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WO2025070541A1 - Composition de revêtement - Google Patents

Composition de revêtement Download PDF

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Publication number
WO2025070541A1
WO2025070541A1 PCT/JP2024/034277 JP2024034277W WO2025070541A1 WO 2025070541 A1 WO2025070541 A1 WO 2025070541A1 JP 2024034277 W JP2024034277 W JP 2024034277W WO 2025070541 A1 WO2025070541 A1 WO 2025070541A1
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WO
WIPO (PCT)
Prior art keywords
polymer compound
graft
group
meth
crosslinkable
Prior art date
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PCT/JP2024/034277
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English (en)
Japanese (ja)
Inventor
敬亘 辻井
健 玉本
公洋 松川
雄司 黄瀬
工司 大野
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University Public Corporation Osaka
Kyoto University NUC
Original Assignee
University Public Corporation Osaka
Kyoto University NUC
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Filing date
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Publication of WO2025070541A1 publication Critical patent/WO2025070541A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • 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
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • 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
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/06—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds

Definitions

  • the present invention relates to a coating composition that can form a coating film (film) that has low friction and excellent mechanical strength.
  • polymers composed of various vinyl monomers such as polystyrene, poly(meth)acrylate, polyacrylamide, and copolymers of the monomers that compose these polymers have been used as film components incorporated into coating compositions that form coatings (films) that cover the surfaces of various substrates such as paints, gravure inks, and inkjet inks.
  • Such coating compositions are used for the purpose of protecting the surfaces of buildings, building materials, structures, automobiles, vehicles, electrical equipment, precision equipment, food packaging, food containers, furniture, battery materials, electronic components, machine components, etc., composed of materials such as wood, plastic, rubber, metal, ceramics, glass, and leather, as well as imparting design, improving material durability, imparting aesthetics, imparting thermal conductivity, imparting antistatic properties, imparting electrical conductivity, imparting stain resistance, imparting corrosion resistance, etc.
  • Patent Document 1 proposes a graft-type polymer with a specific graft structure as a polymer to be blended into a coating composition as a film component.
  • the technology of Patent Document 1 makes it possible to form a coating film (film) with excellent low friction, the mechanical strength of the coating film (film) formed is not necessarily sufficient, and therefore there has been a demand for improvement in mechanical strength.
  • the present invention was made in consideration of these circumstances, and aims to provide a coating composition capable of forming a coating film (film) that has low friction and excellent mechanical strength.
  • a coating composition comprising a solvent and a polymer,
  • the polymer includes a structural unit represented by the following general formula (1), and includes a graft type polymer compound (A) having a crosslinkable functional group (a), and a crosslinkable polymer compound (B) having two or more reactive functional groups (b) that undergo a crosslinking reaction with the crosslinkable functional group (a), a content ratio of the crosslinkable polymer compound (B) in a total of 100 mass% of the graft type polymer compound (A) and the crosslinkable polymer compound (B) is 0.1 mass% or more and less than 50 mass%.
  • R1 represents a hydrogen atom or a methyl group
  • X represents O or NH
  • R2 represents any organic group
  • R3 and R4 each independently represent a hydrogen atom, an alkyl group, an aryl group, or an acyl group, and the carbon atom to which R3 and R4 are bonded is a tertiary carbon atom or a quaternary carbon atom
  • n represents any number of repetitions
  • Polymer represents a graft chain including a constituent unit derived from at least one graft monomer selected from the group consisting of a (meth)acrylic acid monomer, a (meth)acrylamide monomer, an aromatic vinyl monomer, and (meth)acrylonitrile.
  • Mn number average molecular weight
  • the present invention provides a coating composition that can form a coating film (film) that has low friction and excellent mechanical strength.
  • the coating composition of the present invention is a coating composition comprising a solvent and a polymer
  • the polymer includes a structural unit represented by the following general formula (1), and includes a graft type polymer compound (A) having a crosslinkable functional group (a), and a crosslinkable polymer compound (B) having two or more reactive functional groups (b) that undergo a crosslinking reaction with the crosslinkable functional group (a),
  • the content of the crosslinkable polymer compound (B) is 0.1 mass% or more and less than 50 mass% in a total of 100 mass% of the graft type polymer compound (A) and the crosslinkable polymer compound (B).
  • R1 represents a hydrogen atom or a methyl group
  • X represents O or NH
  • R2 represents any organic group
  • R3 and R4 each independently represent a hydrogen atom, an alkyl group, an aryl group, or an acyl group, and the carbon atom to which R3 and R4 are bonded is a tertiary carbon atom or a quaternary carbon atom
  • n represents any number of repetitions
  • Polymer represents a graft chain including a constituent unit derived from at least one graft monomer selected from the group consisting of a (meth)acrylic acid monomer, a (meth)acrylamide monomer, an aromatic vinyl monomer, and (meth)acrylonitrile.
  • the coating composition of the present invention comprises, as a polymer, A graft type polymer compound (A) containing a constitutional unit represented by the above general formula (1) and having a crosslinkable functional group (a); a crosslinkable polymer compound (B) having two or more reactive functional groups (b) which undergo a crosslinking reaction with the crosslinkable functional group (a) of the graft type polymer compound (A); Includes.
  • the graft type polymer compound (A) has a structural unit represented by the general formula (1).
  • the graft type polymer compound (A) preferably contains the structural unit represented by the general formula (1) as a main component, and the content of the structural unit represented by the general formula (1) is preferably 80 to 95 mol% from the viewpoint of mechanical strength.
  • the graft type polymer compound (A) is called, for example, a bottle brush type polymer or a cylinder type polymer, and since the graft chain represented by Polymer in the general formula (1) is densely bonded to the main chain, it can be highly elongated and oriented in a good solvent to a degree comparable to the extended chain length.
  • a coating film (coating) having properties attributable to such a graft type polymer compound (A) can be formed.
  • R 1 is a hydrogen atom or a methyl group
  • X is O or NH
  • the main chain of the graft polymer is formed by polymerization of unsaturated groups such as (meth)acryloyloxy groups and (meth)acryloylamino groups. That is, the graft polymer compound (A) has a structure in which a graft chain (side chain) represented by Polymer is grafted to the main chain via a linking group.
  • X is preferably O
  • the main chain of the graft polymer is preferably formed by polymerization of a (meth)acryloyloxy group.
  • the graft polymer compound (A) may contain a structural unit represented by the general formula (1), and may contain structural units (other structural units) other than the structural unit represented by the general formula (1).
  • a monomer constituting the other structural units a conventionally known monomer capable of radical polymerization having an unsaturated bond such as a vinyl group, a vinylidene group, or a vinylene group can be used.
  • n (the number of repetitions) is preferably 2 or more, and more preferably 10 or more. By making the number of n 2 or more, the main chain functions more easily as a polymer.
  • the upper limit of n (the number of repetitions) is not particularly limited, but is preferably 10,000 or less.
  • the structural unit represented by general formula (1) may be a homopolymer or a random polymer containing other structural units. Furthermore, it may have a structure such as a block structure, a gradient structure, a graft structure, or a multi-branched structure.
  • Polymer is a graft chain bonded (grafted) to the main chain, and contains a constituent unit derived from at least one graft monomer selected from the group consisting of (meth)acrylic acid monomers, (meth)acrylamide monomers, aromatic vinyl monomers, and (meth)acrylonitrile.
  • Examples of the (meth)acrylic acid monomer include Methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, 2-methylpropane (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, tetradecyl (meth)acrylate, octadecyl (meth)acrylate, behemo aliphatic, alicyclic, and aromatic alkyl (meth)acrylates such as aryl (meth)acrylate
  • (Meth)acrylates having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, and cyclohexanediol mono(meth)acrylate;
  • (meth)acrylic acid monomers having a carboxy group such as monomers obtained by reacting acrylic acid, methacrylic acid, and hydroxyalkyl (meth)acrylates with acid anhydrides, such as maleic anhydride, succinic anhydride, and phthalic anhydride;
  • (meth)acrylic acid monomers having a sulfonic acid group such as ethyl sulfonate (meth)acrylate;
  • (Meth)acrylic acid monomers having a phosphate group such as (di- or tri-)(meth)acryloyloxyethyl phosphate esters;
  • Oxygen-containing (meth)acrylates such as glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, oxetanylmethyl (meth)acrylate, morpholino (meth)acrylate, methylmorpholino (meth)acrylate, and methylmorpholinoethyl (meth)acrylate;
  • (Meth)acrylates having an amino group such as 2-aminoethyl (meth)acrylate, t-butylaminoethyl (meth)acrylate, tetramethylpiperidyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, pentamethylpiperidyl (meth)acrylate, N-ethylmorpholino (meth)acrylate, trimethylaminoethyl chloride (meth)acrylate, diethylmethylaminoethyl chloride (meth)acrylate, benzyldimethylaminoethyl chloride (meth)acrylate, and trimethylaminoethyl (meth)acrylate methyl sulfate;
  • an amino group such as 2-aminoethyl (meth)acrylate, t-butylaminoethyl (meth)acrylate,
  • Isocyanate group-containing (meth)acrylates such as (meth)acryloyloxyethyl isocyanate and (meth)acryloyloxyethoxyethyl isocyanate; blocked isocyanate-containing (meth)acrylates in which the isocyanate groups of isocyanate-containing (meth)acrylates are blocked with caprolactone, a pyrazole compound, MEK oxime, or the like;
  • Alkoxysilyl group-containing (meth)acrylates such as 3-(trimethoxysilyl)propyl (meth)acrylate, 3-(triethoxysilyl)propyl (meth)acrylate, 3-(meth)acryloxypropylmethyldimethoxysilane, and 3-(meth)acryloxypropylmethyldiethoxysilane; etc.
  • (Meth)acrylamide monomers include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, (meth)acryloylmorpholine, etc.
  • Aromatic vinyl monomers include styrene, vinyl toluene, vinyl hydroxybenzene, chloromethyl styrene, vinyl naphthalene, vinyl biphenyl, vinyl ethyl benzene, vinyl dimethyl benzene, and ⁇ -methyl styrene.
  • R 2 represents an arbitrary organic group.
  • alkylene groups such as ethylene, propylene, butylene, and methylpropylene; polyethylene glycol, propylene glycol, and the like are preferred because of their high versatility and easy availability.
  • R3 and R4 each independently represent a hydrogen atom, an alkyl group, an aryl group, or an acyl group.
  • the carbon atom to which R3 and R4 are bonded is a tertiary carbon atom or a quaternary carbon atom.
  • Specific examples of the ester group bonded to R2 include groups represented by the following formulas (1-1) to (1-6). Note that "*" in the following formulas (1-1) to (1-6) indicates the bond position with R2 in general formula (1).
  • the number average molecular weight (Mn) of the graft polymer compound (A) is preferably 10,000 to 1,000,000, more preferably 20,000 to 800,000, and even more preferably 30,000 to 500,000.
  • the molecular weight distribution (dispersity PDI) of the graft polymer compound (A) is preferably 1.0 to 3.0, more preferably 1.3 to 3.0, and even more preferably 1.6 to 2.5.
  • the number average molecular weight (Mn) and molecular weight distribution (dispersity PDI) of the graft polymer compound (A) can be determined, for example, in terms of polymethyl methacrylate by gel permeation chromatography (GPC) measurement.
  • the graft type polymer compound (A) may be either one in which the molecular weight of the polymer in the general formula (1) is small and the number of graft chains is large, or one in which the molecular weight of the polymer in the general formula (1) is large and the number of graft chains is small.
  • the graft type polymer compound (A) also has a crosslinkable functional group (a).
  • the crosslinkable functional group (a) may be any functional group that exhibits crosslinkability, and is not particularly limited.
  • Examples of the crosslinkable functional group (a) include a carboxyl group, a phosphoric acid group, a phosphoric acid ester group, a hydroxyl group, a glycidyl group, an isocyanate group, a blocked isocyanate group, an alkoxysilyl group, a (meth)acryloyl group, and a halogen atom.
  • a hydroxyl group, an isocyanate group, a blocked isocyanate group, and an alkoxysilyl group are preferred, a hydroxyl group, an isocyanate group, and a blocked isocyanate group are more preferred, and a hydroxyl group and a blocked isocyanate group are even more preferred.
  • the alkoxysilyl group include a trimethoxysilyl group, a triethoxysilyl group, and a tripropoxysilyl group.
  • the crosslinkable functional group (a) is introduced to crosslink with the reactive functional group (b) contained in the crosslinkable polymer compound (B) described below.
  • the coating film (film) formed using the coating composition of the present invention can have excellent mechanical strength while retaining the excellent properties (e.g., low friction and high swelling) derived from the graft polymer compound (A).
  • the crosslinkable functional group (a) may be contained in either the polymer main chain or the graft chain in the graft type polymer compound (A), but from the viewpoint of reactivity, it is preferable that it is contained in the graft chain, and more preferably in the polymer chain represented by Polymer in general formula (1).
  • the method of introducing the crosslinkable functional group (a) into the graft type polymer compound (A) is not particularly limited, but examples thereof include a method of using a monomer having a crosslinkable functional group (a) as a monomer for introducing a graft chain.
  • examples of the method include a method of using a (meth)acrylate having a hydroxyl group or a mono(meth)acrylate of a polyalkylene glycol.
  • examples of the method include a method of using a (meth)acrylate having a hydroxyl group or a mono(meth)acrylate of a polyalkylene glycol.
  • the crosslinkable functional group (a) is an isocyanate group or a blocked isocyanate group
  • a method using an isocyanate group-containing (meth)acrylate or a blocked isocyanate group-containing (meth)acrylate can be used
  • the crosslinkable functional group (a) is an alkoxysilyl group
  • a method using an alkoxysilyl group-containing (meth)acrylate can be used.
  • the method of introducing the crosslinkable functional group (a) into the graft type polymer compound (A) may be a method of introducing the functional group by modification after the preparation of the graft
  • the amount of structural units derived from monomers having a crosslinkable functional group (a) in the graft chain is not particularly limited, but is preferably 1 to 20% by mass, and more preferably 5 to 10% by mass.
  • the external shape of the graft type polymer compound (A) can be considered as a cylinder with the surface including the ends as its side.
  • the surface occupancy ( ⁇ * ) of the graft chains can be calculated by the following formula.
  • DP n,graft is the number average degree of polymerization of the graft chain
  • x is the number of graft chains per unit length of the trunk polymer (pieces / nm)
  • r is the radius of the backbone polymer (nm) (for example, 0.8 nm for poly 2-(2-bromoisobutyryloxy)ethyl methacrylate) (PBIEM))
  • a 2 is the cross-sectional area of the monomer (nm 2 ) (for example, 3.3 nm 2 for methoxypoly(ethylene glycol) methacrylate (PEGMA))
  • l is the total length of the repeating unit of the polymer chain (nm) (for example, 0.25 for polymethacrylate)
  • 2 ⁇ (DP n,graft ⁇ l + r) is the circumference (nm) of the cross section of the graft type polymer compound (A)
  • l / x is the distance (nm) between adjacent
  • the surface occupancy rate of the graft chains is a value between 0 and 1, and the larger the value, the greater the proportion of the ends of the graft chains on the side of the polymer, and the more restricted the degree of freedom of the graft chains.
  • the surface occupancy rate of the graft chains is a value that reflects the degree of freedom of the graft chains, and the higher the surface occupancy rate of the graft chains ( ⁇ * ), the more restricted the structural freedom of the graft chains.
  • the surface occupancy rate of the graft chains of the graft type polymer compound (A) is preferably 0.05 or more and less than 0.75, more preferably 0.10 or more and 0.65 or less, and even more preferably 0.20 or more and 0.50 or less.
  • the surface occupancy rate is within the above range, the density of the graft chains is in an appropriate range, and the effect of the present invention can be further enhanced.
  • the density of the graft chains of the graft polymer compound (A) is preferably 0.01 chains/ nm2 or more, more preferably 0.05 chains/ nm2 or more, even more preferably 0.1 chains/ nm2 or more, and particularly preferably 0.2 chains/nm2 or more .
  • the upper limit is not particularly limited, but may be 1.0 chains/nm2 or less , or may be 0.9 chains/ nm2 or less.
  • the graft type polymer compound (A) can be produced, for example, by polymerizing a polymer containing a structural unit derived from a monomer represented by the following general formula (2) with at least one graft monomer selected from the group consisting of (meth)acrylic acid monomers, (meth)acrylamide monomers, aromatic vinyl monomers, and (meth)acrylonitrile in the presence of a copper catalyst or in the presence of at least one of a quaternary ammonium salt and a quaternary phosphonium salt that generate chloride ions, bromine ions, or iodine ions.
  • R 1 to R 4 and X are the same as R 1 to R 4 and X in the above general formula (1), and Y represents a chlorine atom, a bromine atom, or an iodine atom.
  • the group represented by Y becomes a radical and is eliminated, and the carbon atom to which the halogen atom was bonded becomes a radical.
  • the generated radical of the carbon atom then reacts with the graft monomer to generate a radical.
  • the detached halogen radical immediately bonds to the generated radical to stabilize it.
  • the graft monomer is polymerized sequentially to form a graft chain represented by Polymer in general formula (1), and the desired graft-type polymer can be obtained.
  • the crosslinkable functional group (a) can be introduced into the polymer chain represented by Polymer in general formula (1).
  • the desired graft polymer compound (A) can also be produced by polymerizing a macromonomer represented by the following general formula (4):
  • a macromonomer represented by the following general formula (4) since the reaction site of the macromonomer represented by the following general formula (4) is present at the polymer end, the macromonomer tends to remain unpolymerized and the molecular weight of the obtained polymer is difficult to increase.
  • R 1 to R 4 , X, and Polymer are the same as R 1 to R 4 , X, and Polymer in the above general formula (1).
  • the above-mentioned method using a polymer (hereinafter also referred to as "initiator polymer”) containing a structural unit derived from the monomer represented by the above general formula (2) makes it possible to efficiently produce the desired graft-type polymer compound (A).
  • a specific example of the monomer represented by the above general formula (2) is a monomer represented by the following general formula (3).
  • R1 and R2 have the same meanings as R1 and R2 in the above general formula (1).
  • the monomer represented by the above general formula (3) may be a commercially available product or may be synthesized.
  • the monomer represented by the general formula (3) can be synthesized by reacting a (meth)acrylate having a hydroxyl group or a glycidyl group with 2-bromo-2-methylpropionic acid (2-bromoisobutyric acid).
  • a polymer (initiator polymer) containing a constituent unit derived from the monomer represented by the above general formula (2) can be obtained.
  • the copper catalyst it is preferable to use a copper complex, more preferably a complex of a monovalent copper compound and an organic ligand, and even more preferably a combination of a complex of a monovalent copper compound and an organic ligand and a complex of a divalent copper compound and an organic ligand.
  • monovalent copper compounds include cuprous chloride and cuprous bromide
  • divalent copper compounds include cupric chloride and cupric bromide.
  • organic ligands examples include 2,2'-bipyridyl or a derivative thereof, 1,10-phenanthroline or a derivative thereof, polyamines (tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris(2-aminoethyl)amine, etc.), polycyclic alkaloids such as L-(-)-sparteine, etc.
  • copper compounds and organic ligands may be used alone or in combination of two or more.
  • the molar ratio of the monovalent copper compound to the divalent copper compound based on copper is preferably 1 or more, more preferably 2 or more, and may be 100 or less, or may be 50 or less.
  • the copper complex When mixing a copper complex in radical polymerization, the copper complex may be formed in advance and then used in radical polymerization, or the copper compound and the organic ligand may be mixed in a ratio that forms a copper complex and radical polymerization may be performed.
  • the ratio of the copper compound and the organic ligand to be mixed in radical polymerization is preferably 1 to 3 times the molar number of the organic ligand relative to the molar number of the copper compound, more preferably 1.5 to 2.5 times, since the organic ligand is sufficiently coordinated to the copper compound and the copper complex is well dissolved.
  • quaternary ammonium salt or quaternary phosphonium salt Conventionally known compounds can be used as the quaternary ammonium salt or quaternary phosphonium salt. These quaternary salts are preferably soluble in the polymerization solvent. These quaternary salts can be appropriately selected depending on the type of monomer and polymerization solvent used, etc.
  • Examples of quaternary ammonium salts include tetramethylammonium salts, tetraethylammonium salts, tetrabutylammonium salts, methylimidazolium salts, and methylpyridinium salts.
  • Examples of quaternary phosphonium salts include tetrabutylphosphonium salts, tributylmethylphosphonium salts, and triphenylmethylphosphonium salts.
  • a graft monomer When a graft monomer is reacted with an initiator polymer in the presence of an equimolar or greater amount of a copper catalyst (equal or greater number of copper atoms) or an equimolar or greater amount of a quaternary salt, all initiator groups undergo halogen exchange to form graft chains, and the desired graft-type polymer compound (A) can be obtained.
  • a copper catalyst equal or greater number of copper atoms
  • a quaternary salt all initiator groups undergo halogen exchange to form graft chains, and the desired graft-type polymer compound (A) can be obtained.
  • a graft polymer by solution polymerization in the presence of a polymerization solvent such as an organic solvent.
  • a polymerization solvent such as an organic solvent.
  • the polymerization solvent include anisole, hydrocarbon solvents, ketone solvents, alcohol solvents, glycol solvents, amide solvents, ester solvents, urea solvents, and ionic liquids.
  • polymerization solvents examples include anisole; alcohol solvents such as methanol, ethanol, and isopropanol; glycol solvents such as ethylene glycol, propylene glycol, glycerin, diethylene glycol, and propylene glycol monomethyl ether; amide solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, 3-methoxy-N,N-dimethylpropanamide, and 3-butoxy-N,N-dimethylpropanamide; sulfoxide solvents such as dimethyl sulfoxide; and ionic liquids such as imidazolium salts and quaternary ammonium salts.
  • alcohol solvents such as methanol, ethanol, and isopropanol
  • glycol solvents such as ethylene glycol, propylene glycol, glycerin, diethylene glycol, and propylene glycol monomethyl ether
  • amide solvents such as dimethylformamide, dimethylacetamide, N-methylpyr
  • the amount of polymerization solvent during polymerization is preferably 30 to 80 mass % based on the entire polymerization reaction system, and more preferably 40 to 70 mass %. If the amount of polymerization solvent is less than 30 mass %, the amount of solids may be too high, resulting in an excessively high viscosity. On the other hand, if the amount of polymerization solvent is more than 80 mass %, the monomer concentration may be too low, resulting in a decrease in the polymerization rate.
  • the graft type polymer compound (A) may be used as it is (dissolved in the polymerization solvent), or it may be precipitated in a poor solvent, extracted, and then dissolved in another solvent for use.
  • the graft polymer compound (A) can also be produced by forming a graft polymer as an intermediate in the same manner as above, and then modifying the graft chain.
  • a graft polymer as an intermediate wherein the graft chain is a precursor of the polymer chain represented by Polymer in general formula (1)
  • a compound containing a crosslinkable functional group (a) can be used to modify the graft chain to form a graft chain containing a crosslinkable functional group (a) (polymer chain represented by Polymer in general formula (1)).
  • the graft polymer as an intermediate does not have to contain a crosslinkable functional group (a).
  • the method of modifying the graft chain is not limited.
  • a graft monomer for forming a graft polymer as an intermediate is called a first graft monomer
  • the graft chain may be extended by further carrying out a graft polymerization reaction using a second graft monomer different from the first graft monomer.
  • the second graft monomer it is preferable to use at least one graft monomer selected from the group consisting of (meth)acrylic acid monomers, (meth)acrylamide monomers, aromatic vinyl monomers, and (meth)acrylonitrile.
  • the crosslinkable polymer compound (B) is a polymer having two or more reactive functional groups (b) which undergo a crosslinking reaction with the crosslinkable functional group (a) contained in the above-mentioned graft type polymer compound (A).
  • the reactive functional group (b) may be any group capable of crosslinking with the crosslinkable functional group (a), and may include, but is not limited to, a carboxyl group, a phosphate group, a phosphate ester group, a hydroxyl group, a glycidyl group, an isocyanate group, a blocked isocyanate group, an alkoxysilyl group, a (meth)acryloyl group, and a halogen atom.
  • a hydroxyl group, an isocyanate group, a blocked isocyanate group, and an alkoxysilyl group are preferred, a hydroxyl group, an isocyanate group, and a blocked isocyanate group are more preferred, and a hydroxyl group and a blocked isocyanate group are even more preferred.
  • the alkoxysilyl group include a trimethoxysilyl group, a triethoxysilyl group, and a tripropoxysilyl group.
  • the crosslinkable functional group (a) is a hydroxyl group
  • the reactive functional group (b) may be an isocyanate group or a blocked isocyanate group.
  • the reactive functional group (b) can be a hydroxyl group
  • the reactive functional group (b) can be an alkoxysilyl group
  • the crosslinkable polymer compound (B) by making the crosslinkable polymer compound (B) contain two or more reactive functional groups (b) capable of undergoing a crosslinking reaction with the crosslinkable functional group (a), the crosslinkable polymer compound (B) can suitably crosslink multiple graft-type polymer compounds (A) together, and this makes it possible for the coating film (film) formed using the coating composition of the present invention to have excellent mechanical strength while still retaining the excellent properties (e.g., low friction and high swelling) derived from the graft-type polymer compound (A).
  • the coating film (film) formed using the coating composition of the present invention to have excellent mechanical strength while still retaining the excellent properties (e.g., low friction and high swelling) derived from the graft-type polymer compound (A).
  • the crosslinkable polymer compound (B) may contain two or more reactive functional groups (b).
  • the crosslinkable polymer compound (B) include a copolymer of a monomer having a reactive functional group (b) and a monomer copolymerizable with such a monomer; cellulose nanofiber; and the like.
  • the crosslinkable polymer compound (B) is the above-mentioned copolymer, from the viewpoint of crosslinkability, it is preferable that the crosslinkable polymer compound (B) contains 1 to 20 mol % of structural units derived from a monomer having a reactive functional group (b), and more preferably contains 5 to 10 mol % of structural units derived from a monomer having a reactive functional group (b).
  • the reactive functional group (b) may be any group capable of crosslinking with the crosslinkable functional group (a) contained in the graft-type polymer compound (A).
  • the reactive functional group (b) may be the same group as the crosslinkable functional group (a) or a different group.
  • the crosslinkable functional group (a) and the reactive functional group (b) are different groups. More specifically, it is preferable that the crosslinkable functional group (a) and the reactive functional group (b) are different groups, and that while the crosslinkable functional group (a) and the reactive functional group (b) can crosslink, they do not crosslink with each other, and that the reactive functional groups (a) and (b) do not crosslink with each other.
  • the crosslinkable functional group (a) is a hydroxyl group
  • the reactive functional group (b) is an isocyanate group or a blocked isocyanate.
  • the number average molecular weight (Mn) of the crosslinkable polymer compound (B) is not particularly limited, but from the viewpoint of further enhancing the effect of mechanical strength, it is preferably 5,000 to 3,000,000, more preferably 10,000 to 1,000,000, and even more preferably 15,000 to 500,000.
  • the molecular weight distribution (dispersity PDI) of the crosslinkable polymer compound (B) is preferably 1.0 to 4.0, more preferably 1.2 to 3.0.
  • the number average molecular weight (Mn) and molecular weight distribution (dispersity PDI) of the crosslinkable polymer compound (B) can be determined, for example, by gel permeation chromatography (GPC) measurement in terms of polymethyl methacrylate.
  • the crosslinkable polymer compound (B) can be a linear polymer without graft chains (for example, a linear polymer with an average molecular weight of the side chain of 600 or less).
  • the method for producing the crosslinkable polymer compound (B) is not particularly limited.
  • the crosslinkable polymer compound (B) has a structural unit derived from a monomer having a reactive functional group (b)
  • it can be produced by copolymerizing a monomer having the reactive functional group (b) with a monomer copolymerizable with such a monomer.
  • the above-mentioned monomers exemplified as the monomers for forming the graft chain of the graft type polymer compound (A) can be used. That is, the above-mentioned (meth)acrylic acid-based monomers, (meth)acrylamide-based monomers, aromatic vinyl-based monomers, and (meth)acrylonitrile exemplified as the monomers for forming the graft chain of the graft type polymer compound (A) can be used.
  • the (meth)acrylic acid-based monomer the above-mentioned aliphatic, alicyclic, and aromatic alkyl (meth)acrylates; (meth)acrylates having a hydroxyl group; mono(meth)acrylates of polyalkylene glycols; mono(meth)acrylates of (polyalkylene)glycol monoalkyls, alkylenes, and alkyne ethers or esters; (meth)acrylic acid-based monomers; (meth)acrylic acid-based monomers having a sulfonic acid group; (meth)acrylic acid-based monomers having a phosphoric acid group; (meth)acrylic acid-based monomers having an oxygen atom; (meth)acrylates having an amino group; (meth)acrylates containing an isocyanate group; (meth)acrylates containing a blocked isocyanate group; and (meth)acrylates containing an alkoxysilyl group.
  • the crosslinkable polymer compound (B) may be produced by using an isocyanate group-containing (meth)acrylate or a blocked isocyanate-containing (meth)acrylate as a monomer having the reactive functional group (b) and copolymerizing a monomer not having the reactive functional group (b) (for example, an aliphatic, alicyclic, or aromatic alkyl (meth)acrylate, or a (polyalkylene) glycol monoalkyl, alkylene, alkyne ether, or ester mono(meth)acrylate) as a copolymerizable monomer.
  • a monomer not having the reactive functional group (b) for example, an aliphatic, alicyclic, or aromatic alkyl (meth)acrylate, or a (polyalkylene) glycol monoalkyl, alkylene, alkyne ether, or ester mono(meth)acrylate
  • the crosslinkable polymer compound (B) may be produced by using a (meth)acrylate having a hydroxyl group or a mono(meth)acrylate of a polyalkylene glycol as a monomer having the reactive functional group (b) and copolymerizing a monomer not having the reactive functional group (b) as a copolymerizable monomer.
  • the crosslinkable polymer compound (B) may be produced by using an alkoxysilyl group-containing (meth)acrylate as a monomer having the reactive functional group (b) and copolymerizing a monomer not having the reactive functional group (b) as a copolymerizable monomer.
  • the graft chain constituting the graft type polymer compound (A) is obtained by polymerizing a mono(meth)acrylate having a polyalkylene glycol backbone
  • a mono(meth)acrylate having a polyalkylene glycol backbone is preferable to use as the copolymerizable monomer for forming the crosslinkable polymer compound (B).
  • the reactive functional group (b) of the crosslinkable polymer compound (B) may be a functional group derived from the monomer used in the above method, or may be a functional group introduced by modification using the functional group of the monomer used in the above method.
  • the content ratio of the structural units derived from monomers having reactive functional groups (b) and the structural units derived from copolymerizable monomers in the crosslinkable polymer compound (B) is not particularly limited and may be appropriately selected depending on the number average molecular weight of the crosslinkable polymer compound (B) and the amount of reactive functional groups (b) to be introduced.
  • the molar ratio of "structural units derived from monomers having reactive functional groups (b):structural units derived from copolymerizable monomers” is preferably 1:100 to 10:100, more preferably 3:100 to 7:100, and even more preferably 4:100 to 6:100.
  • crosslinkable polymer compound (B) When producing the crosslinkable polymer compound (B), it is preferable to produce the crosslinkable polymer compound (B) by solution polymerization in the presence of a polymerization solvent such as an organic solvent.
  • a polymerization solvent such as an organic solvent.
  • anisole, hydrocarbon solvents, ketone solvents, alcohol solvents, glycol solvents, amide solvents, ester solvents, urea solvents, ionic liquids, etc. can be used. Among them, it is preferable to use at least a part of a highly polar solvent that can dissolve the quaternary salt and can perform halogen exchange.
  • polymerization solvents examples include alcohol solvents such as anisole, methanol, ethanol, and isopropanol; glycol solvents such as ethylene glycol, propylene glycol, glycerin, diethylene glycol, and propylene glycol monomethyl ether; amide solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, 3-methoxy-N,N-dimethylpropanamide, and 3-butoxy-N,N-dimethylpropanamide; sulfoxide solvents such as dimethyl sulfoxide; and ionic liquids such as imidazolium salts and quaternary ammonium salts.
  • alcohol solvents such as anisole, methanol, ethanol, and isopropanol
  • glycol solvents such as ethylene glycol, propylene glycol, glycerin, diethylene glycol, and propylene glycol monomethyl ether
  • amide solvents such as dimethylformamide, dimethylacetamide, N
  • the amount of polymerization solvent during polymerization is preferably 30 to 80 mass % based on the entire polymerization reaction system, and more preferably 40 to 70 mass %. If the amount of polymerization solvent is less than 30 mass %, the amount of solids may be too high, resulting in an excessively high viscosity. On the other hand, if the amount of polymerization solvent is more than 80 mass %, the monomer concentration may be too low, resulting in a decrease in the polymerization rate.
  • the crosslinkable polymer compound (B) may be used as is (dissolved in the polymerization solvent), or it may be precipitated in a poor solvent, extracted, and then dissolved in another solvent for use. In addition, any known polymerization initiator may be used as appropriate.
  • the coating composition of the present invention contains a solvent.
  • the solvent for example, in addition to the organic solvents that can be used in the solution polymerization described above, water can also be used.
  • the solvent include anisole; alcohol-based solvents such as methanol, ethanol, and isopropanol; glycol-based solvents such as ethylene glycol, propylene glycol, glycerin, diethylene glycol, and propylene glycol monomethyl ether; amide-based solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, 3-methoxy-N,N-dimethylpropanamide, and 3-butoxy-N,N-dimethylpropanamide; ionic liquids such as imidazolium salts and quaternary ammonium salts; hydrocarbon-based solvents such as toluene, xylene, hexane, and isoparaffin; ketone-based solvents such as methyl ethyl ket
  • the coating composition of the present invention can be prepared by mixing the polymer containing the above-mentioned graft type polymer compound (A) and crosslinkable polymer compound (B) with a solvent.
  • the content of the crosslinkable polymer compound (B) is 0.1% by mass or more and less than 50% by mass, preferably 0.5 to 40% by mass, and more preferably 1 to 30% by mass, based on the total of 100% by mass of the graft-type polymer compound (A) and the crosslinkable polymer compound (B).
  • the crosslinkable polymer compound (B) is cellulose nanofiber
  • the above content is more preferably 20% by mass or less, particularly preferably 15% by mass or less, and most preferably 12% by mass or less. If the amount of the crosslinkable polymer compound (B) is too small or too large, the mechanical strength of the resulting coating film (coating) will decrease.
  • the content of the polymer including the graft type polymer compound (A) and the crosslinkable polymer compound (B) in the coating composition of the present invention is not particularly limited, but from the viewpoint of the formability of the coating film (film), it is preferably 1 to 20 mass %, more preferably 2 to 10 mass %.
  • the coating composition of the present invention may also contain a catalyst for crosslinking the crosslinkable functional group (a) of the graft polymer compound (A) with the reactive functional group (b) of the crosslinkable polymer compound (B).
  • the catalyst may be appropriately selected depending on the type of the crosslinkable functional group (a) and the reactive functional group (b).
  • the crosslinkable functional group (a) or the reactive functional group (b) is a hydroxyl group and the other is an isocyanate group or a blocked isocyanate group
  • an organic tin compound such as dibutyltin dilaurate or dioctyltin dilaurate
  • a metal catalyst such as a bismuth compound
  • a base catalyst such as an organic amine
  • a urethane reaction catalyst such as a DMC catalyst
  • a base catalyst or an acid catalyst may be used.
  • the coating composition of the present invention may be a composition for forming a substantially transparent (clear) coating film, and may contain various additives as necessary.
  • colorants such as dyes and pigments, pigment dispersants, defoamers, leveling agents, preservatives, UV absorbers, light stabilizers, thickeners, photoinitiators, photoacid generators, photobase generators, photosensitizers, antibacterial agents, antifungal agents, antifogging agents, water repellents, antistatic agents, conductive agents, reinforcing materials, fibrous materials, other polymer components, etc. may be added.
  • the coating composition of the present invention can be used, for example, as gravure ink, offset ink, inkjet ink, ultraviolet curable ink, electron beam curable ink, oil-based paint for automobiles and construction, and water-based paint. Furthermore, the coating composition of the present invention can be used as a material for forming a coating film on materials in various fields such as plastics, color filter materials, energy-related materials, machine part-related materials, medical devices, medical materials, pharmaceuticals, health care, battery materials, and organic EL materials.
  • the substrate (carrier) for forming the coating film (film) is not particularly limited, but can be appropriately selected from organic materials, inorganic materials, metal materials, etc.
  • the organic material is not particularly limited, and various resins and rubbers can be used without restrictions.
  • the resin may be either a thermosetting resin or a thermoplastic resin.
  • thermosetting resins include epoxy resins, phenolic resins, amino resins, unsaturated polyester resins, polyurethane resins, urea resins, melamine resins, thermosetting polyimide resins, and diallyl phthalate resins.
  • thermoplastic resins include polyolefin-based resins such as polyethylene, polypropylene, polystyrene, and polycycloolefin; vinyl-based resins such as polystyrene, acrylic resins, polyvinyl chloride resins, and polyvinyl alcohol; fluorine-based resins such as polytetrafluoroethylene; polyester-based resins such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and polyethylene naphthalate; and silicone resins such as polydimethylsiloxane.
  • polyolefin-based resins such as polyethylene, polypropylene, polystyrene, and polycycloolefin
  • vinyl-based resins such as polystyrene, acrylic resins, polyvinyl chloride resins, and polyvinyl alcohol
  • fluorine-based resins such as polytetrafluoroethylene
  • polyester-based resins such as polyethylene
  • Examples of rubber include diene-based rubbers such as butadiene rubber, styrene butadiene rubber, chloroprene rubber, isoprene rubber, natural rubber, nitrile rubber, and butyl rubber; and rubbers other than diene-based rubbers such as ethylene propylene rubber, acrylic rubber, polyether rubber, polyurethane rubber, fluororubber, and silicone rubber.
  • diene-based rubbers such as butadiene rubber, styrene butadiene rubber, chloroprene rubber, isoprene rubber, natural rubber, nitrile rubber, and butyl rubber
  • rubbers other than diene-based rubbers such as ethylene propylene rubber, acrylic rubber, polyether rubber, polyurethane rubber, fluororubber, and silicone rubber.
  • the type of substrate is not particularly limited, and examples include tubes, sheets, fibers, strips, films, plates, foils, membranes, pellets, powders, particles, and molded products (e.g., extrusion molded products, casting molded products, etc.).
  • the substrate may have affinity for the graft-type polymer compound (A) and/or the crosslinkable polymer compound (B), or the substrate may be surface-treated to enhance affinity for the graft-type polymer compound (A) and/or the crosslinkable polymer compound (B).
  • the substrate may be surface-treated with a silane coupling agent such as 3-(2-aminoethylaminopropyl)trimethoxysilane.
  • a primer layer may be formed on the substrate to enhance affinity for the graft-type polymer compound (A) and/or the crosslinkable polymer compound (B), and the primer layer may be, for example, a layer made of the crosslinkable polymer compound (B).
  • a composition containing a polymerization initiator and a monomer for forming a crosslinkable polymer compound (B) in a solution obtained by mixing the above-mentioned graft type polymer compound (A) and a solvent may be prepared, a layer of such a composition may be formed on the substrate, and in the state of being the substrate, the monomer for forming the crosslinkable polymer compound (B) may be polymerized in the solution obtained by mixing the graft type polymer compound (A) and a solvent to form the crosslinkable polymer compound (B), thereby forming a layer of the coating composition of the present invention (i.e., the crosslinkable polymer compound (B) may be formed in situ).
  • the coating film obtained by using the coating composition of the present invention may retain a liquid substance.
  • the liquid substance include water, ionic liquid, fluorine-based solvent, oil (hydrocarbon oil, silicone oil, etc.), and preferably at least one selected from water and ionic liquid.
  • the liquid substance may be a hydrophilic liquid substance or a hydrophobic liquid substance.
  • hydrophilic liquid substances include water and hydrophilic ionic liquid.
  • hydrophobic liquid substances include hydrophobic ionic liquid, fluorine-based solvent, and oil.
  • the liquid substance may be composed of only one type of liquid substance, or may be a mixture of two or more types of liquid substances.
  • the liquid substance may contain an additive. In this embodiment, all or a part of the solvent contained in the coating composition may remain and become the liquid substance contained in the coating film.
  • Ionic liquids are also called ionic liquids or room temperature molten salts, and are salts with ionic conductivity and a low melting point. Many ionic liquids have a relatively low melting point, which is achieved by combining an organic onium ion as the cation and an organic or inorganic anion as the anion.
  • the melting point of an ionic liquid is usually 100°C or lower, and preferably room temperature (25°C) or lower.
  • the melting point of an ionic liquid can be measured by a differential scanning calorimeter (DSC) or the like. Any known ionic liquid can be used as the ionic liquid without any restrictions.
  • the thickness of the coating film formed by the coating composition is preferably 10 nm or more, more preferably 50 nm or more, even more preferably 100 nm or more, and particularly preferably 1000 nm or more, from the viewpoint of superior mechanical strength.
  • the thickness can be 10 ⁇ m or less, or 100 ⁇ m or less.
  • the thickness of the coating film formed by the coating composition can be measured by an ellipsometry method or the like.
  • Example 1 (Preparation of Graft Type Polymer Compound (A-1)) A 2.62 M toluene solution of 2-bromoisobutyryloxyethyl methacrylate (BIEM) was subjected to reversible addition-fragmentation chain transfer polymerization in the presence of 30 mM cumyl dithiobenzoate (CTA) and 6 mM azobisisobutyronitrile (AIBN) at 60° C. for 18 hours to obtain a main chain polymer (PolyBIEM) having an atom transfer radical polymerization (ATRP) initiation point.
  • CTA cumyl dithiobenzoate
  • AIBN mM azobisisobutyronitrile
  • the obtained main chain polymer (PolyBIEM) was characterized by GPC, and the number average molecular weight (Mn) in terms of polymethyl methacrylate was 1.6 ⁇ 10 4 , and the molecular weight distribution (dispersity index PDI) was 1.12.
  • the GPC measurement was performed using a Shodex GPC101 (manufactured by Resonac) as a GPC measurement device, Shodex LF-804 (manufactured by Resonac) and Shodex KF-06L (manufactured by Resonac) as columns, and THF as a developing solvent was passed through at a flow rate of 0.8 mL/min.
  • the oven temperature was set to 40° C.
  • the main chain polymer (PolyBIEM) obtained above was subjected to atom transfer radical polymerization (ATRP) using poly(ethylene glycol) methacrylate (PEGMA-OH, number average molecular weight (Mn): 500) and a copper catalyst to obtain a graft type polymer compound (A-1).
  • A-1 atom transfer radical polymerization
  • the ratio of ethyl 2-bromoisobutyrate (EBIB, initiator): main chain polymer (PolyBIEM): poly(ethylene glycol) methacrylate (PEGMA-OH): CuBr: CuBr 2 : 4,4'-dinonyl-2,2'-bipyridine (diN-bip) was 0.1:1:100:0.8:0.2:2 (molar ratio), anisole was used as a solvent in an amount four times the mass of poly(ethylene glycol) methacrylate (PEGMA-OH), and the reaction conditions were 65°C and 0.5 hours.
  • the obtained graft polymer compound (A-1) was characterized by GPC, and the number average molecular weight (Mn) in terms of polymethyl methacrylate was 9.2 ⁇ 10 4 , and the molecular weight distribution (dispersity PDI) was 2.0.
  • the GPC measurement was performed using Shodex GPC101 (manufactured by Resonac) as a GPC measuring device, Shodex LF-804 (manufactured by Resonac) and Shodex KF-06L (manufactured by Resonac) as columns, and DMF/LiCl as a developing solvent was passed at a flow rate of 0.8 mL/min.
  • the oven temperature was set to 40° C.
  • the surface occupancy of the graft chain of the obtained graft polymer compound (A-1) was measured by the above-mentioned method, the surface occupancy was 0.15.
  • the obtained graft type polymer compound (A-1) was purified by dialysis in a methanol solvent as a poor solvent, dried overnight under vacuum at room temperature, and then stored.
  • the molar ratio of ethyl 2-bromoisobutyrate (EBIB, initiator):poly(ethylene glycol)methyl ether methacrylate (PEGMA-OMe):blocked isocyanate group-containing methacrylate (MOI-BP):CuBr:CuBr 2 :4,4'-dinonyl-2,2'-bipyridine (diN-bip) was 1.1:99.75:5.25:0.8:0.2:2, and anisole was used as a solvent in an amount twice the mass of poly(ethylene glycol)methyl ether methacrylate (PEGMA-OMe).
  • Characterization of the obtained crosslinkable polymer compound (B-1) by GPC showed that the number average molecular weight (Mn) in terms of polymethyl methacrylate was 3.2 ⁇ 10 4 and the molecular weight distribution (dispersity PDI) was 1.3.
  • the GPC measurement was performed by using Shodex GPC101 (manufactured by Resonac) as a GPC measurement device, Shodex LF-804 (manufactured by Resonac) and Shodex KF-06L (manufactured by Resonac) as columns, and flowing DMF/LiCl as a developing solvent at a flow rate of 0.8 mL/min.
  • the oven temperature was set to 40° C. at this time.
  • the polymerization conversion rate of each monomer was determined by 1 H-NMR measurement, and it was 88.4% for poly(ethylene glycol) methyl ether methacrylate (PEGMA-OMe) and 91.2% for blocked isocyanate group-containing methacrylate (MOI-BP).
  • a coating composition containing the graft polymer compound (A-1):crosslinkable polymer compound (B-1) in a ratio of 99.9:0.1 (mass ratio) was prepared.
  • the coating composition used propylene glycol monomethyl ether acetate (PGMAc) as a solvent, and dibutyltin dilaurate was used as a catalyst in a ratio of 1 part by mass per 100 parts by mass of the graft polymer compound (A-1) and the crosslinkable polymer compound (B-1).
  • the total content of the graft polymer compound (A-1) and the crosslinkable polymer compound (B-1) in the coating composition was adjusted to be 2% by mass.
  • a silicon substrate Si-wafer
  • 3-(2-aminoethylaminopropyl)trimethoxysilane was reacted on the silicon substrate under basic conditions, thereby introducing residues derived from 3-(2-aminoethylaminopropyl)trimethoxysilane into the silicon substrate.
  • the coating composition obtained above was spin-coated on the silicon substrate with the residues derived from 3-(2-aminoethylaminopropyl)trimethoxysilane introduced thereon using a spin coater, and then heated at 120°C for 1 hour to promote the crosslinking reaction between the graft type polymer compound (A-1) and the crosslinkable polymer compound (B-1), thereby forming a coating film on the silicon substrate.
  • the thickness of the coating film formed was measured at room temperature by a spectroscopic ellipsometric method (MASS-105 manufactured by Five Labs), and was 105 nm. For optical constants, etc., a file prepared using each test specimen prepared according to the manufacturer's specified method was used.
  • Examples 2 to 5 In preparing the coating compositions, the ratio of the graft type polymer compound (A-1) and the crosslinkable polymer compound (B-1) was changed to 99:1 (Example 2), 90:10 (Example 3), 75:25 (Example 4), and 60:40 (Example 5) in terms of the mass ratio of "graft type polymer compound (A-1):crosslinkable polymer compound (B-1)", respectively. Except for this, the coating compositions were prepared in the same manner as in Example 1. Next, using the obtained coating composition, a coating film was formed on a silicon substrate in the same manner as in Example 1, and the mechanical strength was measured in the same manner as in Example 1. The results are shown in Table 1. The thicknesses of the coating films in Examples 2 to 5 were 100 nm (Example 2), 120 nm (Example 3), 105 nm (Example 4), and 107 nm (Example 5), respectively.
  • Example 6 (Preparation of Graft Type Polymer Compound (A-2))
  • a graft type polymer compound (A-2) was prepared in the same manner as the graft type polymer compound (A-1) in Example 1, except that 2-hydroxyethyl methacrylate (MMA-OH, molecular weight 130.14) was used instead of poly(ethylene glycol) methacrylate (PEGMA-OH).
  • the obtained graft type polymer compound (A-2) was characterized by GPC in the same manner as in Example 1, and the number average molecular weight (Mn) in terms of polymethyl methacrylate was 200,000 and the molecular weight distribution (dispersity index PDI) was 2.3.
  • the surface occupancy of the graft chains of the obtained graft type polymer compound (A-2) was measured by the above-mentioned method, and the surface occupancy was 0.20.
  • ATRP atom transfer radical polymerization
  • the crosslinkable polymer compound (B-1) obtained was characterized by GPC, and the number average molecular weight (Mn) calculated as polymethyl methacrylate was 1.6 x 10 4 , and the molecular weight distribution (dispersity PDI) was 1.4.
  • the GPC measurement was performed by using Shodex GPC101 (manufactured by Resonac) as a GPC measurement device, Shodex LF-804 (manufactured by Resonac) and Shodex KF-06L (manufactured by Resonac) as columns, and flowing THF as a developing solvent at a flow rate of 0.8 mL/min.
  • the oven temperature was set to 40° C.
  • the polymerization conversion rate of each monomer was determined by 1 H-NMR measurement, and it was 33.3% for methyl methacrylate (MMA) and 40.0% for blocked isocyanate group-containing methacrylate (MOI-BP).
  • the obtained crosslinkable polymer compound (B-2) was purified by reprecipitation using methanol as a poor solvent, dried overnight under vacuum at room temperature, and then stored.
  • a coating composition was prepared in the same manner as in Example 1, except that the graft type polymer compound (A-2) and the crosslinkable polymer compound (B-2) obtained above were used, and the ratio of the graft type polymer compound (A-2):crosslinkable polymer compound (B-2) was 60:40 (mass ratio).
  • a coating film was formed on a silicon substrate using the obtained coating composition in the same manner as in Example 1, and the mechanical strength was measured in the same manner as in Example 1. The results are shown in Table 1. The thickness of the coating film in Example 6 was 90 nm.
  • MEMP-TFSI N-(2-methoxyethyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide
  • Example 7 (Preparation of Graft Type Polymer Compound (A-3)) Atom transfer radical polymerization (ATRP) was carried out on the main chain polymer (PolyBIEM) obtained in the same manner as in Example 1, using poly(ethylene glycol) methyl ether methacrylate (PEGMA-OMe, number average molecular weight (Mn): 500) and a copper catalyst.
  • PETA-OMe poly(ethylene glycol) methyl ether methacrylate
  • Mn number average molecular weight
  • EBIB ethyl 2-bromoisobutyrate
  • main chain polymer PolyBIEM
  • PEGMA-OMe poly(ethylene glycol) methyl ether methacrylate
  • CuBr CuBr 2 : 4,4'-dinonyl-2,2'-bipyridine (diN-bip)
  • anisole was used as a solvent in an amount twice the mass of poly(ethylene glycol) methyl ether methacrylate (PEGMA-OMe).
  • the obtained graft type polymer compound (A-3) was characterized by GPC, and as a result, the number average molecular weight (Mn) in terms of polymethyl methacrylate was 1.4 ⁇ 10 5 , and the molecular weight distribution (dispersity index PDI) was 1.1.
  • the GPC measurement was performed using Shodex GPC101 (manufactured by Resonac) as a GPC measurement device, Shodex LF-804 (manufactured by Resonac) and Shodex KF-06L (manufactured by Resonac) as columns, and DMF/LiCl as a developing solvent was passed at a flow rate of 0.8 mL/min.
  • the oven temperature was set to 40° C.
  • the surface occupancy of the graft chain of the obtained graft type polymer compound (A-3) was measured by the above-mentioned method, the surface occupancy was 0.30.
  • anisole was used as a solvent in the same amount as poly(ethylene glycol) methyl ether methacrylate (PEGMA-OMe), and polymerization was performed under the conditions of 60 ° C. and 3 hours.
  • the obtained crosslinkable polymer compound (B-3) was characterized by GPC, and the number average molecular weight (Mn) in terms of polymethyl methacrylate was 2,300,000, and the molecular weight distribution (dispersity PDI) was 3.0.
  • the GPC measurement was performed using Shodex GPC101 (manufactured by Resonac) as a GPC measurement device, Shodex LF-804 (manufactured by Resonac) and Shodex KF-06L (manufactured by Resonac) as columns, and DMF/LiCl as a developing solvent was passed at a flow rate of 0.8 mL/min. In this case, the oven temperature was set to 40°C.
  • a coating composition containing the graft polymer compound (A-3):crosslinkable polymer compound (B-3) in a ratio of 92:8 (mass ratio) was prepared.
  • the coating composition used propylene glycol monomethyl ether acetate (PGMAc) as a solvent, and 0.1N diluted hydrochloric acid was used as a catalyst in a ratio of 1 part by mass per 100 parts by mass of the total of the graft polymer compound (A-3) and the crosslinkable polymer compound (B-3).
  • the total content of the graft polymer compound (A-3) and the crosslinkable polymer compound (B-3) in the coating composition was adjusted to 2% by mass.
  • a coating film was formed on a silicon substrate in the same manner as in Example 1, and the mechanical strength was measured in the same manner as in Example 1. The results are shown in Table 1.
  • the thickness of the coating film in Comparative Example 2 was 98 nm.
  • a coating composition was prepared using the graft polymer compound (A-3) obtained in Example 7.
  • the coating composition used propylene glycol monomethyl ether acetate (PGMAc) as a solvent, and 0.1N diluted hydrochloric acid was used as a catalyst in a ratio of 1 part by mass per 100 parts by mass of the graft polymer compound (A-3).
  • the content of the graft polymer compound (A-3) in the coating composition was adjusted to be 2% by mass.
  • a member having a coating film was formed using the obtained coating composition in the same manner as in Example 1, and the icing stress was measured in the same manner as in Example 1. The measurement results are shown in Table 1.
  • the thickness of the coating film in Comparative Example 1 was 100 nm.
  • Example 2 A coating composition was prepared in the same manner as in Example 7, except that tetraethoxysilane was used instead of the crosslinkable polymer compound (B-3). Next, a coating film was formed on a silicon substrate using the obtained coating composition in the same manner as in Example 1, and the mechanical strength was measured in the same manner as in Example 1. The results are shown in Table 1. The thickness of the coating film in Comparative Example 2 was 100 nm.
  • EBIB ethyl 2-bromoisobutyrate
  • main chain polymer PolyBIEM
  • PEGMA-OMe poly(ethylene glycol) methyl ether methacrylate
  • CuBr CuBr 2 : 4,4'-dinonyl-2,2'-bipyridine (diN-bip)
  • anisole was used as a solvent in an amount twice the mass of poly(ethylene glycol) methyl ether methacrylate (PEGMA-OMe), and the reaction conditions were 65°C and 2 hours.
  • the obtained graft type polymer compound (A-4) was characterized by GPC, and the number average molecular weight (Mn) in terms of polymethyl methacrylate was 1.3 ⁇ 10 5 , and the molecular weight distribution (dispersity index PDI) was 1.1.
  • the GPC measurement was performed using Shodex GPC101 (manufactured by Resonac) as a GPC measuring device, Shodex LF-804 (manufactured by Resonac) and Shodex KF-06L (manufactured by Resonac) as columns, and by flowing DMF/LiCl as a developing solvent at a flow rate of 0.8 mL/min.
  • the oven temperature was set to 40° C.
  • the surface occupancy of the graft chain of the obtained graft type polymer compound (A-4) was measured by the above-mentioned method, the surface occupancy was 0.30.
  • a coating composition was prepared using the graft polymer compound (A-4) obtained above.
  • the coating composition used anisole as a solvent, and tetrakis(dimethylamino)ethylene (a catalyst for crosslinking bromine atoms derived from 2-bromoisobutyryloxyethyl methacrylate (BIEM) contained in the graft polymer compound (A-4)) was used as a catalyst in a ratio of 1 part by mass per 100 parts by mass of the graft polymer compound (A-4).
  • the content of the graft polymer compound (A-4) in the coating composition was adjusted to be 2% by mass.
  • Example 3 a coating film was formed on a silicon substrate using the obtained coating composition in the same manner as in Example 1, and mechanical strength was measured in the same manner as in Example 1. The results are shown in Table 1.
  • the thickness of the coating film in Comparative Example 3 was 105 nm.
  • the silicon substrate used was one reacted with 3-(trimethoxysilyl)propyl-2-bromo-2-methylpyropanoate instead of one reacted with 3-(2-aminoethylaminopropyl)trimethoxysilane.
  • Example 4 A coating composition was prepared in the same manner as in Example 1, except that the ratio of the graft type polymer compound (A-1) and the crosslinkable polymer compound (B-1) used was changed to 50:50 in terms of the mass ratio of "graft type polymer compound (A-1):crosslinkable polymer compound (B-1)" when preparing the coating composition. Next, a coating film was formed on a silicon substrate using the obtained coating composition in the same manner as in Example 1, and the mechanical strength was measured in the same manner as in Example 1. The results are shown in Table 1. The thickness of the coating film in Comparative Example 4 was 93 nm.

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  • Life Sciences & Earth Sciences (AREA)
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Abstract

L'invention concerne une composition de revêtement contenant un solvant et un polymère, le polymère contenant un composé polymère de type greffé (A) qui comprend un motif constitutif représenté par la formule générale (1) et présente un groupe fonctionnel réticulable (a), et un composé polymère réticulable (B) présentant au moins deux groupes fonctionnels réactifs (b) qui subissent une réaction de réticulation avec le groupe fonctionnel réticulable (a), et le rapport de teneur du composé polymère réticulable (B) dans un total de 100 % en masse du composé polymère de type greffé (A) et du composé polymère réticulable (B) est compris entre 0,1 % en masse et 50% en masse.
PCT/JP2024/034277 2023-09-25 2024-09-25 Composition de revêtement Pending WO2025070541A1 (fr)

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JP2023-161622 2023-09-25

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6189216A (ja) * 1984-09-27 1986-05-07 アトケム 射出成形物、ガラス繊維心材又は金属被覆物用ポリマーの製造方法
JPH05239398A (ja) * 1992-02-27 1993-09-17 Mitsui Petrochem Ind Ltd 塗料用樹脂組成物
JPH05331413A (ja) * 1992-05-28 1993-12-14 Kansai Paint Co Ltd 塗料用樹脂組成物
JPH10114849A (ja) * 1996-07-15 1998-05-06 Bayer Ag グラフト化されたポリアクリレートポリオールを含有する高固形分のポリウレタン結合剤組成物
JPH10338723A (ja) * 1997-06-09 1998-12-22 Mitsubishi Rayon Co Ltd 多層構造アクリル重合体、およびそれを用いたメタクリル樹脂組成物
JP2014513174A (ja) * 2011-04-12 2014-05-29 クイーンズ ユニバーシティ アット キングストン 両疎媒性ブロックコポリマーおよびその用途
JP2019525985A (ja) * 2016-07-27 2019-09-12 クラリアント・プラスティクス・アンド・コーティングス・リミテッド 新規ポリアクリレート−ポリシランブロックコポリマー

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6189216A (ja) * 1984-09-27 1986-05-07 アトケム 射出成形物、ガラス繊維心材又は金属被覆物用ポリマーの製造方法
JPH05239398A (ja) * 1992-02-27 1993-09-17 Mitsui Petrochem Ind Ltd 塗料用樹脂組成物
JPH05331413A (ja) * 1992-05-28 1993-12-14 Kansai Paint Co Ltd 塗料用樹脂組成物
JPH10114849A (ja) * 1996-07-15 1998-05-06 Bayer Ag グラフト化されたポリアクリレートポリオールを含有する高固形分のポリウレタン結合剤組成物
JPH10338723A (ja) * 1997-06-09 1998-12-22 Mitsubishi Rayon Co Ltd 多層構造アクリル重合体、およびそれを用いたメタクリル樹脂組成物
JP2014513174A (ja) * 2011-04-12 2014-05-29 クイーンズ ユニバーシティ アット キングストン 両疎媒性ブロックコポリマーおよびその用途
JP2019525985A (ja) * 2016-07-27 2019-09-12 クラリアント・プラスティクス・アンド・コーティングス・リミテッド 新規ポリアクリレート−ポリシランブロックコポリマー

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