore, it is useful as a base material in display devices such as a touch panel display, optical elements, semiconductor elements, building materials, automobile parts, nanoimprint technology, and the like. Furthermore, it is suitably used as an article such as a body, window glass (front glass, side glass, rear glass), mirror, bumper, etc. in transportation equipment such as trains, automobiles, ships, and airplanes.
  • it can also be used for outdoor uses, such as a building outer wall, a tent, a solar power generation module, a sound insulation board, and concrete. It can also be used for fishing nets, insect nets, water tanks, and the like. Furthermore, it can be used for various indoor facilities such as kitchens, bathrooms, washstands, mirrors, toilet articles, ceramics such as chandeliers and tiles, artificial marble, and air conditioners. It can also be used as an antifouling treatment for jigs, inner walls, pipes and the like in factories. It is also suitable for goggles, glasses, helmets, slingshots, textiles, umbrellas, play equipment, soccer balls and the like. Furthermore, it can also be used as an anti-adhesive agent for various packaging materials such as food packaging materials, cosmetic packaging materials, and the inside of pots.

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Abstract

The purpose of the present invention is to provide a composition that can be used to provide a film having excellent water repellency, oil repellency, and sulfuric acid resistance. The present invention pertains to a mixed composition containing an organic silicon compound (a) in which at least one trialkylsilyl group-containing molecular chain and at least one hydrolysable group are bonded to a silicon atom, an organic polysilazane (b), and a solvent (c), wherein the total concentration of the organic silicon compound (a) and the organic polysilazane (b) is not less than 0.2 mass% but less than 2.6 mass% with respect to 100 mass% of the mixed composition.

Description

混合組成物Mixed composition
　本発明は有機ケイ素化合物と有機ポリシラザンの混合組成物に関する。 The present invention relates to a mixed composition of an organosilicon compound and an organic polysilazane.
　各種の表示装置、光学素子、半導体素子、建築材料、自動車部品、ナノインプリント技術等において、基材の表面に液滴が付着することにより、基材の汚れや腐食、さらにこの汚れや腐食に由来する性能低下等の問題が生じる場合がある。そのため、これらの分野において、基材表面の撥水・撥油性が良好であることが求められている。 In various display devices, optical elements, semiconductor elements, building materials, automobile parts, nanoimprint technology, etc., droplets adhere to the surface of the substrate, resulting in contamination and corrosion of the substrate, and further from this contamination and corrosion. Problems such as performance degradation may occur. Therefore, in these fields, it is required that the water / oil repellency of the substrate surface is good.
　このような撥水・撥油性を有する組成物として、特許文献１、２には、ポリシラザン及びシリコーンオイルを含有するコーティング剤が開示されている。 As such water- and oil-repellent compositions, Patent Documents 1 and 2 disclose coating agents containing polysilazane and silicone oil.
特開２０１４－１３９３０１号公報JP 2014-139301 A 特開２０１２－１５３８４９号公報JP 2012-153849 A
　撥水・撥油性の皮膜は、屋外などの用途によっては、紫外線や雨水などの過酷な環境に曝される場合があり、過酷な環境に曝された後にでも良好な性能を維持できることが好ましい。屋外では、大気中のＳＯXやＮＯXと水分とが反応することで生じる硫酸や硝酸が、皮膜の劣化を招くことが検討の結果明らかとなってきた。そのため、耐酸性(特に強い劣化因子である耐硫酸性)の良好な皮膜が求められている。しかしながら、特許文献１、２に開示されているコーティング剤を用いて得られる皮膜は、耐摩耗性、耐硫酸性、外観等において、検討の余地が残されている。 The water / oil-repellent film may be exposed to harsh environments such as ultraviolet rays and rain water depending on the use such as outdoors, and it is preferable that good performance can be maintained even after being exposed to harsh environments. As a result of examination, it has become clear that sulfuric acid and nitric acid produced by the reaction of SO X and NO X in the atmosphere with moisture cause deterioration of the film outdoors. Therefore, there is a demand for a film having good acid resistance (particularly sulfuric acid resistance, which is a strong deterioration factor). However, the film obtained by using the coating agent disclosed in Patent Documents 1 and 2 still has room for study in terms of wear resistance, sulfuric acid resistance, appearance, and the like.
　本発明は上記の様な事情に着目してなされたものであって、撥水・撥油性に優れ、かつ少なくとも耐硫酸性にも優れた皮膜を実現できる組成物を提供することを目的とする。
　本発明の組成物から得られる皮膜は、さらに、液滴滑り性、耐摩耗性、外観、耐温水性の少なくとも１つ以上にも優れることが好ましく、液滴滑り性、耐摩耗性、外観、耐温水性の全てに優れていることがより好ましい。 The present invention has been made paying attention to the above-described circumstances, and an object thereof is to provide a composition capable of realizing a film having excellent water and oil repellency and at least excellent sulfuric acid resistance. .
The film obtained from the composition of the present invention preferably further has at least one of droplet slipperiness, abrasion resistance, appearance, and hot water resistance, preferably droplet slippage, wear resistance, appearance, It is more preferable that all of the hot water resistance is excellent.
　本発明者らは、前記課題を解決するために鋭意研究を重ねた結果、トリアルキルシリル基含有分子鎖と加水分解性基とがケイ素原子に結合している有機ケイ素化合物と有機ポリシラザンを所定の濃度で混合することにより、撥水・撥油性と耐硫酸性に優れ、好ましくは液滴滑り性、耐摩耗性、外観、耐温水性にも優れた皮膜が得られることを見出し、本発明を完成した。本発明は以下の通りである。 As a result of intensive studies in order to solve the above problems, the present inventors have obtained an organic silicon compound and an organic polysilazane in which a trialkylsilyl group-containing molecular chain and a hydrolyzable group are bonded to a silicon atom. By mixing at a concentration, it was found that a film excellent in water repellency / oil repellency and sulfuric acid resistance, and preferably excellent in droplet slippage, abrasion resistance, appearance, and warm water resistance was obtained. completed. The present invention is as follows.
［１］　少なくとも１つのトリアルキルシリル基含有分子鎖と、少なくとも１つの加水分解性基とがケイ素原子に結合している有機ケイ素化合物（ａ）、有機ポリシラザン（ｂ）、及び溶媒（ｃ）の混合組成物であって、
　前記トリアルキルシリル基に含まれる水素原子はフッ素原子に置換されていてもよく、
　前記組成物１００質量％に対して、前記有機ケイ素化合物（ａ）と前記有機ポリシラザン（ｂ）との合計の濃度が０．２質量％以上２．６質量％未満である混合組成物。 [1] An organic silicon compound (a), an organic polysilazane (b), and a solvent (c) in which at least one trialkylsilyl group-containing molecular chain and at least one hydrolyzable group are bonded to a silicon atom. A mixed composition comprising:
The hydrogen atom contained in the trialkylsilyl group may be substituted with a fluorine atom,
The mixed composition in which the total concentration of the organosilicon compound (a) and the organic polysilazane (b) is 0.2% by mass or more and less than 2.6% by mass with respect to 100% by mass of the composition.
［２］　前記有機ポリシラザン（ｂ）が、下記式（Ｂ２）で表される構造単位を有する［１］に記載の組成物。
Figure JPOXMLDOC01-appb-C000005
 ［前記式（Ｂ２）中、Ｒp21、Ｒp22、及びＲp23は、それぞれ独立に、水素原子又は炭素数１～１０の炭化水素基を表す。ただし、Ｒp21及びＲp22の少なくとも一方は、炭素数１～１０の炭化水素基を表す。］ [2] The composition according to [1], wherein the organic polysilazane (b) has a structural unit represented by the following formula (B2).
Figure JPOXMLDOC01-appb-C000005
 [In the formula (B2), R p21 , R p22 and R p23 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. However, at least one of R p21 and R p22 represents a hydrocarbon group having 1 to 10 carbon atoms. ]
［３］　前記有機ケイ素化合物（ａ）が下記式（Ａ１）で表される化合物である［１］又は［２］に記載の組成物。
Figure JPOXMLDOC01-appb-C000006
 ［前記式（Ａ１）中、Ｒa1はトリアルキルシリル基含有分子鎖を表し、
　複数のＡa1は、それぞれ独立に、加水分解性基を表し、
　Ｚa1は、トリアルキルシリル基含有分子鎖、シロキサン骨格含有基、又は炭化水素鎖含有基を表し、
　Ｒa1及びＺa1におけるトリアルキルシリル基に含まれる水素原子はフッ素原子に置換されていてもよく、
　ｘは０または１である。］ [3] The composition according to [1] or [2], wherein the organosilicon compound (a) is a compound represented by the following formula (A1).
Figure JPOXMLDOC01-appb-C000006
 [In the formula (A1), R a1 represents a trialkylsilyl group-containing molecular chain,
Several A <a1> represents a hydrolysable group each independently,
Z a1 represents a trialkylsilyl group-containing molecular chain, a siloxane skeleton-containing group, or a hydrocarbon chain-containing group,
The hydrogen atom contained in the trialkylsilyl group in R a1 and Z a1 may be substituted with a fluorine atom,
x is 0 or 1. ]
［４］　前記有機ケイ素化合物（ａ）が下記式（Ａ２）で表される化合物である［１］～［３］のいずれかに記載の組成物。
Figure JPOXMLDOC01-appb-C000007
 ［前記式（Ａ２）中、複数のＲs1は、それぞれ独立に、炭化水素基又はトリアルキルシリルオキシ基を表し、該炭化水素基又はトリアルキルシリルオキシ基に含まれる水素原子は、フッ素原子に置換されていてもよく、
　複数のＲs2は、それぞれ独立に、炭素数１～１０のアルキル基を表し、
　ｎ１は、１以上の整数を表し、
　Ｚs1は、－Ｏ－又は２価の炭化水素基を表し、該２価の炭化水素基に含まれる－ＣＨ2－は、－Ｏ－に置き換わっていてもよい。
　Ｙs1は単結合又は－Ｓｉ（Ｒs2）2－Ｌs1－を表し、該Ｌs1は、２価の炭化水素基を表し、該２価の炭化水素基に含まれる－ＣＨ2－は、－Ｏ－に置き換わっていてもよい。
　複数のＡa1は、それぞれ独立に、加水分解性基を表し、
　Ｚa1は、トリアルキルシリル基含有分子鎖、シロキサン骨格含有基、又は炭化水素鎖含有基を表し、
　Ｚa1におけるトリアルキルシリル基に含まれる水素原子はフッ素原子に置換されていてもよく、
　ｘは０または１である。］ [4] The composition according to any one of [1] to [3], wherein the organosilicon compound (a) is a compound represented by the following formula (A2).
Figure JPOXMLDOC01-appb-C000007
 [In the formula (A2), a plurality of R s1 each independently represents a hydrocarbon group or a trialkylsilyloxy group, and the hydrogen atom contained in the hydrocarbon group or trialkylsilyloxy group is a fluorine atom. May be replaced,
A plurality of R s2 each independently represents an alkyl group having 1 to 10 carbon atoms;
n1 represents an integer of 1 or more,
Z s1 represents —O— or a divalent hydrocarbon group, and —CH 2 — contained in the divalent hydrocarbon group may be replaced by —O—.
Y s1 represents a single bond or —Si (R s2 ) 2 —L s1 —, the L s1 represents a divalent hydrocarbon group, and —CH 2 — contained in the divalent hydrocarbon group is -O- may be substituted.
Several A <a1> represents a hydrolysable group each independently,
Z a1 represents a trialkylsilyl group-containing molecular chain, a siloxane skeleton-containing group, or a hydrocarbon chain-containing group,
The hydrogen atom contained in the trialkylsilyl group in Z a1 may be substituted with a fluorine atom,
x is 0 or 1. ]
［５］　前記有機ポリシラザン（ｂ）が、下記式（Ｂ１）で表される構造単位をさらに有する［２］～［４］のいずれかに記載の組成物。
Figure JPOXMLDOC01-appb-C000008
 ［前記式（Ｂ１）中、Ｒp10及びＲp11は、それぞれ独立に、水素原子又は炭素数１～１０の炭化水素基を表し、
　Ｙは、炭素数１～１０の２価の炭化水素基を表し、
　複数のＸは、それぞれ独立に、加水分解性基を表す。］ [5] The composition according to any one of [2] to [4], wherein the organic polysilazane (b) further has a structural unit represented by the following formula (B1).
Figure JPOXMLDOC01-appb-C000008
 [In the formula (B1), R p10 and R p11 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms,
Y represents a divalent hydrocarbon group having 1 to 10 carbon atoms,
Several X represents a hydrolysable group each independently. ]
［６］　前記有機ポリシラザン（ｂ）が、前記式（Ｂ１）のＳｉＸ3基を２質量％～５０質量％含有する［５］に記載の組成物。 [6] The composition according to [5], wherein the organic polysilazane (b) contains 2% by mass to 50% by mass of the SiX 3 group of the formula (B1).
［７］　前記有機ケイ素化合物（ａ）と前記有機ポリシラザン（ｂ）との質量比（ａ／ｂ）が０．２以上である［１］～［６］のいずれかに記載の組成物。 [7] The composition according to any one of [1] to [6], wherein a mass ratio (a / b) between the organosilicon compound (a) and the organic polysilazane (b) is 0.2 or more.
［８］　［１］～［７］のいずれかに記載の組成物の硬化物である皮膜。 [8] A film that is a cured product of the composition according to any one of [1] to [7].
［９］　基材上に［８］に記載の皮膜が被覆された被覆体であって、Ｘ線反射率法により求められた基材側の皮膜の密度が０．９ｇ/ｃｍ3以上である被覆体。 [9] A coated body in which the film according to [8] is coated on a substrate, and the density of the film on the substrate side determined by the X-ray reflectance method is 0.9 g / cm 3 or more. Covering.
　本発明によれば有機ケイ素化合物と有機ポリシラザンを所定の濃度で混合することにより、撥水・撥油性及び耐硫酸性に優れた皮膜を実現できる組成物を提供できる。従って、本発明の組成物から得られる皮膜は、屋外であっても撥水・撥油性を長期間維持できる傾向にある。本発明の組成物から得られる皮膜は、さらに、液滴滑り性、耐摩耗性、外観、耐温水性の少なくとも１つ以上にも優れることが好ましく、液滴滑り性、耐摩耗性、外観、耐温水性の全てに優れていることがより好ましい。 According to the present invention, a composition capable of realizing a film excellent in water repellency / oil repellency and sulfuric acid resistance can be provided by mixing an organosilicon compound and an organic polysilazane at a predetermined concentration. Therefore, the film obtained from the composition of the present invention tends to maintain water and oil repellency for a long period of time even outdoors. The film obtained from the composition of the present invention preferably further has at least one of droplet slipperiness, abrasion resistance, appearance, and hot water resistance, preferably droplet slippage, wear resistance, appearance, It is more preferable that all of the hot water resistance is excellent.
ＸＲＲ測定におけるフィッティング処理の一例を示したグラフである。It is the graph which showed an example of the fitting process in a XRR measurement.
　本発明の組成物は、少なくとも１つのトリアルキルシリル基含有分子鎖と、少なくとも１つの加水分解性基とがケイ素原子（以下、このケイ素原子を「中心ケイ素原子」という場合がある）に結合している有機ケイ素化合物（ａ）及び有機ポリシラザン（ｂ）を所定の濃度で混合することで得られ、皮膜とした際の撥水・撥油性及び耐硫酸性（好ましくは、撥水・撥油性及び耐硫酸性に加えて液滴滑り性、耐摩耗性、外観及び耐温水性）が優れることが見出されている。
　なお、本発明の組成物は混合後、例えば保管中に反応が進んだものも含む。 In the composition of the present invention, at least one trialkylsilyl group-containing molecular chain and at least one hydrolyzable group are bonded to a silicon atom (hereinafter, this silicon atom may be referred to as “central silicon atom”). Obtained by mixing the organic silicon compound (a) and the organic polysilazane (b) at a predetermined concentration to form a film with water / oil repellency and sulfuric acid resistance (preferably water / oil repellency and It has been found that in addition to sulfuric acid resistance, droplet slipping, abrasion resistance, appearance and hot water resistance are excellent.
In addition, the composition of the present invention includes those that have reacted after mixing, for example, during storage.
　本発明における有機ケイ素化合物（ａ）は、少なくとも１つのトリアルキルシリル基含有分子鎖と、少なくとも１つの加水分解性基とが中心ケイ素原子に結合している。 In the organosilicon compound (a) in the present invention, at least one trialkylsilyl group-containing molecular chain and at least one hydrolyzable group are bonded to a central silicon atom.
　有機ケイ素化合物（ａ）において、中心ケイ素原子に結合するトリアルキルシリル基含有分子鎖の個数は、１以上であり、３以下であることが好ましく、より好ましくは２以下であり、特に好ましくは１である。 In the organosilicon compound (a), the number of trialkylsilyl group-containing molecular chains bonded to the central silicon atom is 1 or more, preferably 3 or less, more preferably 2 or less, and particularly preferably 1 It is.
　前記加水分解性基としては、加水分解によりヒドロキシ基（シラノール基）を与える基であればよく、例えば、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基等の炭素数１～６のアルコキシ基；ヒドロキシ基；アセトキシ基；塩素原子；イソシアネート基；等を好ましく挙げることができる。中でも、炭素数１～６のアルコキシ基であることが好ましく、炭素数１～４のアルコキシ基であることがより好ましく、炭素数１～２のアルコキシ基であることがさらに好ましい。
　有機ケイ素化合物（ａ）において、中心ケイ素原子に結合する加水分解性基の個数は、１以上であり、２以上であることが好ましく、通常、３以下であることが好ましい。
　なお後述する様に本発明の有機ケイ素化合物（ａ）は多数のケイ素原子を有しており、加水分解性基は、二つ以上のケイ素原子に結合していてもよいが、前記１つの中心ケイ素原子のみに結合していることが特に好ましい。 The hydrolyzable group may be any group that gives a hydroxy group (silanol group) by hydrolysis. Examples thereof include an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group; Preferred examples include a group; an acetoxy group; a chlorine atom; an isocyanate group; Among these, an alkoxy group having 1 to 6 carbon atoms is preferable, an alkoxy group having 1 to 4 carbon atoms is more preferable, and an alkoxy group having 1 to 2 carbon atoms is further preferable.
In the organosilicon compound (a), the number of hydrolyzable groups bonded to the central silicon atom is 1 or more, preferably 2 or more, and usually 3 or less.
As will be described later, the organosilicon compound (a) of the present invention has a large number of silicon atoms, and the hydrolyzable group may be bonded to two or more silicon atoms. It is particularly preferable to bond only to a silicon atom.
　有機ケイ素化合物（ａ）の中心ケイ素原子には、トリアルキルシリル基含有分子鎖、加水分解性基のほか、トリアルキルシリル基含有分子鎖の分子鎖を構成する元素数よりも少ない元素数のシロキサン骨格含有基、又はトリアルキルシリル基含有分子鎖の分子鎖を構成する元素数よりも少ない炭素数の炭化水素鎖を含有する炭化水素鎖含有基が結合していてもよい。 The central silicon atom of the organosilicon compound (a) includes a siloxane having a number of elements smaller than the number of elements constituting the molecular chain of the trialkylsilyl group-containing molecular chain, in addition to the trialkylsilyl group-containing molecular chain and hydrolyzable group. A skeleton-containing group or a hydrocarbon chain-containing group containing a hydrocarbon chain having a carbon number smaller than the number of elements constituting the molecular chain of the trialkylsilyl group-containing molecular chain may be bonded.
　本発明の組成物は、上記有機ケイ素化合物（ａ）を２種以上混合してもよい。 In the composition of the present invention, two or more of the above organosilicon compounds (a) may be mixed.
　前記有機ケイ素化合物（ａ）は、具体的には、下記式（Ａ１）で表される化合物であることが好ましい。 Specifically, the organosilicon compound (a) is preferably a compound represented by the following formula (A1).
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　式（Ａ１）中、Ｒa1はトリアルキルシリル基含有分子鎖を表し、複数のＡa1は、それぞれ独立に、加水分解性基を表し、Ｚa1は、トリアルキルシリル基含有分子鎖、シロキサン骨格含有基、又は炭化水素鎖含有基を表し、Ｒa1及びＺa1におけるトリアルキルシリル基に含まれる水素原子はフッ素原子に置換されていてもよく、ｘは０または１である。 In formula (A1), R a1 represents a trialkylsilyl group-containing molecular chain, a plurality of A a1 each independently represents a hydrolyzable group, and Z a1 represents a trialkylsilyl group-containing molecular chain or a siloxane skeleton. The hydrogen atom contained in the trialkylsilyl group in R a1 and Z a1 may be substituted with a fluorine atom, and x is 0 or 1;
　Ｒa1のトリアルキルシリル基含有分子鎖は、トリアルキルシリル含有基が分子鎖の末端に結合した構造を有する１価の基であり、分子鎖にトリアルキルシリル含有基が結合していることで、本発明の組成物から形成される皮膜の撥水性及び撥油性が向上する。またトリアルキルシリル基含有分子鎖が存在することで、液滴（水滴、油滴等）と該皮膜の間の抵抗が低減され、液滴が移動しやすくなる。トリアルキルシリル含有基のアルキル基がフルオロアルキル基に置き換わっている場合においても、同様に該皮膜界面（表面）の撥水・撥油性を向上することができる。さらにトリアルキルシリル基が該皮膜表面に偏在することで、硫酸や温水が膜中に拡散することを防ぎ、高い耐硫酸性を有する膜が得られ、好ましくは高い耐温水性も有する膜が得られる。 The trialkylsilyl group-containing molecular chain of R a1 is a monovalent group having a structure in which the trialkylsilyl-containing group is bonded to the end of the molecular chain, and the trialkylsilyl-containing group is bonded to the molecular chain. The water repellency and oil repellency of the film formed from the composition of the present invention are improved. Further, the presence of the trialkylsilyl group-containing molecular chain reduces the resistance between the droplet (water droplet, oil droplet, etc.) and the film, and facilitates the movement of the droplet. Even in the case where the alkyl group of the trialkylsilyl-containing group is replaced with a fluoroalkyl group, the water / oil repellency of the film interface (surface) can be similarly improved. Further, the trialkylsilyl group is unevenly distributed on the surface of the film, so that sulfuric acid and hot water are prevented from diffusing into the film, and a film having high sulfuric acid resistance is obtained. Preferably, a film having high hot water resistance is also obtained. It is done.
　前記トリアルキルシリル含有基は、少なくとも１つのトリアルキルシリル基を含む基であり、好ましくは２つ以上、さらに好ましくは３つのトリアルキルシリル基を含む。トリアルキルシリル含有基は、式（ｓ１）で表される基であることが好ましい。
Figure JPOXMLDOC01-appb-C000010
 The trialkylsilyl-containing group is a group containing at least one trialkylsilyl group, preferably two or more, more preferably three trialkylsilyl groups. The trialkylsilyl-containing group is preferably a group represented by the formula (s1).
Figure JPOXMLDOC01-appb-C000010
　式（ｓ１）中、複数のＲs1は、それぞれ独立に、炭化水素基又はトリアルキルシリルオキシ基を表し、該炭化水素基又はトリアルキルシリルオキシ基に含まれる水素原子は、フッ素原子に置換されていてもよい。＊は結合手を表す。 In formula (s1), each of the plurality of R s1 independently represents a hydrocarbon group or a trialkylsilyloxy group, and the hydrogen atom contained in the hydrocarbon group or trialkylsilyloxy group is substituted with a fluorine atom. It may be. * Represents a bond.
　上記式（ｓ１）において、Ｒs1の少なくとも１つがトリアルキルシリルオキシ基であるか、Ｒs1が全てアルキル基であることが好ましい。 In the above formula (s1), or that at least one trialkyl silyl group of R s1, it is preferred that R s1 are all alkyl groups.
　Ｒs1が炭化水素基である場合、その炭素数は、１～４であることが好ましく、より好ましくは１～３、さらに好ましくは１～２である。Ｒs1が炭化水素基である場合、脂肪族炭化水素基が好ましく、アルキル基がより好ましい。該アルキル基としては、メチル基、エチル基、プロピル基、ブチル基等が挙げられる。複数のＲs1は、同一でも異なっていてもよく、同一であることが好ましい。Ｒs1が全て炭化水素基（特にアルキル基）である場合、３つのＲs1の合計の炭素数は、９以下であることが好ましく、より好ましくは６以下、さらに好ましくは４以下である。３つのＲs1のうち少なくとも１つがメチル基であることが好ましく、少なくとも２つがメチル基であることがより好ましく、３つのＲs1全てがメチル基であることが特に好ましい。 When R s1 is a hydrocarbon group, the carbon number thereof is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 to 2. When R s1 is a hydrocarbon group, an aliphatic hydrocarbon group is preferable, and an alkyl group is more preferable. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. A plurality of R s1 may be the same or different and are preferably the same. When all R s1 are hydrocarbon groups (particularly alkyl groups), the total number of carbon atoms of the three R s1 is preferably 9 or less, more preferably 6 or less, and even more preferably 4 or less. Is preferably at least one of methyl group of the three R s1, more preferably at least two of a methyl group, and particularly preferably all three R s1 is a methyl group.
　Ｒs1が全て炭化水素基（アルキル基）である基（トリアルキルシリル基）としては、具体的には、下記式で表される基等が挙げられる。式中、＊は結合手を表す。 Specific examples of the group (trialkylsilyl group) in which R s1 is a hydrocarbon group (alkyl group) include groups represented by the following formulas. In the formula, * represents a bond.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　また、上記式（ｓ１）において、Ｒs1がトリアルキルシリルオキシ基である場合、Ｒs1の少なくとも１つが、トリアルキルシリルオキシ基であることが好ましい。前記トリアルキルシリルオキシ基としては、Ｒs1が全て炭化水素基（アルキル基）である基（トリアルキルシリル基）のケイ素原子に酸素原子が結合している基が挙げられる。上記式（ｓ１）において、より好ましくは２個以上、さらに好ましくは３個のＲs1がトリアルキルシリルオキシ基である。 In the above formula (s1), when R s1 is a trialkylsilyloxy group, at least one of R s1 is preferably a trialkylsilyloxy group. Examples of the trialkylsilyloxy group include a group in which an oxygen atom is bonded to a silicon atom of a group (trialkylsilyl group) in which R s1 is a hydrocarbon group (alkyl group). In the above formula (s1), more preferably 2 or more, and even more preferably 3 R s1 is a trialkylsilyloxy group.
　Ｒs1の少なくとも１つがトリアルキルシリルオキシ基である基としては、下記式で表される基が挙げられる。 Examples of the group in which at least one of R s1 is a trialkylsilyloxy group include groups represented by the following formulae.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　トリアルキルシリル基含有分子鎖において、トリアルキルシリル含有基は、分子鎖の末端（自由端側）、特に分子鎖の主鎖（最長直鎖）の末端（自由端側）に結合していることが好ましい。 In a trialkylsilyl group-containing molecular chain, the trialkylsilyl-containing group must be bonded to the end (free end side) of the molecular chain, particularly the end of the main chain (longest straight chain) (free end side). Is preferred.
　トリアルキルシリル含有基が結合している分子鎖は、直鎖状又は分岐鎖状であることが好ましく、直鎖状であることが好ましい。前記分子鎖は、ジアルキルシロキサン鎖を含むことが好ましく、直鎖状ジアルキルシロキサン鎖を含むことが好ましい。また前記分子鎖は、２価の炭化水素基を含んでいてもよい。分子鎖の一部が２価の炭化水素基であっても、残部がジアルキルシロキサン鎖であるため、得られる皮膜の化学的・物理的耐久性が良好である。 The molecular chain to which the trialkylsilyl-containing group is bonded is preferably linear or branched, and is preferably linear. The molecular chain preferably includes a dialkylsiloxane chain, and preferably includes a linear dialkylsiloxane chain. The molecular chain may contain a divalent hydrocarbon group. Even if a part of the molecular chain is a divalent hydrocarbon group, the remainder is a dialkylsiloxane chain, so that the resulting film has good chemical and physical durability.
　前記分子鎖は、式（ｓ２）で表される基であることが好ましい。 The molecular chain is preferably a group represented by the formula (s2).
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　式（ｓ２）中、複数のＲs2は、それぞれ独立に、炭素数１～１０のアルキル基を表す。Ｚs1は、－Ｏ－又は２価の炭化水素基を表し、該２価の炭化水素基に含まれる－ＣＨ2－は、－Ｏ－に置き換わっていてもよい。Ｙs1は、単結合又は－Ｓｉ（Ｒs2）2－Ｌs1－を表す。Ｌs1は、２価の炭化水素基を表し、該２価の炭化水素基に含まれる－ＣＨ2－は、－Ｏ－に置き換わっていてもよい。左側の＊は、中心ケイ素原子との結合手を表し、右側の＊はトリアルキルシリル含有基との結合手を表す。ｎ１は１以上の整数を表す。 In the formula (s2), a plurality of R s2 each independently represents an alkyl group having 1 to 10 carbon atoms. Z s1 represents —O— or a divalent hydrocarbon group, and —CH 2 — contained in the divalent hydrocarbon group may be replaced by —O—. Y s1 represents a single bond or —Si (R s2 ) 2 —L s1 —. L s1 represents a divalent hydrocarbon group, and —CH 2 — contained in the divalent hydrocarbon group may be replaced by —O—. * On the left side represents a bond with a central silicon atom, and * on the right side represents a bond with a trialkylsilyl-containing group. n1 represents an integer of 1 or more.
　Ｒs2の炭素数は、１～４であることが好ましく、より好ましくは１～３、さらに好ましくは１～２である。 R s2 preferably has 1 to 4 carbon atoms, more preferably 1 to 3, and still more preferably 1 to 2.
　ｎ１は、１～１００であることが好ましく、より好ましくは１～８０、さらに好ましくは１～６０、ことさら好ましくは１～４５の整数、特に好ましくは１～３０である。 N1 is preferably 1 to 100, more preferably 1 to 80, further preferably 1 to 60, even more preferably 1 to 45, and particularly preferably 1 to 30.
　Ｚs1及びＬs1における２価の炭化水素基の炭素数は、１～１０であることが好ましく、より好ましくは１～６、さらに好ましくは１～４である。前記２価の炭化水素基は、鎖状であることが好ましく、鎖状である場合、直鎖状、分岐鎖状のいずれであってもよい。また、前記２価の炭化水素基は、２価の脂肪族炭化水素基であることが好ましく、アルカンジイル基であることが好ましい。２価の炭化水素基としては、メチレン基、エチレン基、プロピレン基、ブチレン基等が挙げられる。 The number of carbon atoms of the divalent hydrocarbon group in Z s1 and L s1 is preferably 1 to 10, more preferably 1 to 6, and further preferably 1 to 4. The divalent hydrocarbon group is preferably chain-like, and when it is chain-like, it may be either linear or branched. The divalent hydrocarbon group is preferably a divalent aliphatic hydrocarbon group, and preferably an alkanediyl group. Examples of the divalent hydrocarbon group include a methylene group, an ethylene group, a propylene group, and a butylene group.
　さらに、前記２価の炭化水素基に含まれる一部の－ＣＨ2－は－Ｏ－に置き換わっていてもよい。この場合連続する２つの－ＣＨ2－が同時に－Ｏ－に置き換わることはなく、Ｓｉ原子に隣接する－ＣＨ2－が－Ｏ－に置き換わることはない。２つ以上の－ＣＨ2－が－Ｏ－に置き換わっている場合、－Ｏ－と－Ｏ－の間の炭素原子数は、２～４であることが好ましく、２～３であることがさらに好ましい。２価の炭化水素基の一部が－Ｏ－に置き換わった基としては、具体的には、（ポリ）エチレングリコール単位を有する基、（ポリ）プロピレングリコール単位を有する基等を例示することができる。 Furthermore, a part of —CH 2 — contained in the divalent hydrocarbon group may be replaced by —O—. In this case, two consecutive —CH 2 — are not simultaneously replaced with —O—, and —CH 2 — adjacent to the Si atom is not replaced with —O—. When two or more —CH 2 — are replaced by —O—, the number of carbon atoms between —O— and —O— is preferably 2 to 4, and more preferably 2 to 3 preferable. Specific examples of the group in which a part of the divalent hydrocarbon group is replaced by —O— include a group having a (poly) ethylene glycol unit, a group having a (poly) propylene glycol unit, and the like. it can.
　前記式（ｓ２）において、Ｚs1が－Ｏ－であり、Ｙs1が単結合であること、すなわち前記分子鎖が、ジアルキルシリルオキシ基の繰り返しのみからなることが好ましい。ジアルキルシロキサン鎖がジアルキルシリルオキシ基の繰り返しのみからなる場合、得られる皮膜の化学的・物理的耐久性が良好である。 In the formula (s2), it is preferable that Z s1 is —O— and Y s1 is a single bond, that is, the molecular chain consists only of repeating dialkylsilyloxy groups. When the dialkylsiloxane chain consists only of repeating dialkylsilyloxy groups, the resulting film has good chemical and physical durability.
　トリアルキルシリル基含有分子鎖に含まれる分子鎖としては、下記式で表される分子鎖を挙げることができる。式中、ｑ１は１～６０の整数を表し、左側の＊は中心ケイ素原子との結合手を表し、右側の＊はトリアルキルシリル含有基との結合手を表すものとする。ｑ１は、１～４５の整数であることが好ましく、より好ましくは１～３０の整数である。 Examples of the molecular chain contained in the trialkylsilyl group-containing molecular chain include a molecular chain represented by the following formula. In the formula, q1 represents an integer of 1 to 60, * on the left side represents a bond with a central silicon atom, and * on the right side represents a bond with a trialkylsilyl-containing group. q1 is preferably an integer of 1 to 45, more preferably an integer of 1 to 30.
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　また、トリアルキルシリル基含有分子鎖を構成する元素の合計数は、２４以上であることが好ましく、より好ましくは４０以上、さらに好ましくは５０以上であり、また５０００以下が好ましく、より好ましくは４０００以下、さらに好ましくは２０００以下、よりさらに好ましくは１２００以下、ことさら好ましくは７００以下、特に好ましく２５０以下である。 The total number of elements constituting the trialkylsilyl group-containing molecular chain is preferably 24 or more, more preferably 40 or more, still more preferably 50 or more, and preferably 5000 or less, more preferably 4000. Hereinafter, it is more preferably 2000 or less, even more preferably 1200 or less, even more preferably 700 or less, and particularly preferably 250 or less.
　トリアルキルシリル基含有分子鎖は、下記式（ｓ３）で表される基であることが好ましい。 The trialkylsilyl group-containing molecular chain is preferably a group represented by the following formula (s3).
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　式（ｓ３）中、Ｒs1、Ｒs2、Ｚs1、Ｙs1、ｎ１は、上記と同義である。＊は、中心ケイ素原子との結合手を表す。 In the formula (s3), R s1 , R s2 , Z s1 , Y s1 , and n1 are as defined above. * Represents a bond with the central silicon atom.
　トリアルキルシリル基含有分子鎖は、下記式（ｓ３－１）で表される基であることが好ましく、下記式（ｓ３－１－１）で表される基であることがより好ましい。 The trialkylsilyl group-containing molecular chain is preferably a group represented by the following formula (s3-1), and more preferably a group represented by the following formula (s3-1-1).
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　式（ｓ３－１）及び式（ｓ３－１－１）中、Ｒs2、Ｙs1、Ｚs1、ｎ１は上記と同義である。Ｒs3は、それぞれ独立に、炭素数１～４のアルキル基を表す。＊は、中心ケイ素原子との結合手を表す。 In formula (s3-1) and formula (s3-1-1), R s2 , Y s1 , Z s1 , and n1 have the same meanings as described above. R s3 each independently represents an alkyl group having 1 to 4 carbon atoms. * Represents a bond with the central silicon atom.
　Ｒs3で表されるアルキル基の炭素数は１～３であることが好ましく、より好ましくは１～２である。また、式（ｓ３－１）及び式（ｓ３－１－１）中、－Ｓｉ（Ｒs3）3に含まれるＲs3の合計の炭素数は、９以下であることが好ましく、より好ましくは６以下、さらに好ましくは４以下である。さらに、－Ｓｉ（Ｒs3）3に含まれるＲs3のうち、Ｒs3は少なくとも１つがメチル基であることが好ましく、２つ以上のＲs3がメチル基であることが好ましく、３つのＲs3全てがメチル基であることが特に好ましい。 The number of carbon atoms of the alkyl group represented by R s3 is preferably 1 to 3, more preferably 1 to 2. In the formulas (s3-1) and (s3-1-1), the total carbon number of R s3 contained in —Si (R s3 ) 3 is preferably 9 or less, more preferably 6 Hereinafter, it is more preferably 4 or less. Further, among R s3 contained in —Si (R s3 ) 3 , at least one R s3 is preferably a methyl group, and two or more R s3 are preferably methyl groups, and three R s3 It is particularly preferred that all are methyl groups.
　また、トリアルキルシリル基含有分子鎖は、下記式（ｓ３－２）で表される基であることがさらに好ましく、下記式（ｓ３－２－１）で表される基であることが特に好ましい。 Further, the trialkylsilyl group-containing molecular chain is more preferably a group represented by the following formula (s3-2), and particularly preferably a group represented by the following formula (s3-2-1). .
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　式（ｓ３－２）及び（ｓ３－２－１）中、Ｒs2、Ｙs1、Ｚs1、ｎ１は上記と同義である。Ｒs4は、それぞれ独立に、炭素数１～４のアルキル基を表す。＊は中心ケイ素原子との結合手を表す。 In the formulas (s3-2) and (s3-2-1), R s2 , Y s1 , Z s1 , and n1 have the same meanings as described above. R s4 independently represents an alkyl group having 1 to 4 carbon atoms. * Represents a bond with the central silicon atom.
　Ｒs4で表される炭素数１～４のアルキル基としては、上記Ｒs3で説明した基が挙げられ、その好ましい範囲も同様である。 Examples of the alkyl group having 1 to 4 carbon atoms represented by R s4 include the groups described above for R s3 , and the preferred ranges thereof are also the same.
　トリアルキルシリル基含有分子鎖としては式（ｓ３－Ｉ）で表される基が挙げられる。式（ｓ３－Ｉ）中、＊は中心ケイ素原子との結合手を表す。 Examples of the trialkylsilyl group-containing molecular chain include a group represented by the formula (s3-I). In the formula (s3-I), * represents a bond with the central silicon atom.
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-T000021
Figure JPOXMLDOC01-appb-T000021
Figure JPOXMLDOC01-appb-T000022
Figure JPOXMLDOC01-appb-T000022
　上記表１、表２に示したｎ３０は、１～３０であることが好ましい。 N30 shown in Tables 1 and 2 above is preferably 1 to 30.
　次に、式（Ａ１）におけるＡa1について説明する。複数のＡa1は、それぞれ独立に、加水分解性基であり、加水分解によりヒドロキシ基（シラノール基）を与える基であればよく、例えば、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基等の炭素数１～６のアルコキシ基；ヒドロキシ基；アセトキシ基；塩素原子；イソシアネート基；等を好ましく挙げることができる。中でも、炭素数１～６のアルコキシ基であることが好ましく、炭素数１～４のアルコキシ基であることがより好ましく、炭素数１～２のアルコキシ基がさらに好ましい。 Next, A a1 in the formula (A1) will be described. A plurality of A a1 are each independently a hydrolyzable group and may be any group that gives a hydroxy group (silanol group) by hydrolysis. For example, carbon such as methoxy group, ethoxy group, propoxy group, butoxy group, etc. Preferred examples include an alkoxy group of 1 to 6; a hydroxy group; an acetoxy group; a chlorine atom; an isocyanate group; Among these, an alkoxy group having 1 to 6 carbon atoms is preferable, an alkoxy group having 1 to 4 carbon atoms is more preferable, and an alkoxy group having 1 to 2 carbon atoms is more preferable.
　式（Ａ１）におけるＺa1は、トリアルキルシリル基含有分子鎖、シロキサン骨格含有基、又は炭化水素鎖含有基を表す。Ｚa1がトリアルキルシリル基含有分子鎖である場合は、上記Ｒa1と同様のものが挙げられる。 Z a1 in the formula (A1) represents a trialkylsilyl group-containing molecular chain, a siloxane skeleton-containing group, or a hydrocarbon chain-containing group. When Z a1 is a trialkylsilyl group-containing molecular chain, the same as the above R a1 can be mentioned.
　また、Ｚa1がシロキサン骨格含有基である場合、前記シロキサン骨格含有基は、シロキサン単位（Ｓｉ－Ｏ－）を含有する１価の基であり、Ｒa1のトリアルキルシリル基含有分子鎖を構成する元素数よりも少ない数の元素で構成されるものであることが好ましい。これにより、シロキサン骨格含有基は、トリアルキルシリル基含有分子鎖よりも長さが短いか、立体的な広がり（かさ高さ）が小さな基となる。シロキサン骨格含有基には、２価の炭化水素基が含まれていてもよい。 In the case where Z a1 is a siloxane skeleton-containing group, the siloxane skeleton-containing group is a monovalent group containing a siloxane unit (Si—O—), and constitutes a trialkylsilyl group-containing molecular chain of R a1. It is preferable that the number of elements is smaller than the number of elements to be formed. As a result, the siloxane skeleton-containing group is a group having a shorter length than the trialkylsilyl group-containing molecular chain or a small steric spread (bulk height). The siloxane skeleton-containing group may contain a divalent hydrocarbon group.
　シロキサン骨格含有基は、下記式（ｓ４）で表される基であることが好ましい。 The siloxane skeleton-containing group is preferably a group represented by the following formula (s4).
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
　式（ｓ４）中、Ｒs2、Ｚs1、及びＹs1は上記と同義である。Ｒs5は、炭化水素基又はヒドロキシ基を表し、該炭化水素基に含まれる－ＣＨ2－は、－Ｏ－に置き換わっていても
よく、該炭化水素基に含まれる水素原子は、フッ素原子に置換されていてもよい。ｎ３は、０～５の整数を表す。＊は、中心ケイ素原子との結合手を表す。 In formula (s4), R s2 , Z s1 , and Y s1 have the same meanings as described above. R s5 represents a hydrocarbon group or a hydroxy group, —CH 2 — contained in the hydrocarbon group may be replaced by —O—, and the hydrogen atom contained in the hydrocarbon group is a fluorine atom. May be substituted. n3 represents an integer of 0 to 5. * Represents a bond with the central silicon atom.
　Ｒs5で表される炭化水素基としては、Ｒs1で表される炭化水素基と同様の基が挙げられ、脂肪族炭化水素基であることが好ましく、アルキル基であることがより好ましい。炭素数は１～４であることが好ましく、より好ましくは１～３、さらに好ましくは１～２である。 Examples of the hydrocarbon group represented by R s5 include the same groups as the hydrocarbon group represented by R s1 , preferably an aliphatic hydrocarbon group, and more preferably an alkyl group. The number of carbon atoms is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 to 2.
　ｎ３は、１～５であることが好ましく、より好ましくは１～３である。 N3 is preferably 1 to 5, and more preferably 1 to 3.
　シロキサン骨格含有基の元素数の合計は、１００以下であることが好ましく、より好ましくは５０以下、さらに好ましくは３０以下であり、１０以上であることが好ましい。また、Ｒa1のトリアルキルシリル基含有分子鎖とＺa1のシロキサン骨格含有基の元素数の差は、１０以上であることが好ましく、より好ましくは２０以上であり、１０００以下であることが好ましく、より好ましくは５００以下、さらに好ましくは２００以下である。 The total number of elements of the siloxane skeleton-containing group is preferably 100 or less, more preferably 50 or less, still more preferably 30 or less, and preferably 10 or more. The difference in the number of elements between the molecular chain containing R a1 trialkylsilyl group and the group containing Z a1 siloxane skeleton is preferably 10 or more, more preferably 20 or more, and preferably 1000 or less. More preferably, it is 500 or less, More preferably, it is 200 or less.
　シロキサン骨格含有基としては、具体的には、下記式で表される基が挙げられる。 Specific examples of the siloxane skeleton-containing group include groups represented by the following formulas.
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
　Ｚa1が炭化水素鎖含有基である場合、トリアルキルシリル基含有分子鎖の分子鎖を構成する元素数よりも炭化水素鎖部分の炭素数が少ないものであればよい。また、トリアルキルシリル基含有分子鎖の最長直鎖を構成する元素数よりも、炭化水素鎖の最長直鎖の炭素数が少ないものであることが好ましい。炭化水素鎖含有基は、通常、炭化水素基（炭化水素鎖）のみから構成されるが、必要により、この炭化水素鎖の一部のメチレン基（－ＣＨ2－）が酸素原子に置き換わった基であってもよい。また、Ｓｉ原子に隣接するメチレン基（－ＣＨ2－）は酸素原子に置き換わることはなく、また連続する２つのメチレン基（－ＣＨ2－）が同時に酸素原子に置き換わることもない。
　なお、炭化水素鎖部分の炭素数とは、酸素非置換型の炭化水素鎖含有基では炭化水素基（炭化水素鎖）を構成する炭素原子の数を意味し、酸素置換型の炭化水素鎖含有基では、酸素原子をメチレン基（－ＣＨ2－）と仮定して数えた炭素原子の数を意味するものとする。
　以下、特に断りがない限り、酸素非置換型の炭化水素鎖含有基（すなわち１価の炭化水素基）を例にとって炭化水素鎖含有基について説明するが、いずれの説明でも、そのメチレン基（－ＣＨ2－）のうち一部を酸素原子に置き換えることが可能である。 In the case where Za1 is a hydrocarbon chain-containing group, it is sufficient if the hydrocarbon chain portion has a smaller number of carbon atoms than the number of elements constituting the molecular chain of the trialkylsilyl group-containing molecular chain. The number of carbon atoms of the longest straight chain of the hydrocarbon chain is preferably smaller than the number of elements constituting the longest straight chain of the trialkylsilyl group-containing molecular chain. The hydrocarbon chain-containing group is usually composed only of a hydrocarbon group (hydrocarbon chain), but if necessary, a group in which a part of the methylene group (—CH 2 —) of the hydrocarbon chain is replaced with an oxygen atom. It may be. Further, the methylene group (—CH 2 —) adjacent to the Si atom is not replaced with an oxygen atom, and two consecutive methylene groups (—CH 2 —) are not replaced with an oxygen atom at the same time.
In addition, the carbon number of the hydrocarbon chain portion means the number of carbon atoms constituting the hydrocarbon group (hydrocarbon chain) in the oxygen non-substituted hydrocarbon chain-containing group, and includes the oxygen-substituted hydrocarbon chain. In the group, the number of carbon atoms is assumed assuming that the oxygen atom is a methylene group (—CH 2 —).
Hereinafter, unless otherwise specified, the hydrocarbon chain-containing group will be described by taking an oxygen-nonsubstituted hydrocarbon chain-containing group (that is, a monovalent hydrocarbon group) as an example. In any description, the methylene group (— Part of CH 2 —) can be replaced with oxygen atoms.
　前記炭化水素鎖含有基は、それが炭化水素基の場合には、炭素数は１以上、３以下であることが好ましく、より好ましくは１である。また、前記炭化水素鎖含有基は、分岐鎖であっても直鎖であってもよい。前記炭化水素鎖含有基は、飽和又は不飽和の脂肪族炭化水素鎖含有基であることが好ましく、飽和脂肪族炭化水素鎖含有基であることがより好ましい。前記飽和脂肪族炭化水素鎖含有基としては、飽和脂肪族炭化水素基がより好ましい。飽和脂肪族炭化水素基には、例えば、メチル基、エチル基、プロピル基等が含まれる。 When the hydrocarbon chain-containing group is a hydrocarbon group, the number of carbon atoms is preferably 1 or more and 3 or less, more preferably 1. Further, the hydrocarbon chain-containing group may be branched or linear. The hydrocarbon chain-containing group is preferably a saturated or unsaturated aliphatic hydrocarbon chain-containing group, and more preferably a saturated aliphatic hydrocarbon chain-containing group. The saturated aliphatic hydrocarbon chain-containing group is more preferably a saturated aliphatic hydrocarbon group. Examples of the saturated aliphatic hydrocarbon group include a methyl group, an ethyl group, and a propyl group.
　飽和脂肪族炭化水素基の一部のメチレン基（－ＣＨ2－）が酸素原子に置き換わる場合、具体的には、（ポリ）エチレングリコール単位を有する基等を例示することができる。 When a partial methylene group (—CH 2 —) of a saturated aliphatic hydrocarbon group is replaced with an oxygen atom, specific examples include a group having a (poly) ethylene glycol unit.
　式（Ａ１）におけるｘは０または１であり、好ましくは０である。 X in the formula (A1) is 0 or 1, preferably 0.
　式（Ａ１）で表される有機ケイ素化合物（ａ）は、下記式（Ａ２）で表される化合物であることが好ましい。 The organosilicon compound (a) represented by the formula (A1) is preferably a compound represented by the following formula (A2).
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
　式（Ａ２）中、Ｒs1、Ｒs2、Ｚs1、Ｙs1、ｎ１、Ａa1、Ｚa1、ｘは、それぞれ上記と同義である。 In the formula (A2), R s1 , R s2 , Z s1 , Y s1 , n1, A a1 , Z a1 , and x are as defined above.
　式（Ａ２）で表される有機ケイ素化合物（ａ）は、下記式（Ａ２－１）で表される化合物であることが好ましく、式（Ａ２－１－１）で表される化合物であることがより好ましい。 The organosilicon compound (a) represented by the formula (A2) is preferably a compound represented by the following formula (A2-1), and is a compound represented by the formula (A2-1-1) Is more preferable.
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
　式（Ａ２－１）及び式（Ａ２－１－１）中、Ｒs2、Ｒs3、Ｙs1、Ｚs1、ｎ１、Ａa1は上記と同義である。 In formula (A2-1) and formula (A2-1-1), R s2 , R s3 , Y s1 , Z s1 , n1 and A a1 are as defined above.
　式（Ａ２）で表される有機ケイ素化合物（ａ）は、下記式（Ａ２－２）で表される化合物であることがさらに好ましく、特に好ましくは式（Ａ２－２－１）で表される化合物である。 The organosilicon compound (a) represented by the formula (A2) is more preferably a compound represented by the following formula (A2-2), particularly preferably represented by the formula (A2-2-1). A compound.
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
　式（Ａ２－２）及び式（Ａ２－２－１）中、Ｒs2、Ｒs4、Ｙs1、Ｚs1、ｎ１、Ａa1は上記と同義である。 In the formula (A2-2) and the formula (A2-2-1), R s2 , R s4 , Y s1 , Z s1 , n1 and A a1 are as defined above.
　式（Ａ２）で表される有機ケイ素化合物（ａ）としては、具体的には、式（Ａ－Ｉ）で表される化合物が挙げられる。 Specific examples of the organosilicon compound (a) represented by the formula (A2) include a compound represented by the formula (AI).
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-T000029
Figure JPOXMLDOC01-appb-T000029
Figure JPOXMLDOC01-appb-T000030
Figure JPOXMLDOC01-appb-T000030
Figure JPOXMLDOC01-appb-T000031
Figure JPOXMLDOC01-appb-T000031
Figure JPOXMLDOC01-appb-T000032
Figure JPOXMLDOC01-appb-T000032
　上記表３－１、表３－２、表４－１、表４－２に示したｎ１０は、好ましくは１～３０である。 N10 shown in the above Table 3-1, Table 3-2, Table 4-1, and Table 4-2 is preferably 1-30.
　上記（Ａ－Ｉ）式の中でも、（Ａ－Ｉ－２６）で表されるものがより好ましい。すなわち、式（Ａ２）で表される有機ケイ素化合物（ａ）としては、下記式（Ａ２－２６）で表されるものが好ましい。 Among the above formulas (AI), those represented by (AI-26) are more preferable. That is, as the organosilicon compound (a) represented by the formula (A2), those represented by the following formula (A2-26) are preferable.
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
　式（Ａ２－２６）中、ｎは１～６０であり、好ましくは１～３０である。 In the formula (A2-26), n is 1 to 60, preferably 1 to 30.
　上記有機ケイ素化合物（ａ）の量としては、組成物１００質量％中、０．１質量％以上であることが好ましく、より好ましくは０．２質量％以上、さらに好ましくは０．３質量％以上である。また、上限としては、２．６質量％未満であることが好ましく、より好ましくは２．０質量％以下、さらに好ましくは１．５質量％以下、特に好ましくは１．０質量％以下である。上記の有機ケイ素化合物（ａ）の量は、組成物の調製時の配合量及び組成物の分析結果から算出した値のいずれかが、上記範囲を満たすことが好ましい。なお、本明細書において、各成分の量（濃度）または質量比の範囲を記載している場合、上記と同様に、組成物の調製時の配合量及び組成物の分析結果から算出した値のいずれかが、該範囲を満たすことが好ましい。 The amount of the organosilicon compound (a) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and further preferably 0.3% by mass or more in 100% by mass of the composition. It is. Moreover, as an upper limit, it is preferable that it is less than 2.6 mass%, More preferably, it is 2.0 mass% or less, More preferably, it is 1.5 mass% or less, Most preferably, it is 1.0 mass% or less. As for the amount of the above-mentioned organosilicon compound (a), it is preferable that either the blending amount at the time of preparing the composition or the value calculated from the analysis result of the composition satisfies the above range. In addition, in the present specification, when the amount (concentration) or mass ratio range of each component is described, the value calculated from the blending amount at the time of preparing the composition and the analysis result of the composition, as described above. It is preferable that either satisfies the range.
　有機ケイ素化合物（ａ）の合成方法の例としては、特開２０１７－２０１００９号公報に記載の方法が挙げられる。 Examples of the method for synthesizing the organosilicon compound (a) include the method described in JP-A-2017-201109.
　本発明における有機ポリシラザン（ｂ）は、下記式（Ｂ２）で表される構造単位を有することが好ましい。 The organic polysilazane (b) in the present invention preferably has a structural unit represented by the following formula (B2).
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
　式（Ｂ２）中、Ｒp21、Ｒp22及びＲp23は、それぞれ独立に、水素原子又は炭素数１～１０の炭化水素基を表す。ただし、Ｒp21及びＲp22の少なくとも一方は、炭素数１～１０の炭化水素基を表す。 In formula (B2), R p21 , R p22 and R p23 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. However, at least one of R p21 and R p22 represents a hydrocarbon group having 1 to 10 carbon atoms.
　Ｒp21、Ｒp22及びＲp23が炭化水素基である場合、その炭素数は１～４であることが好ましく、より好ましくは１～３、さらに好ましくは１～２である。該炭化水素基は、脂肪族炭化水素基が好ましく、アルキル基がより好ましい。該アルキル基としては、メチル基、エチル基、プロピル基、ブチル基等が挙げられ、中でもメチル基が好ましい。
　Ｒp23は、水素原子であることがより好ましい。 When R p21 , R p22 and R p23 are hydrocarbon groups, the carbon number thereof is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 to 2. The hydrocarbon group is preferably an aliphatic hydrocarbon group, and more preferably an alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group, and among them, a methyl group is preferable.
R p23 is more preferably a hydrogen atom.
　前記有機ポリシラザン（ｂ）は、下記式（Ｂ１）で表される構造単位をさらに有することが好ましい。 The organic polysilazane (b) preferably further has a structural unit represented by the following formula (B1).
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
　式（Ｂ１）中、Ｒp10及びＲp11は、それぞれ独立に、水素原子又は炭素数１～１０の炭化水素基を表し、Ｙは、炭素数１～１０の２価の炭化水素基を表し、複数のＸは、それぞれ独立に、加水分解性基を表す。 In formula (B1), R p10 and R p11 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, Y represents a divalent hydrocarbon group having 1 to 10 carbon atoms, Several X represents a hydrolysable group each independently.
　Ｒp10及びＲp11における炭化水素基の炭素数は１～４であることが好ましく、より好ましくは１～３、さらに好ましくは１～２である。Ｒp10及びＲp11における炭化水素基としては、脂肪族炭化水素基が好ましく、アルキル基がより好ましい。該アルキル基としては、メチル基、エチル基、プロピル基、ブチル基等が挙げられ、中でもメチル基が好ましい。 The hydrocarbon group in R p10 and R p11 preferably has 1 to 4 carbon atoms, more preferably 1 to 3, and still more preferably 1 to 2. The hydrocarbon group for R p10 and R p11 is preferably an aliphatic hydrocarbon group, more preferably an alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group, and among them, a methyl group is preferable.
　Ｙの２価の炭化水素基としては、その炭素数が１～４であることが好ましく、より好ましくは１～３、さらに好ましくは１～２である。前記２価の炭化水素基は、鎖状であることが好ましく、鎖状である場合、直鎖状、分岐鎖状のいずれであってもよい。また、前記２価の炭化水素基は、２価の脂肪族炭化水素基であることが好ましく、アルカンジイル基であることが好ましい。２価の炭化水素基としては、メチレン基、エチレン基、プロピレン基、ブチレン基等が挙げられる。 The divalent hydrocarbon group for Y preferably has 1 to 4 carbon atoms, more preferably 1 to 3, and still more preferably 1 to 2. The divalent hydrocarbon group is preferably chain-like, and when it is chain-like, it may be either linear or branched. The divalent hydrocarbon group is preferably a divalent aliphatic hydrocarbon group, and preferably an alkanediyl group. Examples of the divalent hydrocarbon group include a methylene group, an ethylene group, a propylene group, and a butylene group.
　さらに、前記２価の炭化水素基に含まれる一部の－ＣＨ2－は－Ｏ－に置き換わっていてもよい。この場合連続する２つの－ＣＨ2－が同時に－Ｏ－に置き換わることはなく、Ｓｉ原子に隣接する－ＣＨ2－が－Ｏ－に置き換わることはない。２つ以上の－ＣＨ2－が－Ｏ－に置き換わっている場合、－Ｏ－と－Ｏ－の間の炭素原子数は、２～４であることが好ましく、２～３であることがさらに好ましい。２価の炭化水素基の一部が－Ｏ－に置き換わった基としては、具体的には、（ポリ）エチレングリコール単位を有する基、（ポリ）プロピレングリコール単位を有する基等を例示することができる。 Furthermore, a part of —CH 2 — contained in the divalent hydrocarbon group may be replaced by —O—. In this case, two consecutive —CH 2 — are not simultaneously replaced with —O—, and —CH 2 — adjacent to the Si atom is not replaced with —O—. When two or more —CH 2 — are replaced by —O—, the number of carbon atoms between —O— and —O— is preferably 2 to 4, and more preferably 2 to 3 preferable. Specific examples of the group in which a part of the divalent hydrocarbon group is replaced by —O— include a group having a (poly) ethylene glycol unit, a group having a (poly) propylene glycol unit, and the like. it can.
　Ｘの加水分解性基としては、加水分解によりヒドロキシ基（シラノール基）を与える基であればよく、例えば、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基等の炭素数１～４のアルコキシ基；ヒドロキシ基；アセトキシ基；塩素原子；イソシアネート基；等を好ましく挙げることができる。中でも、炭素数１～４のアルコキシ基が好ましく、炭素数１～２のアルコキシ基がより好ましい。複数のＸは、同一でも異なっていてもよく、同一であることが好ましい。 The hydrolyzable group of X may be any group that gives a hydroxy group (silanol group) by hydrolysis, and examples thereof include an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group; Preferred examples include hydroxy group; acetoxy group; chlorine atom; isocyanate group; Among these, an alkoxy group having 1 to 4 carbon atoms is preferable, and an alkoxy group having 1 to 2 carbon atoms is more preferable. A plurality of X may be the same or different and are preferably the same.
　本発明の組成物は、上記有機ポリシラザン（ｂ）を２種以上混合してもよい。 In the composition of the present invention, two or more organic polysilazanes (b) may be mixed.
　前記有機ポリシラザン（ｂ）は、前記有機ポリシラザン（ｂ）１００質量％に対して、前記式（Ｂ１）のＳｉＸ3基を２質量％以上含有することが好ましく、より好ましくは５質量％以上、さらに好ましくは８質量％以上である。上限は限定されないが、５０質量％以下であってもよく、４０質量％以下であってもよく、３０質量％以下であってもよい。 The organic polysilazane (b) preferably contains 2% by mass or more of the SiX 3 group of the formula (B1) with respect to 100% by mass of the organic polysilazane (b), more preferably 5% by mass or more. Preferably it is 8 mass% or more. Although an upper limit is not limited, 50 mass% or less may be sufficient, 40 mass% or less may be sufficient, and 30 mass% or less may be sufficient.
　前記有機ケイ素化合物（ａ）と前記有機ポリシラザン（ｂ）との合計の濃度は、本発明の組成物１００質量％に対して、０．２質量％以上２．６質量％未満である。下限は、０．３質量％以上であることが好ましく、より好ましくは０．５質量％以上である。上限は２．０質量％以下であることが好ましく、より好ましくは１．８質量％以下、さらに好ましくは１．３質量％以下、特に好ましくは１．０質量％以下である。前記有機ケイ素化合物（ａ）と前記有機ポリシラザン（ｂ）との合計の濃度を上記の範囲に調整することで、皮膜とした際、耐硫酸性を良好にできる。さらに耐摩耗性、耐温水性なども良好にでき、また白濁や塗り斑がないなど外観も良好にできる。 The total concentration of the organosilicon compound (a) and the organic polysilazane (b) is 0.2% by mass or more and less than 2.6% by mass with respect to 100% by mass of the composition of the present invention. The lower limit is preferably 0.3% by mass or more, and more preferably 0.5% by mass or more. The upper limit is preferably 2.0% by mass or less, more preferably 1.8% by mass or less, further preferably 1.3% by mass or less, and particularly preferably 1.0% by mass or less. By adjusting the total concentration of the organosilicon compound (a) and the organopolysilazane (b) to the above range, the sulfuric acid resistance can be improved when a film is formed. Furthermore, wear resistance, hot water resistance, etc. can be improved, and the appearance can be improved such as no cloudiness or smears.
　本発明の組成物において、前記有機ケイ素化合物（ａ）と前記有機ポリシラザン（ｂ）との質量比（ａ／ｂ）は、０．２以上であることが好ましく、より好ましくは０．４以上、さらに好ましくは０．５以上である。上限は、１００以下であることが好ましく、より好ましくは５０以下、さらに好ましくは１０以下、特に好ましくは８以下である。 In the composition of the present invention, the mass ratio (a / b) between the organosilicon compound (a) and the organopolysilazane (b) is preferably 0.2 or more, more preferably 0.4 or more. More preferably, it is 0.5 or more. The upper limit is preferably 100 or less, more preferably 50 or less, still more preferably 10 or less, and particularly preferably 8 or less.
　前記有機ポリシラザン（ｂ）におけるＳｉ－Ｈの水素原子、及びＳｉに結合した炭素数１～１０の炭化水素基の含有比は適宜選択できるが、例えば炭化水素基／水素原子のモル比は０．１～５０であり、好ましくは０．２～１０である。なお、これらのモル比は、ＮＭＲ測定等から算出できる。 The content ratio of the Si—H hydrogen atom in the organic polysilazane (b) and the hydrocarbon group having 1 to 10 carbon atoms bonded to Si can be appropriately selected. For example, the molar ratio of hydrocarbon group / hydrogen atom is 0.00. 1 to 50, preferably 0.2 to 10. These molar ratios can be calculated from NMR measurements and the like.
　本発明の組成物は、溶媒（ｃ）が混合されている。 The composition of the present invention is mixed with the solvent (c).
　溶媒（ｃ）としては、アルコール系溶媒、エーテル系溶媒、ケトン系溶媒、エステル系溶媒、アミド系溶媒、脂肪族炭化水素系溶媒、芳香族炭化水素系溶媒等が挙げられる。 Examples of the solvent (c) include alcohol solvents, ether solvents, ketone solvents, ester solvents, amide solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, and the like.
　前記アルコール系溶媒としては、メタノール、エタノール、プロパノール、ブタノール、エチレングリコール、プロピレングリコール、ジエチレングリコール、１－プロポキシ２－プロパノール等が挙げられ、前記エーテル系溶媒としては、ジメトキシエタン、テトラヒドロフラン、ジオキサン、ジブチルエーテル等が挙げられ、ケトン系溶媒としては、アセトン、メチルエチルケトン（２－ブタノン）等が挙げられ、エステル系溶媒としては、酢酸エチル、酢酸ブチル等が挙げられ、アミド系溶媒としては、ジメチルホルムアミド等が挙げられ、脂肪族炭化水素系溶媒としては、ペンタン、ヘキサン、ヘプタン、オクタン、イソオクタン、シクロペンタン、シクロヘキサン、シクロヘプタン、メチルシクロヘキサン、ミネラルスピリット等が挙げられ、芳香族炭化水素系溶媒としては、ベンゼン、トルエン、キシレン、クロロベンゼン、ジクロロベンゼン等が挙げられる。中でも、ケトン系溶媒、エーテル系溶媒、エステル系溶媒、脂肪族炭化水素系溶媒が好ましく、脂肪族炭化水素系溶媒がより好ましい。これらの溶媒は１種類を用いても良いし、２種類以上を適宜混合して用いても良い。コーティング液の安定性が増し、塗工ブレや塗工時の異物が低減できることから、溶媒（ｃ）は、水分を有していないことが好ましい。 Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, 1-propoxy 2-propanol, and the ether solvent includes dimethoxyethane, tetrahydrofuran, dioxane, dibutyl ether. Examples of ketone solvents include acetone and methyl ethyl ketone (2-butanone), examples of ester solvents include ethyl acetate and butyl acetate, and examples of amide solvents include dimethylformamide and the like. Examples of aliphatic hydrocarbon solvents include pentane, hexane, heptane, octane, isooctane, cyclopentane, cyclohexane, cycloheptane, methylcyclohexane, mineral spirits. . Examples of the aromatic hydrocarbon solvents, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, and the like. Among these, ketone solvents, ether solvents, ester solvents, and aliphatic hydrocarbon solvents are preferable, and aliphatic hydrocarbon solvents are more preferable. One type of these solvents may be used, or two or more types may be appropriately mixed and used. It is preferable that the solvent (c) does not have moisture because stability of the coating liquid is increased and coating blur and foreign matters at the time of coating can be reduced.
　組成物１００質量％に対する溶媒（ｃ）の濃度は、５０質量％以上であることが好ましく、より好ましくは８０質量％以上、さらに好ましくは９０質量％以上、特に好ましくは９５質量％以上である。上限は、有機ケイ素化合物（ａ）、有機ポリシラザン（ｂ）、及びこれら以外の添加成分（以下、第三成分（ｄ）という）の量に応じて設定され、有機ケイ素化合物（ａ）、有機ポリシラザン（ｂ）、及び第三成分（ｄ）以外が溶媒（ｃ）であってもよい The concentration of the solvent (c) with respect to 100% by mass of the composition is preferably 50% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and particularly preferably 95% by mass or more. The upper limit is set according to the amount of the organic silicon compound (a), the organic polysilazane (b), and other additive components (hereinafter referred to as the third component (d)), and the organic silicon compound (a) and the organic polysilazane. The solvent (c) may be other than (b) and the third component (d).
　本発明の組成物は、触媒を共存させてもよい。本発明において、前記触媒は、有機ポリシラザンを硬化させ得る触媒であれば、特に制限されないが、例えば、１－メチルピペラジン、１－メチルピペリジン、４，４’－トリメチレンジピペリジン、４，４’－トリメチレンビス（１－メチルピペリジン）、ジアザビシクロ－［２，２，２］オクタン、シス－２，６－ジメチルピペラジン、４－（４－メチルピペリジン）ピリジン、ピリジン、ジピリジン、α－ピコリン、β－ピコリン、γ－ピコリン、ピペリジン、ルチジン、ピリミジン、ピリダジン、４，４’－トリメチレンジピリジン、２－（メチルアミノ）ピリジン、ピラジン、キノリン、キノキサリン、トリアジン、ピロール、３－ピロリン、イミダゾール、トリアゾール、テトラゾール、１－メチルピロリジンなどのＮ－ヘテロ環状化合物、例えば、メチルアミン、ジメチルアミン、トリメチルアミン、エチルアミン、ジエチルアミン、トリエチルアミン、プロピルアミン、ジプロピルアミン、トリプロピルアミン、ブチルアミン、ジブチルアミン、トリブチルアミン、ペンチルアミン、ジペンチルアミン、トリペンチルアミン、ヘキシルアミン、ジヘキシルアミン、トリヘキシルアミン、ヘプチルアミン、ジヘプチルアミン、オクチルアミン、ジオクチルアミン、トリオクチルアミン、フェニルアミン、ジフェニルアミン、トリフェニルアミンなどのアミン類、例えば、１，８－ジアザビシクロ［５，４，０］７－ウンデセン（ＤＢＵ）、１，５－ジアザビシクロ［４，３，０］５－ノネン（ＤＢＮ）、１，５，９－トリアザシクロドデカン、１，４，７－トリアザシクロノナンなどが挙げられる。
　また、触媒としては上記触媒の他、例えば、酸性化合物；塩基性化合物；有機金属化合物；等が挙げられる。前記酸性化合物としては、塩酸、硝酸、硫酸、リン酸、過酸化水素、塩素酸、次亜塩素酸等の無機酸；酢酸、プロピオン酸、酪酸、吉草酸、マレイン酸、ステアリン酸等の有機酸；等が挙げられる。前記塩基性化合物としては、アンモニア等が挙げられる。前記有機金属化合物としては、Ａｌ、Ｆｅ、Ｚｎ、Ｓｎ等の金属元素を中心金属とする有機金属化合物が挙げられ、カルボン酸アルミニウム、アルミニウムアセチルアセトン錯体、アルミニウムエチルアセトアセテート錯体等の有機アルミニウム化合物；カルボン酸鉄（オクチル酸鉄など）等の有機鉄化合物；亜鉛アセチルアセトナートモノハイドレート、ナフテン酸亜鉛、オクチル酸亜鉛等の有機亜鉛化合物；ジブチル錫ジアセテート錯体等の有機錫化合物；その他、有機金属化合物としては、Ｎｉ、Ｔｉ、Ｐｔ、Ｒｈ、Ｃｏ、Ｒｕ、Ｏｓ、Ｐｄ、Ｉｒ、などを含む金属カルボン酸塩；Ｎｉ、Ｐｔ、Ｐｄ、Ｒｈなどを含むアセチルアセトナ錯体；Ａｕ、Ａｇ、Ｐｄ、Ｎｉ、Ｚｎ、Ｔｉなどの金属微粒子；金属過酸化物；メタルクロライド；フェロセン、ジルコノセンなどの金属のシクロペンタジエニル錯体等が挙げられる。 The composition of the present invention may coexist with a catalyst. In the present invention, the catalyst is not particularly limited as long as it is a catalyst capable of curing organic polysilazane. For example, 1-methylpiperazine, 1-methylpiperidine, 4,4′-trimethylenedipiperidine, 4,4 ′ -Trimethylenebis (1-methylpiperidine), diazabicyclo- [2,2,2] octane, cis-2,6-dimethylpiperazine, 4- (4-methylpiperidine) pyridine, pyridine, dipyridine, α-picoline, β -Picoline, γ-picoline, piperidine, lutidine, pyrimidine, pyridazine, 4,4'-trimethylenedipyridine, 2- (methylamino) pyridine, pyrazine, quinoline, quinoxaline, triazine, pyrrole, 3-pyrroline, imidazole, triazole N-heterocyclization of tetrazole, 1-methylpyrrolidine, etc. Products such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, butylamine, dibutylamine, tributylamine, pentylamine, dipentylamine, tripentylamine, hexylamine, Amines such as dihexylamine, trihexylamine, heptylamine, diheptylamine, octylamine, dioctylamine, trioctylamine, phenylamine, diphenylamine, triphenylamine, such as 1,8-diazabicyclo [5,4,0 ] 7-Undecene (DBU), 1,5-diazabicyclo [4,3,0] 5-nonene (DBN), 1,5,9-triazacyclododecane, 1,4,7-triazacyclo Nan and the like.
In addition to the above-mentioned catalyst, examples of the catalyst include acidic compounds; basic compounds; organometallic compounds; Examples of the acidic compound include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, hydrogen peroxide, chloric acid, and hypochlorous acid; organic acids such as acetic acid, propionic acid, butyric acid, valeric acid, maleic acid, and stearic acid. And the like. Examples of the basic compound include ammonia. Examples of the organometallic compound include organometallic compounds having a metal element such as Al, Fe, Zn, and Sn as a central metal, and organoaluminum compounds such as aluminum carboxylate, aluminum acetylacetone complex, and aluminum ethylacetoacetate complex; Organic iron compounds such as iron oxide (such as iron octylate); Organic zinc compounds such as zinc acetylacetonate monohydrate, zinc naphthenate and zinc octylate; Organic tin compounds such as dibutyltin diacetate complex; Other organic metals As compounds, metal carboxylates containing Ni, Ti, Pt, Rh, Co, Ru, Os, Pd, Ir, etc .; acetylacetona complexes containing Ni, Pt, Pd, Rh, etc .; Au, Ag, Pd Metal fine particles such as Ni, Zn, Ti; metal peroxides; metal chlorides; Erosen include cyclopentadienyl complexes of metals such as zirconocene.
　本発明の組成物は、効果を阻害しない範囲で、酸化防止剤、防錆剤、紫外線吸収剤、光安定剤、防カビ剤、抗菌剤、生物付着防止剤、消臭剤、顔料、難燃剤、帯電防止剤等の各種の添加剤を共存させてもよい。 The composition of the present invention is an antioxidant, a rust inhibitor, a UV absorber, a light stabilizer, a fungicide, an antibacterial agent, an anti-bioadhesive agent, a deodorant, a pigment, a flame retardant, as long as the effect is not impaired Various additives such as an antistatic agent may coexist.
　上記の組成物の硬化物である皮膜、及び基材上に該皮膜が被覆された被覆体も本発明に含まれる。 A film that is a cured product of the above composition and a coated body in which the film is coated on a substrate are also included in the present invention.
　本発明の組成物から得られる皮膜は、通常、基材上に形成されており、基材と接触させる方法としては、例えば組成物を基材にコーティングする方法が挙げられ、スピンコーティング法、ディップコーティング法、スプレーコーティング法、ロールコート法、バーコート法、手塗り(布等に液を染み込ませ、基材に塗りこむ方法)、かけ流し(液をスポイト
などを用いて基材にそのままかけ、塗布する方法)、霧吹き（霧吹きを用いて基材に塗布する方法）などが挙げられる。
　上記のようにして基材上に接触させた組成物を、空気中、常温で静置（例えば１時間～４８時間）するか又は加熱（例えば３００℃以下）することで、空気中の水分と反応し、分解とシロキシ基化が進行し、基材上にＳｉ-Ｏ骨格含有皮膜を形成できる。皮膜の膜厚
は例えば０．１～５００ｎｍ程度とできる。好ましくは０．２～２００ｎｍ、より好ましくは、０．３～１００ｎｍである。これらの膜厚に調整することで、膜内部まで均一に硬化した膜を得ることができ、また、耐摩耗性が良好な膜を得ることが出来る。 The film obtained from the composition of the present invention is usually formed on a substrate, and examples of the method of contacting the substrate include a method of coating the composition on the substrate, such as a spin coating method, dip coating, and the like. Coating method, spray coating method, roll coating method, bar coating method, hand-painting (a method of soaking a liquid in a cloth, etc., applying to a substrate), pouring (spraying the liquid directly onto the substrate using a dropper, etc. Application method), spraying (method of applying to a substrate using spraying), and the like.
The composition brought into contact with the substrate as described above is allowed to stand in the air at room temperature (for example, 1 hour to 48 hours) or heated (for example, 300 ° C. or less), so that moisture in the air By reacting, decomposition and siloxy grouping proceed, and a Si—O skeleton-containing film can be formed on the substrate. The film thickness can be, for example, about 0.1 to 500 nm. The thickness is preferably 0.2 to 200 nm, more preferably 0.3 to 100 nm. By adjusting to these film thicknesses, it is possible to obtain a film that is uniformly cured up to the inside of the film, and it is possible to obtain a film with good wear resistance.
　本発明の皮膜上の液滴の接触角は、９０°以上であることが好ましく、より好ましくは９８°以上、さらに好ましくは１００°以上である。この接触角は後述する実施例の測定法に従って決定できる。
　本発明の皮膜上の液滴の滑落速度は、１０ｍｍ／秒以上であることが好ましく、より好ましくは２５ｍｍ／秒以上、さらに好ましくは３０ｍｍ／秒以上、特に好ましくは４５ｍｍ／秒以上である。この滑落速度は後述する実施例の測定法に従って決定できる。
　本発明の皮膜は、後述する実施例の耐摩耗性の測定において、好ましくは３０００回以上、より好ましくは５０００回以上、さらに好ましくは８０００回以上の耐摩耗性を示す。
　本発明の皮膜の外観は、製膜後目視で判る異物や白靄等が無いことが好ましい。異物や白靄があると、液滴を滑落させる際に液滴が引っかかって滑らなくなり、あるいは、有効成分が液滴と共に流れ落ちて性能が失われることがある。異物や白靄が発生した場合、布などで拭き取って皮膜を使用することもできるが、拭き取る作業によって撥水・撥油性に寄与する成分が取り除かれすぎて性能が低下したり、膜の面内の性能のばらつきを誘発したりすることがあるため、拭き取りなしで諸性能を発現することが好ましい。
　温水試験後の本発明の皮膜上の液滴の接触角は、９０°以上であることが好ましく、より好ましくは９７°以上、さらに好ましくは１０２°以上である。この温水試験後の接触角は、後述する実施例の測定法に従って決定できる。
　温水試験後の本発明の皮膜上の液滴の滑落速度は、２０ｍｍ／秒以上であることが好ましく、より好ましくは２５ｍｍ／秒以上、さらに好ましくは２７ｍｍ／秒以上である。この温水試験後の滑落速度は、後述する実施例の測定法に従って決定できる。
　本発明の皮膜は、後述する実施例の耐硫酸試験の評価において、マジック痕が１点以上拭き取れることが好ましく、２点以上拭き取れることがより好ましく、３点とも拭き取れることが特に好ましい。 The contact angle of the droplet on the film of the present invention is preferably 90 ° or more, more preferably 98 ° or more, and further preferably 100 ° or more. This contact angle can be determined according to the measurement method of the Example mentioned later.
The sliding speed of the droplet on the film of the present invention is preferably 10 mm / second or more, more preferably 25 mm / second or more, further preferably 30 mm / second or more, and particularly preferably 45 mm / second or more. This sliding speed can be determined according to the measurement method of the Example mentioned later.
The film of the present invention preferably has a wear resistance of 3000 times or more, more preferably 5000 times or more, and still more preferably 8000 times or more in the measurement of wear resistance of Examples described later.
It is preferable that the appearance of the film of the present invention is free from foreign matter, white glaze and the like that can be visually observed after film formation. When there is a foreign object or a white glaze, when the liquid droplet is slid down, the liquid droplet is caught and does not slide, or the active ingredient may flow down together with the liquid droplet and the performance may be lost. If foreign matter or white mist occurs, the film can be used by wiping with a cloth, etc., but the component that contributes to water and oil repellency is removed too much by the wiping work, and the performance deteriorates or the in-plane of the film It is preferable to develop various performances without wiping off.
The contact angle of the droplet on the film of the present invention after the hot water test is preferably 90 ° or more, more preferably 97 ° or more, and further preferably 102 ° or more. The contact angle after this hot water test can be determined according to the measurement method of the Example mentioned later.
The sliding speed of the droplet on the film of the present invention after the hot water test is preferably 20 mm / second or more, more preferably 25 mm / second or more, and further preferably 27 mm / second or more. The sliding speed after this hot water test can be determined according to the measuring method of the Example mentioned later.
In the evaluation of the sulfuric acid resistance test of the examples described later, the film of the present invention preferably has one or more magic marks wiped off, more preferably two or more points wiped off, and particularly preferably all three points wiped off.
　本発明の皮膜の膜厚は、厚すぎると本発明の皮膜が吸湿硬化性であるため、内部まで十分に硬化が進行せず、皮膜が柔らかくなることで耐摩耗性が悪くなる。そのため、皮膜は適切な膜厚であることが好ましい。また、皮膜が厚くなりすぎると皮膜表面の凹凸やブリードした成分により、皮膜表面が白濁し外観が悪くなる傾向がある。皮膜が耐摩耗性を発現する程度に硬化が進行したかどうかの目安としては、皮膜の密度を測定することで評価することができる。特に、基材近傍の皮膜の密度が０．９０ｇ/ｃｍ3以上であることが好ましく、０．９５ｇ/ｃｍ3以上であることがより好ましい。上限は特に限定されないが、例えば２．２ｇ/ｃｍ3程度である。基材近傍の皮膜の密度とは、基材上に本発明の皮膜が被覆された被覆体において、該皮膜における基材側の皮膜の密度をいう。膜の密度の測定方法としては、例えばＸ線反射率法を用いることができる。 If the film of the present invention is too thick, the film of the present invention is hygroscopic and curable, so that curing does not proceed sufficiently to the inside, and the film becomes soft, resulting in poor wear resistance. Therefore, it is preferable that the film has an appropriate film thickness. On the other hand, when the film becomes too thick, the film surface tends to become cloudy and the appearance tends to deteriorate due to unevenness of the film surface and bleeding components. As an indication of whether the coating has progressed to such an extent that the coating exhibits wear resistance, it can be evaluated by measuring the density of the coating. In particular, the density of the film in the vicinity of the substrate is preferably 0.90 g / cm 3 or more, and more preferably 0.95 g / cm 3 or more. Although an upper limit is not specifically limited, For example, it is about 2.2 g / cm < 3 >. The density of the film in the vicinity of the substrate refers to the density of the film on the substrate side in the film in the coated body in which the film of the present invention is coated on the substrate. As a method for measuring the density of the film, for example, an X-ray reflectivity method can be used.
　組成や膜構造等が未知の多層薄膜の積層構造、膜厚或いは密度を測定する手段としてＸ線反射率法が用いられている。このＸ線反射率法は密度の異なる層が接する界面で反射するＸ線の干渉振動を利用して測定するものであり、例えば、電極上に形成した酸化膜等の膜厚の測定やスピンバルブ膜の積層構造の解析に用いられている。 The X-ray reflectivity method is used as a means for measuring the laminated structure, film thickness or density of multilayer thin films whose composition and film structure are unknown. This X-ray reflectivity method is a measurement using interference vibration of X-rays reflected at an interface where layers having different densities are in contact. For example, measurement of a film thickness of an oxide film or the like formed on an electrode or a spin valve It is used to analyze the laminated structure of films.
　このようなＸ線反射率測定（ＸＲＲ）は、主に膜の各界面で反射したＸ線が干渉する現象を上記のように観測し、この測定結果をシミュレーション演算データを用いてフィッティングすることによって、各層の密度、膜厚およびラフネスを解析することが可能となる。上記した基材側の皮膜の密度は、フィッティング処理した値を意味し、フィッティング処理を行い皮膜が複数の層にフィッティングされた場合は、基材に最も近い層の密度が基材側の皮膜の密度となる。また、皮膜が単層にフィッティングされた場合は、その密度を基材側の皮膜の密度として採用する。ここでフィッティングとは、Ｘ線測定した際に、検出されるＸ線スペクトルについて、スペクトル強度の理論計算値と実測強度との差を補正することである。 In such X-ray reflectivity measurement (XRR), the phenomenon in which X-rays reflected mainly at each interface of the film interfere with each other is observed as described above, and this measurement result is fitted using simulation calculation data. It becomes possible to analyze the density, film thickness and roughness of each layer. The density of the film on the base material side means a value obtained by fitting treatment. When the film is fitted to a plurality of layers after fitting processing, the density of the layer closest to the base material is the density of the film on the base material side. It becomes density. Further, when the film is fitted into a single layer, the density is adopted as the density of the film on the substrate side. Here, the fitting is to correct the difference between the theoretical calculated value of the spectrum intensity and the actually measured intensity for the detected X-ray spectrum when X-ray measurement is performed.
　図１に、皮膜のＸＲＲ測定結果をフィッティング処理した一例を示す。最表面から数十ｎｍの膜厚を有する薄膜の密度は、全反射臨界角度から算出することが可能であり、それ以外の層の密度は、干渉縞の振幅の大きさから算出することができる。 FIG. 1 shows an example of fitting the XRR measurement result of the film. The density of a thin film having a film thickness of several tens of nanometers from the outermost surface can be calculated from the total reflection critical angle, and the density of other layers can be calculated from the amplitude of interference fringes. .
　また各層の膜厚は振動の周期から算出することが可能である。さらに、ラフネスについては、例えば特開２００１－３４９８４９号公報に記載されているように、反射率測定データ全体の減衰率や高角度側における干渉縞の振幅の減衰から算出することができる。 The film thickness of each layer can be calculated from the period of vibration. Further, the roughness can be calculated from the attenuation factor of the entire reflectance measurement data and the attenuation of the interference fringe amplitude on the high angle side, as described in, for example, Japanese Patent Laid-Open No. 2001-349849.
　フィッティング処理の手順を以下に具体的に説明する。まず、単層膜または多層膜からなる膜試料の表面に対する臨界角近傍の角度からのＸ線入射により測定データを得る。データの測定点数をＮｐとし、ある測定箇所ｎでの入射Ｘ線の角度をα(ｎ)としたとき、たとえばα(ｎ)を０．０５°～５°での反射Ｘ線強度を各々観測し、入射Ｘ線の強度で規格化することで、入射角度α（ｎ）でのＸ線の反射率Ｒ｛α（ｎ）｝を得る。Ｒ｛α（ｎ）｝に対するα（ｎ）の相関図をＸＲＲプロファイルと呼ぶ。試料の基板や膜厚により、適切な条件で測定する必要があり、適切な条件とは具体的に、入射Ｘ線の角度α（ｎ）の測定範囲や入射Ｘ線の発散角［°］である。 The specific procedure of the fitting process is described below. First, measurement data is obtained by X-ray incidence from an angle near the critical angle with respect to the surface of a film sample composed of a single layer film or a multilayer film. When the number of data measurement points is Np and the angle of incident X-rays at a measurement point n is α (n), for example, the reflected X-ray intensity is observed when α (n) is 0.05 ° to 5 °. Then, by normalizing with the intensity of the incident X-ray, the X-ray reflectivity R {α (n)} at the incident angle α (n) is obtained. A correlation diagram of α (n) with respect to R {α (n)} is referred to as an XRR profile. It is necessary to measure under appropriate conditions depending on the substrate and film thickness of the sample. Specifically, the appropriate conditions are the measurement range of the angle α (n) of incident X-rays and the divergence angle [°] of incident X-rays. is there.
　α（ｎ）において、測定開始の角度は入射Ｘ線が全反射する条件を満たす必要がある。一般的にＸ線が全反射する条件は元素種および密度から推算可能であり、ガラス基板やＳｉ基板などでは全反射臨界角が０．２３°と言われている。さらに測定終了角度はバックグラウンドと同程度の信号強度となる角度であるほうが好ましい。 In α (n), the measurement start angle needs to satisfy the conditions for total reflection of incident X-rays. In general, the conditions for total reflection of X-rays can be estimated from the element type and density, and the critical angle for total reflection is said to be 0.23 ° for glass substrates, Si substrates, and the like. Furthermore, it is preferable that the measurement end angle is an angle at which the signal intensity is about the same as the background.
　入射Ｘ線の発散角について、基板上の膜の膜厚が厚くなるほど、Ｘ線の干渉の周期［°］が短くなることが知られており、膜厚が厚いほど、入射Ｘ線の発散角［°］を小さくする必要がある。一般的に膜の厚みが１００ｎｍ以上だと、発散角は、０．０１５°以下、３００ｎｍ以上だと、発散角が０．００３°以下とする必要があると言われている。発散角を０．０１５°以下にするためには、Ｇｅ（１１０）などの分光結晶で１回反射させるなどの方法がある。さらに発散角が０．００３°以下にするためには、Ｇｅ（１１０）などの分光結晶で２回反射させるなどの方法がある。これらの分光結晶はＸ線を反射する際に入射強度が激減する。そのため、必要以上に分光結晶を導入しないほうがよい。 As for the divergence angle of incident X-rays, it is known that as the film thickness of the film on the substrate increases, the period [°] of X-ray interference decreases. The divergence angle of incident X-rays increases as the film thickness increases. [°] needs to be reduced. Generally, it is said that when the film thickness is 100 nm or more, the divergence angle needs to be 0.015 ° or less, and when it is 300 nm or more, the divergence angle needs to be 0.003 ° or less. In order to set the divergence angle to 0.015 ° or less, there is a method of reflecting once with a spectral crystal such as Ge (110). Furthermore, in order to make a divergence angle 0.003 degrees or less, there exists a method of reflecting twice with spectral crystals, such as Ge (110). These spectroscopic crystals drastically reduce the incident intensity when reflecting X-rays. Therefore, it is better not to introduce spectroscopic crystals more than necessary.
　このようにして測定して得られた実測プロファイルに対し、基板および膜あるいは多層膜のそれぞれに対して、膜厚、密度、ラフネス（空気と膜の界面、膜と間の界面、膜と基板の界面）のパラメーターを初期設定し、これらのパラメーターを少なくとも１個以上変化させてシミュレーション演算により得られるシミュレーション演算プロファイルと呼ぶ。このシミュレーション演算プロファイルが実測プロファイルに近くなるようにフィッティングすることにより、膜試料の密度を決定する。 With respect to the actual profile obtained by measurement in this way, the film thickness, density, and roughness (the interface between the air and the film, the interface between the films, the film and the substrate The interface parameters are initially set, and at least one of these parameters is changed, which is called a simulation calculation profile obtained by simulation calculation. The density of the film sample is determined by fitting so that the simulation calculation profile is close to the actual measurement profile.
　フィッティング処理の手順としては、例えば、最小２乗法による解析が用いられる。シミュレーション演算プロファイルと実測プロファイルとの残差二乗和を最小にするようなパラメーターを決定する。これが測定データに最もフィッティングする一組のパラメーターである。 As the procedure of the fitting process, for example, analysis by the least square method is used. Parameters that minimize the residual sum of squares between the simulation calculation profile and the actual measurement profile are determined. This is the set of parameters that best fits the measurement data.
　残差二乗和（χ2）は、スペクトル強度の計算反射率(Ｉcal)と実験反射率(Ｉexp)との差であり、式（Ｙ）にて表され、０．０１以下であることが望ましい。ここで、Ｎｐはフィッティング範囲内のデータ点数である。αiは入射Ｘ線の角度である。 The residual sum of squares (χ 2 ) is the difference between the calculated reflectance (Ical) of the spectral intensity and the experimental reflectance (Iexp), and is expressed by the formula (Y) and is preferably 0.01 or less. . Here, Np is the number of data points within the fitting range. α i is the angle of the incident X-ray.
Figure JPOXMLDOC01-appb-M000036
Figure JPOXMLDOC01-appb-M000036
　上述のフィッティング処理は、リガク社製解析ソフト（ＧｌｏｂａｌＦｉｔ）などを用いることで、解析することができる。 The above-described fitting process can be analyzed by using analysis software (GlobalFit) manufactured by Rigaku Corporation.
　本発明の組成物を接触させる基材は特に限定されず、基材の形状は平面、曲面のいずれでもよいし、多数の面が組み合わさった三次元的構造でもよい。また基材の材質も限定されず、有機系材料、無機系材料のいずれで構成されていてもよい。前記有機系材料としては、アクリル樹脂、ポリカーボネート樹脂、ポリエステル樹脂、スチレン樹脂、アクリル－スチレン共重合樹脂、セルロース樹脂、ポリオレフィン樹脂等の熱可塑性樹脂；フェノール樹脂、ユリア樹脂、メラミン樹脂、エポキシ樹脂、不飽和ポリエステル、シリコーン樹脂、ウレタン樹脂等の熱硬化性樹脂；等が挙げられ、無機系材料としては、セラミックス；ガラス；鉄、シリコン、銅、亜鉛、アルミニウム等の金属；前記金属を含む合金；等が挙げられる。 The substrate to which the composition of the present invention is contacted is not particularly limited, and the shape of the substrate may be a flat surface or a curved surface, or may be a three-dimensional structure in which a large number of surfaces are combined. Further, the material of the base material is not limited and may be composed of either an organic material or an inorganic material. Examples of the organic material include thermoplastic resins such as acrylic resin, polycarbonate resin, polyester resin, styrene resin, acrylic-styrene copolymer resin, cellulose resin, and polyolefin resin; phenol resin, urea resin, melamine resin, epoxy resin, Examples of inorganic materials include ceramics; glass; metals such as iron, silicon, copper, zinc, and aluminum; alloys containing the above metals; etc. Is mentioned.
　前記基材には予め易接着処理を施しておいてもよい。易接着処理としては、コロナ処理、プラズマ処理、紫外線処理等の親水化処理が挙げられる。また、樹脂、シランカップリング剤、テトラアルコキシシラン等によるプライマー処理を施しても良いし、ポリシラザンなどのガラス皮膜を基材に予め塗布しておいてもよい。 The substrate may be subjected to an easy adhesion treatment in advance. Examples of the easy adhesion treatment include hydrophilic treatment such as corona treatment, plasma treatment, and ultraviolet treatment. In addition, primer treatment with a resin, a silane coupling agent, tetraalkoxysilane, or the like may be performed, or a glass film such as polysilazane may be preliminarily applied to the substrate.
　以下、実施例を挙げて本発明をより具体的に説明するが、本発明はもとより下記実施例によって制限を受けるものではなく、前・後記の趣旨に適合し得る範囲で適当に変更を加えて実施することも勿論可能であり、それらはいずれも本発明の技術的範囲に包含される。
　本発明の実施例で用いた測定法は下記の通りである。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention.
The measurement methods used in the examples of the present invention are as follows.
　接触角の測定
　協和界面化学社製「ＤＭ７００」を使用し、液量を３μＬとして、θ／２法にて透明皮膜表面の水に対する接触角を測定した。 Measurement of Contact Angle Using “DM700” manufactured by Kyowa Interface Chemical Co., Ltd., the liquid volume was 3 μL, and the contact angle of water on the surface of the transparent film was measured by the θ / 2 method.
　滑落速度の測定
　皮膜表面に水滴を滴下したときの滑落速度によって水滴の滑落性を評価した。具体的には、協和界面科学株式会社製の接触角測定装置（ＤＭ７００）を用い、２０°に傾けたガラス基板上の皮膜の上に５０μＬの水滴を滴下し、水滴が、初期滴下位置から１５ｍｍ滑落するまでの時間を測定し、皮膜表面における水滴の滑落速度（ｍｍ／秒）を算出した。 Measurement of sliding speed The sliding characteristics of water droplets were evaluated based on the sliding speed when water droplets were dropped on the film surface. Specifically, using a contact angle measuring device (DM700) manufactured by Kyowa Interface Science Co., Ltd., 50 μL of water droplets were dropped on the film on the glass substrate inclined at 20 °, and the water droplets were 15 mm from the initial dropping position. The time until sliding down was measured, and the sliding speed (mm / sec) of water droplets on the film surface was calculated.
　耐摩耗性の測定
　荷重１０００g／ｃｍ3、往復速度が毎分１６００ｍｍの速度にて、２０ｍｍの距離をザヴィーナＭＸ（登録商標）にて２０００回擦った後、１０００回刻みで擦り、摩耗した部位の中央部分３点における接触角をそれぞれ測定し、３点中２点が９０°以下に低下するまでの回数を測定した。 Measurement of wear resistance A load of 1000 g / cm 3 , a reciprocating speed of 1600 mm / min, a distance of 20 mm was rubbed 2000 times with a Savina MX (registered trademark), and then rubbed in 1000 increments. The contact angles at three points in the central portion were measured, and the number of times until two of the three points dropped to 90 ° or less was measured.
　外観評価
　照度１０００ルクスの環境において、皮膜を目視にて観察し、白靄や異物の有無（以下、まとめて「汚れ」と記載する）を官能評価にて、以下の通り評価した。
　○：全く汚れがない
　△：膜の部分的な汚れが確認できる
　×：膜の全体的な汚れが確認できる Appearance Evaluation In an environment with an illuminance of 1000 lux, the film was visually observed, and the presence or absence of white glaze or foreign matter (hereinafter collectively referred to as “dirt”) was evaluated by sensory evaluation as follows.
○: No contamination at all Δ: Partial contamination of the membrane can be confirmed ×: Overall contamination of the membrane can be confirmed
　耐温水性の測定
　７０℃のイオン交換水にサンプルを１２時間浸漬し、浸漬前後の水接触角及び滑落速度を測定した。 Measurement of hot water resistance The sample was immersed in ion-exchanged water at 70 ° C. for 12 hours, and the water contact angle and sliding speed before and after immersion were measured.
　耐硫酸性及び撥油性の測定
　皮膜の上に、０．１Ｍ硫酸０．０３５ｇを３か所にそれぞれ滴下し、１２時間室温で放置して水分を蒸発させた。水分蒸発後、硫酸を滴下した部位にマジック(サクラ製ペンタッチ油性中字)を用いて丸を描き、その後、ワイピングクロスのザビーナ（登録商標）で拭き取った。マジック痕が３点とも拭き取れた場合は、○、拭き取れない点があった場合は、×とした。また、マジック痕が拭き取れるということは撥油性も良好であることを示す。 Measurement of sulfuric acid resistance and oil repellency 0.035 g of 0.1 M sulfuric acid was dropped on each of three places on the film and allowed to stand at room temperature for 12 hours to evaporate water. After evaporating the water, a circle was drawn on the site where sulfuric acid was dropped using a magic (Sakura pen touch oily middle character), and then wiped off with a wiping cloth Zabina (registered trademark). When all three magic marks were wiped off, it was marked as ◯, and when there were points that could not be wiped off, it was marked as x. In addition, the fact that the magic mark can be wiped off indicates that the oil repellency is also good.
　皮膜密度の測定
　皮膜密度の測定には、リガク社製Ｘ線反射率測定装置（ＳｍａｒｔＬａｂ）を用いた。Ｘ線源として４５ｋＷのＸ線発生装置、ＣｕターゲットによるＣｕＫα線の波長λ＝０．１５４１８ｎｍまたはＣｕＫα１線の波長λ＝０．１５４０６ｎｍを使用し、また、モノクロメータは、用いないかあるいはＧｅ（２２０）モノクロ結晶を使用した。設定条件として、サンプリング幅は０．０１°または０．００２°、捜査範囲０．０～２．５°または０．０～１．６°に設定した。そして、上記設定条件により測定し、反射率測定値を得た。得られた測定値を同社解析ソフト（ＧｌｏｂａｌＦｉｔ）を用いて解析した。 Measurement of film density For measurement of film density, an Rigaku X-ray reflectivity measuring device (SmartLab) was used. An X-ray generator of 45 kW is used as an X-ray source, a wavelength λ = 0.15418 nm of CuKα ray by a Cu target or a wavelength λ = 0.15406 nm of CuKα1 ray, and a monochromator is not used or Ge (220 ) Monochrome crystals were used. As setting conditions, the sampling width was set to 0.01 ° or 0.002 °, and the search range was set to 0.0 to 2.5 ° or 0.0 to 1.6 °. And it measured on the said setting conditions, and obtained the reflectance measured value. The obtained measured value was analyzed using company analysis software (GlobalFit).
　実施例１
　上記の式（Ａ２－２６）におけるｎの平均が２４である化合物（１）０．０３ｇ、Ｄｕｒａｚａｎｅ（登録商標）　１５００　ｓｌｏｗ　ｃｕｒｅ（ＭＥＲＣＫ社製）０．０３ｇを、イソオクタン９．９４ｇに溶解させ、室温で１分間、ボルテックスを用いて混合し、コーティング液を得た。前記コーティング液をプラズマ処理を行った無アルカリガラス（イーグルＸＧ）に、スピンコータ（ＭＩＫＡＳＡ社製）により、回転数３０００ｒｐｍ、２０ｓｅｃの条件で製膜した後、２００℃で３時間熱処理を行って基材上に皮膜を得た。その後、前記の測定方法にて皮膜の評価を行った。なお、Ｄｕｒａｚａｎｅ（登録商標）　１５００　ｓｌｏｗ　ｃｕｒｅは、以下の下記式（Ｂ３）で表される構造単位を有する。 Example 1
0.03 g of the compound (1) having an average n of 24 in the above formula (A2-26) and 0.03 g of Durazan (registered trademark) 1500 slow cure (manufactured by MERCK) were dissolved in 9.94 g of isooctane, Mixing was performed using a vortex at room temperature for 1 minute to obtain a coating solution. The coating solution is formed on a non-alkali glass (Eagle XG) that has been plasma-treated with a spin coater (manufactured by MIKASA) under the conditions of a rotation speed of 3000 rpm and 20 seconds, and then subjected to a heat treatment at 200 ° C. for 3 hours. A film was obtained on top. Thereafter, the film was evaluated by the measurement method described above. Note that Durazan (registered trademark) 1500 slow cure has a structural unit represented by the following formula (B3).
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
　式（Ｂ３）中、Ｒは水素原子又はメチル基を表す。 In the formula (B3), R represents a hydrogen atom or a methyl group.
　実施例２～１１、比較例１～２
　有機ケイ素化合物（ａ）、有機ポリシラザン（ｂ）、及び溶媒（ｃ）の種類及び／又は量を、表５の割合に変更した以外は実施例１と同様にして、皮膜を作製した。なお、Ｄｕｒａｚａｎｅ（登録商標）　１５００　ｒａｐｉｄ　ｃｕｒｅ（ＭＥＲＣＫ社製）も上記（Ｂ３）と同様の構造単位を有している。Ｄｕｒａｚａｎｅ（登録商標）　１５００　ｓｌｏｗ　ｃｕｒｅ及びＤｕｒａｚａｎｅ（登録商標）　１５００　ｒａｐｉｄ　ｃｕｒｅのいずれも９～２７質量％のＳｉ（ＯＣ2Ｈ5）3基を有しており、また、上記（Ｂ３）中の構造における、ＳｉＨ基の水素原子とＳｉ－ＣＨ3基のメチル基のモル比（メチル基／水素原子）は、いずれも１．５～３．０であった。
　前記Ｓｉ（ＯＣ2Ｈ5）3基の質量比、及び水素原子とメチル基のモル比は、1Ｈ－ＮＭＲ（４００ＭＨｚ，基準：ＣＤＣｌ3（＝７．２４ｐｐｍ））の積分値に基づいて定めた。すなわち、積分値から有機ポリシラザン中のＳｉＨ、ＳｉＣＨ3、及びＳｉ（ＯＣＨ2ＣＨ3）3のモル比を求め、水素原子とメチル基のモル比を算出した。また、それぞれを質量比に換算して、有機ポリシラザン中に含まれるＳｉ（ＯＣ2Ｈ5）3基の質量％を算出した。
　比較例１で用いた化合物（２）は、片末端型反応性シリコーンオイル(Ｘ－２４－９０１１、信越化学工業社製)を用いた。 Examples 2-11, Comparative Examples 1-2
A film was prepared in the same manner as in Example 1 except that the types and / or amounts of the organosilicon compound (a), the organic polysilazane (b), and the solvent (c) were changed to the ratios shown in Table 5. Note that Durazan (registered trademark) 1500 rapid cure (manufactured by MERCK) also has the same structural unit as (B3) above. Each of Durazan (registered trademark) 1500 slow cure and Durazan (registered trademark) 1500 rapid cure has 9 to 27% by mass of Si (OC 2 H 5 ) 3 groups, and the structure in (B3) above The molar ratio (methyl group / hydrogen atom) between the hydrogen atom of the SiH group and the methyl group of the Si—CH 3 group was 1.5 to 3.0.
The mass ratio of the Si (OC 2 H 5 ) 3 group and the molar ratio of the hydrogen atom to the methyl group are determined based on an integral value of 1 H-NMR (400 MHz, standard: CDCl 3 (= 7.24 ppm)). It was. That is, the molar ratio of SiH, SiCH 3 , and Si (OCH 2 CH 3 ) 3 in the organic polysilazane was determined from the integrated value, and the molar ratio of hydrogen atoms to methyl groups was calculated. Also, in terms of the respective mass ratio was calculated by mass% of Si (OC 2 H 5) 3 groups contained in the organic polysilazane.
The compound (2) used in Comparative Example 1 was a one-end type reactive silicone oil (X-24-9011, manufactured by Shin-Etsu Chemical Co., Ltd.).
Figure JPOXMLDOC01-appb-T000038
Figure JPOXMLDOC01-appb-T000038
　得られた皮膜の評価結果を表６及び表７に示す。 Table 6 and Table 7 show the evaluation results of the obtained film.
Figure JPOXMLDOC01-appb-T000039
Figure JPOXMLDOC01-appb-T000039
Figure JPOXMLDOC01-appb-T000040
Figure JPOXMLDOC01-appb-T000040
　有機ケイ素化合物（ａ）と有機ポリシラザン（ｂ）を所定の濃度で混合している実施例１～１１では、撥水・撥油性、液滴滑り性、耐摩耗性、耐硫酸性及び耐温水性、及び外観に優れた皮膜を作成することができた。有機ケイ素化合物は光に対する安定性は非常に高いが、一方でシロキサン結合を有することから、有機ケイ素化合物を混合した組成物から得られる皮膜は水や温水に対する耐久性を持たせることが容易ではないことが分かってきた。そのため、有機ケイ素化合物を混合した組成物から得られる皮膜において、過酷な環境に曝された後にでも良好な性能を維持させるためには、耐温水性の高い膜であることが、実使用環境においても性能を維持させるために重要な性能となると言える。また、一般的な仕様条件下で、様々な物や雨などと擦れたり、それらが衝突することで皮膜が剥離すると、撥水・撥油性能を維持することが困難になるため、耐摩耗性も皮膜の特性として重要である。従って、耐温水性及び耐摩耗性を有する皮膜であることも好ましい。 In Examples 1 to 11 in which the organosilicon compound (a) and the organic polysilazane (b) are mixed at a predetermined concentration, water repellency / oil repellency, droplet slipperiness, abrasion resistance, sulfuric acid resistance, and hot water resistance And a film excellent in appearance could be produced. Organosilicon compounds have very high stability to light, but on the other hand, since they have a siloxane bond, it is not easy to make the film obtained from the composition containing the organosilicon compound durable against water and warm water. I understand that. Therefore, in a film obtained from a composition in which an organosilicon compound is mixed, in order to maintain good performance even after being exposed to a harsh environment, a film having high resistance to warm water is required in an actual use environment. It can be said that this is an important performance for maintaining the performance. In addition, if the film peels off due to rubbing against or collision with various objects or rain under general specification conditions, it will be difficult to maintain water and oil repellency, so wear resistance Is also important as a characteristic of the film. Therefore, it is also preferable that the film has hot water resistance and wear resistance.
　本発明の組成物から得られる皮膜は、撥水・撥油性及び耐硫酸性（好ましくは、撥水・撥油性及び耐硫酸性に加えて液滴滑り性、耐摩耗性、外観及び耐温水性）に優れている。そのため、タッチパネルディスプレイ等の表示装置、光学素子、半導体素子、建築材料、自動車部品、ナノインプリント技術等における基材として有用である。さらに、電車、自動車、船舶、航空機等の輸送機器におけるボディー、窓ガラス(フロントガラス、サイドガラス、リアガラス)、ミラー、バンパー等の物品として好適に用いられる。また、建築物外壁、テント、太陽光発電モジュール、遮音板、コンクリート、などの屋外用途にも用いることができる。漁網、虫取り網、水槽などにも用いることができる。更に、台所、風呂場、洗面台、鏡、トイレ周りの各部材の物品、シャンデリア、タイルなどの陶磁器、人工大理石、エアコン等の各種屋内設備にも利用可能である。また、工場内の治具や内壁、配管等の防汚処理としても用いることができる。ゴーグル、眼鏡、ヘルメット、パチンコ、繊維、傘、遊具、サッカーボールなどにも好適である。更に、食品用包材、化粧品用包材、ポットの内部、など、各種包材の付着防止剤としても用いることができる。 The film obtained from the composition of the present invention has water repellency / oil repellency and sulfuric acid resistance (preferably, in addition to water repellency / oil repellency and sulfuric acid resistance, droplet slipping, abrasion resistance, appearance and warm water resistance. ). Therefore, it is useful as a base material in display devices such as a touch panel display, optical elements, semiconductor elements, building materials, automobile parts, nanoimprint technology, and the like. Furthermore, it is suitably used as an article such as a body, window glass (front glass, side glass, rear glass), mirror, bumper, etc. in transportation equipment such as trains, automobiles, ships, and airplanes. Moreover, it can also be used for outdoor uses, such as a building outer wall, a tent, a solar power generation module, a sound insulation board, and concrete. It can also be used for fishing nets, insect nets, water tanks, and the like. Furthermore, it can be used for various indoor facilities such as kitchens, bathrooms, washstands, mirrors, toilet articles, ceramics such as chandeliers and tiles, artificial marble, and air conditioners. It can also be used as an antifouling treatment for jigs, inner walls, pipes and the like in factories. It is also suitable for goggles, glasses, helmets, slingshots, textiles, umbrellas, play equipment, soccer balls and the like. Furthermore, it can also be used as an anti-adhesive agent for various packaging materials such as food packaging materials, cosmetic packaging materials, and the inside of pots.

Claims (9)

  1. 　少なくとも１つのトリアルキルシリル基含有分子鎖と、少なくとも１つの加水分解性基とがケイ素原子に結合している有機ケイ素化合物（ａ）、有機ポリシラザン（ｂ）、及び溶媒（ｃ）の混合組成物であって、
    　前記トリアルキルシリル基に含まれる水素原子はフッ素原子に置換されていてもよく、
    　前記組成物１００質量％に対して、前記有機ケイ素化合物（ａ）と前記有機ポリシラザン（ｂ）との合計の濃度が０．２質量％以上２．６質量％未満である混合組成物。     A mixed composition of an organosilicon compound (a), an organopolysilazane (b), and a solvent (c) in which at least one trialkylsilyl group-containing molecular chain and at least one hydrolyzable group are bonded to a silicon atom Because
    The hydrogen atom contained in the trialkylsilyl group may be substituted with a fluorine atom,
    The mixed composition in which the total concentration of the organosilicon compound (a) and the organic polysilazane (b) is 0.2% by mass or more and less than 2.6% by mass with respect to 100% by mass of the composition.
  2. 　前記有機ポリシラザン（ｂ）が、下記式（Ｂ２）で表される構造単位を有する請求項１に記載の組成物。
    Figure JPOXMLDOC01-appb-C000001
     ［前記式（Ｂ２）中、Ｒp21、Ｒp22、及びＲp23は、それぞれ独立に、水素原子又は炭素数１～１０の炭化水素基を表す。ただし、Ｒp21及びＲp22の少なくとも一方は、炭素数１～１０の炭化水素基を表す。］     The composition according to claim 1, wherein the organic polysilazane (b) has a structural unit represented by the following formula (B2).
    Figure JPOXMLDOC01-appb-C000001
     [In the formula (B2), R p21 , R p22 and R p23 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. However, at least one of R p21 and R p22 represents a hydrocarbon group having 1 to 10 carbon atoms. ]
  3. 　前記有機ケイ素化合物（ａ）が下記式（Ａ１）で表される化合物である請求項１又は２に記載の組成物。
    Figure JPOXMLDOC01-appb-C000002
     ［前記式（Ａ１）中、Ｒa1はトリアルキルシリル基含有分子鎖を表し、
    　複数のＡa1は、それぞれ独立に、加水分解性基を表し、
    　Ｚa1は、トリアルキルシリル基含有分子鎖、シロキサン骨格含有基、又は炭化水素鎖含有基を表し、
    　Ｒa1及びＺa1におけるトリアルキルシリル基に含まれる水素原子はフッ素原子に置換されていてもよく、
    　ｘは０または１である。］     The composition according to claim 1 or 2, wherein the organosilicon compound (a) is a compound represented by the following formula (A1).
    Figure JPOXMLDOC01-appb-C000002
     [In the formula (A1), R a1 represents a trialkylsilyl group-containing molecular chain,
    Several A <a1> represents a hydrolysable group each independently,
    Z a1 represents a trialkylsilyl group-containing molecular chain, a siloxane skeleton-containing group, or a hydrocarbon chain-containing group,
    The hydrogen atom contained in the trialkylsilyl group in R a1 and Z a1 may be substituted with a fluorine atom,
    x is 0 or 1. ]
  4. 　前記有機ケイ素化合物（ａ）が下記式（Ａ２）で表される化合物である請求項１～３のいずれかに記載の組成物。
    Figure JPOXMLDOC01-appb-C000003
     ［前記式（Ａ２）中、複数のＲs1は、それぞれ独立に、炭化水素基又はトリアルキルシリルオキシ基を表し、該炭化水素基又はトリアルキルシリルオキシ基に含まれる水素原子は、フッ素原子に置換されていてもよく、
    　複数のＲs2は、それぞれ独立に、炭素数１～１０のアルキル基を表し、
    　ｎ１は、１以上の整数を表し、
    　Ｚs1は、－Ｏ－又は２価の炭化水素基を表し、該２価の炭化水素基に含まれる－ＣＨ2－は、－Ｏ－に置き換わっていてもよい。
    　Ｙs1は単結合又は－Ｓｉ（Ｒs2）2－Ｌs1－を表し、該Ｌs1は、２価の炭化水素基を表し、該２価の炭化水素基に含まれる－ＣＨ2－は、－Ｏ－に置き換わっていてもよい。
    　複数のＡa1は、それぞれ独立に、加水分解性基を表し、
    　Ｚa1は、トリアルキルシリル基含有分子鎖、シロキサン骨格含有基、又は炭化水素鎖含有基を表し、
    　Ｚa1におけるトリアルキルシリル基に含まれる水素原子はフッ素原子に置換されていてもよく、
    　ｘは０または１である。］     The composition according to any one of claims 1 to 3, wherein the organosilicon compound (a) is a compound represented by the following formula (A2).
    Figure JPOXMLDOC01-appb-C000003
     [In the formula (A2), a plurality of R s1 each independently represents a hydrocarbon group or a trialkylsilyloxy group, and the hydrogen atom contained in the hydrocarbon group or trialkylsilyloxy group is a fluorine atom. May be replaced,
    A plurality of R s2 each independently represents an alkyl group having 1 to 10 carbon atoms;
    n1 represents an integer of 1 or more,
    Z s1 represents —O— or a divalent hydrocarbon group, and —CH 2 — contained in the divalent hydrocarbon group may be replaced by —O—.
    Y s1 represents a single bond or —Si (R s2 ) 2 —L s1 —, the L s1 represents a divalent hydrocarbon group, and —CH 2 — contained in the divalent hydrocarbon group is -O- may be substituted.
    Several A <a1> represents a hydrolysable group each independently,
    Z a1 represents a trialkylsilyl group-containing molecular chain, a siloxane skeleton-containing group, or a hydrocarbon chain-containing group,
    The hydrogen atom contained in the trialkylsilyl group in Z a1 may be substituted with a fluorine atom,
    x is 0 or 1. ]
  5. 　前記有機ポリシラザン（ｂ）が、下記式（Ｂ１）で表される構造単位をさらに有する請求項２～４のいずれかに記載の組成物。
    Figure JPOXMLDOC01-appb-C000004
     ［前記式（Ｂ１）中、Ｒp10及びＲp11は、それぞれ独立に、水素原子又は炭素数１～１０の炭化水素基を表し、
    　Ｙは、炭素数１～１０の２価の炭化水素基を表し、
    　複数のＸは、それぞれ独立に、加水分解性基を表す。］     The composition according to any one of claims 2 to 4, wherein the organic polysilazane (b) further has a structural unit represented by the following formula (B1).
    Figure JPOXMLDOC01-appb-C000004
     [In the formula (B1), R p10 and R p11 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms,
    Y represents a divalent hydrocarbon group having 1 to 10 carbon atoms,
    Several X represents a hydrolysable group each independently. ]
  6. 　前記有機ポリシラザン（ｂ）が、前記式（Ｂ１）のＳｉＸ3基を２質量％～５０質量％含有する請求項５に記載の組成物。 The composition according to claim 5, wherein the organic polysilazane (b) contains 2% by mass to 50% by mass of the SiX 3 group of the formula (B1).
  7. 　前記有機ケイ素化合物（ａ）と前記有機ポリシラザン（ｂ）との質量比（ａ／ｂ）が０．２以上である請求項１～６のいずれかに記載の組成物。 The composition according to any one of claims 1 to 6, wherein a mass ratio (a / b) between the organosilicon compound (a) and the organopolysilazane (b) is 0.2 or more.
  8. 　請求項１～７のいずれかに記載の組成物の硬化物である皮膜。 A film that is a cured product of the composition according to any one of claims 1 to 7.
  9. 　基材上に請求項８に記載の皮膜を被覆してなる被覆体であって、Ｘ線反射率法により求められた基材側の皮膜の密度が０．９ｇ/ｃｍ3以上である被覆体。 A coated body obtained by coating the base material with the film according to claim 8, wherein the density of the base-side film determined by the X-ray reflectivity method is 0.9 g / cm 3 or more. .
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