WO2019189792A1 - Composition mixte - Google Patents

Composition mixte 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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English (en)
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/ko
Priority to CN201980020778.XA priority patent/CN111936583B/zh
Publication of WO2019189792A1 publication Critical patent/WO2019189792A1/fr

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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

L'objet de la présente invention est de fournir une composition qui peut être utilisée pour fournir un film présentant d'excellentes propriétés d'effet déperlant, de caractère oléofuge et de résistance à l'acide sulfurique. La présente invention concerne une composition mixte contenant un composé de silicium organique (a) dans lequel au moins une chaîne moléculaire contenant un groupe trialkylsilyle et au moins un groupe hydrolysable sont liés à un atome de silicium, un polysilazane organique (b), et un solvant (c), la concentration totale du composé de silicium organique (a) et du polysilazane organique (b) étant supérieure ou égale à 0,2 % en masse mais inférieure à 2,6 % en masse par rapport aux 100 % en masse de la composition mixte.
PCT/JP2019/014074 2018-03-30 2019-03-29 Composition mixte WO2019189792A1 (fr)

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JP6960194B1 (ja) * 2021-05-12 2021-11-05 株式会社アイセル ガラスを用いた構造体の製造方法、コーティング層の形成方法およびコーティング液

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TWI767115B (zh) 2022-06-11
JP2019183149A (ja) 2019-10-24

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