WO2012091178A1 - Additif pour agent de revêtement et agent de revêtement le contenant - Google Patents

Additif pour agent de revêtement et agent de revêtement le contenant Download PDF

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Publication number
WO2012091178A1
WO2012091178A1 PCT/JP2011/080604 JP2011080604W WO2012091178A1 WO 2012091178 A1 WO2012091178 A1 WO 2012091178A1 JP 2011080604 W JP2011080604 W JP 2011080604W WO 2012091178 A1 WO2012091178 A1 WO 2012091178A1
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group
coating agent
additive
copolymer
groups
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PCT/JP2011/080604
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English (en)
Inventor
Akito Hayashi
Tomohiro Iimura
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Dow Corning Toray Co., Ltd.
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Publication of WO2012091178A1 publication Critical patent/WO2012091178A1/fr

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    • 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
    • C09D183/10—Block or graft copolymers containing polysiloxane sequences

Definitions

  • the present invention relates to an additive for a coating agent (also referred to hereafter as a coating agent additive) wherein the additive exhibits an excellent compatibil ity with resins— and particularly with acryl ic resins that are cured by an isocyanate-based curing agent— and, even when added in a very small amount, imparts an excel lent uniformity, transparency, solvent resistance, staining/soiling resistance, and water repellency to the cured coating layer.
  • the invention of the present application further relates to a coating agent that contains this coating agent additive.
  • Silicone-modified vinyl resins comprising a vinyl polymer having a straight chain polyorganosiloxane group in side chain position are known. These resins are obtained by the copolymerization of a vinylic compound with a straight chain
  • Patent Document 1 polyorganosiloxane having a polymerizable group at one terminal. Due to the effect of the polyorganosiloxane group in side chain position, these silicone- modified vinyl resins exhibit an excellent staining/soiling resistance and water repellency and are incorporated in diverse coating agents in order to impart these functionalities.
  • the post-polymerization resin solution is transparent, but because organosiloxane exhibits a low compatibility with various materials, the problem has arisen of poor incorporation into cured systems, and a coating agent that uses such a silicone-modified vinyl resin provides, after application, a film with an unsatisfactory staining/soiling resistance and an unsatisfactory water repellency.
  • Patent Documents 2 to 6 examine the use of vinyl polymers containing a carbosiloxane dendrimer structure as additives in coating agents, but in these instances integration into a desired cured system cannot be achieved due to the absence of functional groups and the solvent resistance has been low as a result.
  • Patent Document 1 JP 61 -078806 A
  • Patent Document 4 JP 2001 - 192424 A
  • An object of the present invention is to provide a coating agent additive that exhibits an excellent compatibility with various types of curable resin solutions and that provides the cured coating layer with an excellent uniformity, transparency, solvent resistance, staining/soi l ing resistance, and water repel lency.
  • a further object of the present invention is to provide a coating agent.
  • the present inventors achieved the present invention as a result of intensive investigations in order to solve the problems identified above.
  • the problems identified for the present invention are solved by a coating agent additive that contains a copolymer (A) that has in the molecule a hydroxyl group and a special carbosi loxane dendrimer structure and are solved by a coating agent that contains this additive.
  • This copolymer (A) can be obtained by a copolymerization reaction among an unsaturated monomer containing a carbosi loxane dendrimer structure, a hydroxyl group-containing unsaturated monomer, and optionally an unsaturated monomer that does not contain the hydroxyl group.
  • This copolymer (A) molecule has a hydroxyl group, which is reactive with curable resins, and also has a carbosiloxane dendrimer structure that exhibits an excellent compatibility with curable resin solutions. Due to this, the use of this copolymer (A) as a coating agent additive not only makes possible the efficient introduction into a cured resin system, but even at very small amounts of addition can impart a satisfactory compatibility, solvent resistance, staining/soiling resistance, and water resistance, which originate with the carbosiloxane dendrimer structure, to the cured coating layer.
  • An additive for a coating agent wherein the additive comprises (A) a copolymer that contains in the molecule a hydroxyl group and a group having a carbosiloxane dendrimer structure given by the fol lowing formula ( 1 )
  • Z is a divalent organic group
  • p 0 or 1
  • R and R are each independently a C i _ i o alkyl group, an aryl group, or an aralkyi group, and
  • R and R are defined as above,
  • i is an integer from 1 to 10 that indicates the total number of generations of the silylalkyl group
  • Y is a group that contains radically polymerizable unsaturation
  • Z, p, R , R , L , and a are as defined above.
  • R is the hydrogen atom or a methyl group and R 5 is a Cj_io alkylene group
  • R and R are defined as above,
  • alkenylaryl group-containing organic groups given by the following general formula
  • R is the hydrogen atom or a methyl group
  • R is a Cj.io alkyl group, R is a C 1 _ 10 alkylene group,
  • b is an integer from 0 to 4, and
  • c is 0 or 1 , and C2- 1 0 alkenyl groups.
  • copolymer (A) is a copolymer provided by the copolymerization additionally of at least one or more (a3) unsaturated monomer that does not contain the hydroxyl group in the molecule.
  • the additive for a coating agent according to any one of [ 1 ] to [5], wherein the unsaturated monomer (a l ) constituting the copolymer (A) is at least one unsaturated monomer containing the hydroxyl group and selected from the group consisting of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate.
  • a coating agent comprising the additive for a coating agent according to any one of [ 1 ] to [6], an acrylic resin wherein this acrylic resin does not contain a carbosiloxane dendrimer structure in its side chains, and a curing agent.
  • a coating agent comprising an additive for a coating agent according to any one of [ 1 ] to [6], an acrylic resin wherein this acryl ic resin does not contain a carbosiloxane dendrimer structure in its side chains, and a curing agent comprising an isocyanate group-containing compound, wherein the molar equivalent for the NCO group in the isocyanate compound, expressed per 1 equivalent of hydroxyl groups in the coating agent, is in the range from 0. 1 to 2.O.” .
  • the present invention provides a coating agent additive that exhibits an excellent compatibility with various types of curable resin solutions and that provides the cured coating layer with an excellent uniformity, transparency, solvent resistance, staining/soiling resistance, and water repellency.
  • the present invention also provides a coating agent.
  • the coating agent additive according to the product of the present invention characteristically contains a copolymer (A) that contains in the molecule a hydroxyl group and a specific carbosiloxane dendrimer structure.
  • This copolymer (A) is a copolymer obtained by the copolymerization of an unsaturated monomer having the hydroxyl group in the molecule and an unsaturated monomer having the carbosiloxane dendrimer structure in the molecule, and vinyl polymers are a favorable example of the copolymer (A).
  • a first characteristic feature of the copolymer (A) according to the product of the present invention is that it contains a group that has a carbosiloxane dendrimer structure.
  • This carbosiloxane dendrimer structure denotes a high molecular weight group that is highly regularly branched in a radiating manner from a single core or nucleus.
  • a highly branched siloxane ⁇ silalkylene copolymer is an example of a carbosiloxane dendrimer having such a structure; refer in this regard to JP 1 1 -001 530 A.
  • the carbosiloxane dendrimer structure in the vinyl polymer in the present invention is a group given by the following formula ( 1 ).
  • Z in formula ( 1 ) is a divalent organic group, and the number of repeat units p thereof is 0 or 1 .
  • the divalent organic group Z is not particularly limited, but can be exemplified by alkylene groups, arylene groups, aralkylene groups, ester-containing divalent organic groups, ether-containing divalent organic groups, ketone-containing divalent organic groups, and amide group-containing divalent organic groups.
  • Organic groups preferred among the preceding are given by the following formulas.
  • R in the preceding formulas is a CJ.JO alkylene group, for example, methylene, ethylene, propylene, and butylene. Methylene and propylene are preferred among the preceding.
  • R 10 is a C ⁇ . ⁇ Q alkyl group, for example, methyl, ethyl, propyl, and butyl.
  • R 11 is a Cj.io alkylene group, for example, an alkylene group such as methylene, ethylene, propylene, and butylene.
  • Ethylene is preferred among the preceding, d is an integer from 0 to 4, and e is 0 or 1.
  • R and R are independently a CJ.JO alkyl group, an aryl group, or an aralkyl group, for example, a C1.30 straight-chain or branched-chain alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and so forth; a C3.10 cyclic alkyl group such as cyclopentyl, cyclohexyl, and so forth; a Cg.jo aryl group such as phenyl, tolyl, xylyl, and so forth; a C7.10 aralkyl group such as benzyl; and groups provided by at least partially replacing the carbon-bonded hydrogen in the preceding groups with a halogen atom, e.g., fluorine, or with an organic group that contains, e.g., a carbinol group, epoxy group, glycidyl group,
  • the alkyl group, aryl group, or aralkyl group is preferably an unsubstituted C 1 _ 10 alkyl group, aryl group, or aralkyl group; is more preferably an unsubstituted C j _6 alkyl group or aryl group; and particularly preferably is methyl, ethyl, or phenyl.
  • Z and p in the formula are defined as above, and R and R are defined as above, i in the preceding formula is an integer from 1 to 10 that indicates the total number of
  • silylalkyl group is preferably from 1 to 5 from the perspective of synthesis and more preferably is from 1 to 3.
  • i is preferably at least 2 from the standpoint of properties such as the hardness, solvent resistance,
  • the aforementioned carbosiloxane dendrimer structure is a chemical structure that is highly branched in a radiative configuration from a single silicon atom, and i, which indicates the total number of generations for this silylalkyl group, indicates the degree of branching. For example, when the total number of generations i is 1 and L' is, for example, the methyl group, the aforementioned carbosiloxane dendrimer structure denotes the following structure
  • Z, p, R , and R are defined as above and a is an integer from 0 to 3.
  • the carbosiloxane dendrimer structure indicated by the following structure is called a "second generation type", and the copolymer (A) according to the present invention particularly preferably has a group that has this carbosiloxane dendrimer structure
  • the carbosiloxane dendrimer structure indicated by the following structure is called a "third generation type", and the copolymer (A) according to the present invention particularly preferably has a group that has this carbosiloxane dendrimer structure
  • Z, R , and R are defined as above and a , a , and a are integers from 0 to 3.
  • the carbosiloxane dendrimer structure given by formula (2-5) is particularly preferred from the standpoint of the properties of the coating layer, e.g., the hardness, solvent resistance, staining/soiling resistance, water repellency, and so forth.
  • a group having the carbosiloxane dendrimer structure described above is a functional group that, in comparison to a chain-form polysi loxane unit or a simple branched polysiloxane unit, exhibits a better compatibility with curable resins, can impart a higher water repellency (water resistance) to a coating layer, and can prevent the surface of the coating film from becoming extremely smooth.
  • a group having the previously described carbosi loxane dendrim er structure is chemically stable and as a consequence can be used in combination with a wide range of coating agents.
  • a group having the carbosiloxane dendrimer structure described above can be introduced into the copolymer by the copolymerization with the other unsaturated monomer of (a2) a radically copolymerizable unsaturated monomer given by the following formula ( ) [0038]
  • Y is a group containing radical ly polymerizable unsaturation and Z, p, R , R , L 1 , and a' are defined as above.
  • the unsaturation-containing group has a radically polymerizable unsaturated bond but is not otherwise particularly limited, and can be exemplified by the vinyl grou allyl group, (meth)acryl group, and so forth.
  • Y in formula ( ) preferably has a group selected from the group consisting of acryl ic group-containing organic groups and methacrylic group-containing organic groups given by the fol lowing general formulas
  • R is the hydrogen atom or a methyl group
  • alkenylaryl group-containing organic groups given by the following general formula
  • R 6 is the hydrogen atom or a methyl group
  • R is a Ci_io alkyl group
  • R is a Ci_io alkylene group
  • b is an integer from 0 to 4, and
  • c is 0 or 1
  • This component (a2) can be exemplified by the following formulas.
  • carbosiioxane dendrimer structure-containing unsaturated monomers can be produced, for example, according to the method for producing branched siloxane ⁇ silalkylene copolymers described in JP 1 1 -001 530 A (Japanese Patent Application 09- 1 71 1 54).
  • a second characteristic feature of the copolymer (A) according to the product of the present invention is that it has, in addition to the carbosiioxane dendrimer structure, the hydroxyl group in its molecu le.
  • the hydroxyl group (-OH) is a component that is reactive with resins and particularly with acryl ic resins that are cured by an isocyanate- type curing agent, and, when the curable resin undergoes curing mainly by a
  • the copolymer (A) is then efficiently incorporated into the cured resin system.
  • the copolymer (A) according to the product of the present invention exhibits an improved affinity for curable resins, and the compatibility during curing and the transparency (uniformity) of the coating layer are improved.
  • Th is hydroxyl group (-OH) may be directly bonded to the main chain of the copolymer (A) or may be bonded to the main chain of the copolymer (A) across a divalent organic group (Z) as -Z-OH.
  • This Z can be exemplified by the same divalent organic groups as already described above.
  • This hydroxyl group is introduced into the copolymer by the copolymerization with the other unsaturated monomer of (a l ) an unsaturated monomer that contains at least one hydroxyl group in the molecule.
  • This component (a l ) can be exemplified by vinyl monomers that have the hydroxyl group in the molecule, for example, acrylate esters that have the hydroxyl group in the molecule, methacrylate esters that have the hydroxyl group in the molecule, allyl compounds that have the hydroxyl group in the molecule, vinyl ether compounds that have the hydroxyl group in the molecule, unsaturated carboxamide compounds that have the hydroxyl group in the molecule, unsaturated fatty acids that have the hydroxyl group in the molecule, unsaturated fatty acid esters that have the hydroxyl group in the molecule, and monomers obtained by addition reacting various hydroxyl group-containing monomers with an ⁇ -caprolactone adduct.
  • Component (a l ) can be specifical ly exemplified by the following:
  • (meth)acrylate esters such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl
  • (meth)acrylate 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4- hydroxybutyl (meth)acrylate, methyl 2-(hydroxymethyl)acrylate, ethyl 2- (hydroxymethyl)acrylate, butyl 2-(hydroxymethyl)acrylate, (4- hydroxymethylcyclohexyl)methyl (meth)acrylate, glycerol mono(meth)acrylate, 2- (meth)acryloyloxyethyl 2-hydroxypropyl phthalate, 2-hydroxy-3-phenoxypropyl
  • (meth)acrylate, and so forth allyl compounds such as allyl alcohol, 2-hydroxyethyl allyl ether, and so forth; vinyl ether compounds such as 2-hydroxyethyl vinyl ether, 4- hydroxybutyl vinyl ether, 6-hydroxyhexyl vinyl ether, and so forth; unsaturated carboxamide compounds such as N-methylol(meth)acrylamide, N-methylolcrotonamide, and so forth; hydroxyl group-containing unsaturated fatty acids such as ricinoleic acid and so forth; hydroxyl group-containing unsaturated fatty acid esters such as alkyl ricinoleate and so forth; and monomers obtained by addition reacting these hydroxyl group-containing monomers with an ⁇ -caprolactone adduct.
  • allyl compounds such as allyl alcohol, 2-hydroxyethyl allyl ether, and so forth
  • vinyl ether compounds such as 2-hydroxyethyl vinyl ether, 4- hydroxybutyl vinyl ether, 6-
  • component (a l ) are acrylate esters and methacrylate esters, in each case having a hydroxyalkyl group in the molecule, and these can be more specifically exemplified by hydroxyl group-containing vinyl monomers such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate.
  • the copolymer (A) according to the product of the present invention contains the hydroxyl group and the previously described carbosiloxane dendrimer structure in its molecule and is obtained by the copolymerizati on of the previously described components (a l ) and (a2), but may also optionally be a copolymer obtained using (a3) an unsaturated monomer that does not contain the hydroxyl group in the molecule.
  • the component (a3) unsaturated monomer favorably forms a portion of the main chain of the copolymer (A) and is advantageously used as desired as a means for introducing different types of functional groups into the copolymer (A) according to the product of the present invention.
  • the co-use of these monomers makes it possible to obtain the copolymer in an economically advantageous manner while imparting desired properties, such as blocking resistance or a leveling property, to the coating layer. It may also be possible to obtain additional improvements in properties such as the solubil ity through the selection of a unsaturated monomer.
  • the component (a3) unsaturated monomer can be favorably exempl ified by vinyl monomers that do not have a hydroxyl group.
  • Specific examples are as follows: lower alkyl acrylates and lower alkyl methacrylates such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, and isopropyl methacrylate; glycidyl acrylate and glycidyl methacrylate; lower acrylates and methacrylates that have a C i _6 lower alkyl group, such as n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert- butyl acrylate, tert-butyl methacrylate, n-hexyl
  • cyclohexyl acrylate, and cyclohexyl methacrylate higher acrylates and methacrylates such as 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl acrylate, octyl
  • vinyl esters of lower fatty acids such as vinyl acetate and vinyl propionate
  • esters of h igher fatty acids such as vinyl butyrate, vinyl caproate, vinyl 2- ethylhexanoate, vinyl laurate, and vinyl stearate
  • aromatic vinyl monomers such as styrene, vinyltoluene, benzyl acrylate, benzyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, and vinylpyrrolidone
  • amino group-containing vinyl monomers such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, and diethylaminoethyl methacrylate
  • amide group-containing vinyl monomers such as acrylamide, methacrylamide, N-methylolacrylamide, N- methylolmethacrylamide, N-methylolacrylamide
  • Component (a3) may also be an unsaturated monomer that has a silicon-bonded alkoxy group, and specific examples in this regard are
  • vinyltriethoxysi lane vinyltrimethoxysilane, and vinyltris(2-methoxyethoxy)si lane.
  • Multifunctional vinyl monomers may also be used as component (a3), for example, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1 ,4-butanediol diacrylate, 1 ,4- butanediol dimethacrylate, 1 ,6-hexanediol diacrylate, 1 ,6-hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trioxyethylacrylate, trimethylolpropane trioxyethylmethacrylate, and unsaturated group- containing silicone compounds such as a polydimethylsiloxane endblocked by an alkenylaryl group at both molecular chain terminals.
  • unsaturated group- containing silicone compounds such as a polydimethyl
  • a vinyl monomer containing a fluorinated organic group may also be used as component (a3).
  • CH2 CCH 3 COO-CH2(CF 2 )8F
  • CH 2 CCH 3 COO-CH 2 CH 2 CF 3
  • CH 2 CCH 3 COO- CH 2 CH2(CF 2 ) 2 F
  • CH2 CCH 3 COO-CH 2 CH2(CF 2 ) 3 F
  • CH 2 CCH 3 COO- CH 2 CH 2 (CF 2 )4F
  • CH2 CCH 3 COO-CH 2 CH2(CF2)6F
  • CH 2 CCH 3 COO- CH 2 CH 2 (CF 2 ) 8 F
  • CH 2 CCH 3 COO-CH 2 CH 2 (CF2) i oF
  • CH 2 CCH 3 COO- CH 2 CH 2 (CF 2 ) i 2F
  • CH 2 CCH 3 COO-CH2CH2(CF2) i 4F
  • CH 2 CCH 3 COO- CH 2 CH 2 (CF 2 ) i 6F
  • CH 2 CCH 3 COO-CH2CH2CH 2 CF3
  • CH 2 CCH 3 COO
  • CH2 CCH 3 COO-CH 2 CH2(CF2)6F
  • CH2 CCH 3 COO-CH2CH 2 (CF2)8F
  • CH 2 CHCOO-
  • CH 2 CF 3 and CH2 CCH 3 COO-CH 2 CF3.
  • the copolymer (A) offers the advantage of being able to provide a cured coating layer with a better uniformity, transparency, solvent resistance, staining/soiling resistance, and water repellency than does a copolymer lacking the hydroxyl group and the carbosiloxane dendrimer structure.
  • Radical polymerization methods and ionic polymerization methods can be used for the copolymerization method, but radical polymerization methods are preferred therebetween and the use of solution polymerization methods is particularly favorable.
  • This solution polymerization is carried out by reacting the previously described unsaturated monomers in a solvent for 3 to 20 hours at a temperature of 50 to 1 50°C in the presence of a radical initiator.
  • the solvent used here can be exemplified by aliphatic hydrocarbons such as hexane, octane, decane, cyclohexane, and so forth; aromatic hydrocarbons such as benzene, toluene, xylene, and so forth; ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, dioxane, and so forth; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and so forth ; esters such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, and so forth; alcohols such as methanol, ethanol , isopropyl alcohol, butanol, and so forth; and organosiloxane oligomers such as octamethylcyclotetrasi lox
  • the heretofore known compounds typically used in radical polymerization methods can be used as the radical initiator, and specific examples are azobis compounds such as 2,2'- azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitri le), 2,2'-azobis(2,4- dimethylvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), and so forth, and organic peroxides such as benzoyl peroxide, lauroyl peroxide, tert-butylperoxy benzoate, tert-butylperoxy 2-ethylhexanoate, and so forth.
  • a single radical initiator may be used by itself, or two or more may be used in combination.
  • the amount of radical initiator used is preferably in the range from 0. 1 to 5 mass parts per 1 00 mass parts for the total of components (a l ) to (a3).
  • a chain transfer agent may also be added to the polymerization.
  • This chain transfer agent can be specifically exemplified by mercapto compounds such as 2-mercaptoethanol, butyl mercaptan, n-dodecyl mercaptan, 3- mercaptopropyltrimethoxysilane, a polydimethylsiloxane that has the mercaptopropyl group, and so forth, and by halides such as methylene chloride, chloroform, carbon tetrachloride, butyl bromide, 3-chloropropyltrimethoxysi lane, and so forth .
  • purification can be carried out by a method in which the unreacted residual vinyl monomer is removed by treatment under reduced pressure with heating, or by a method in which a deodorization treatment is carried out by running a hydrogenation reaction in the presence of a hydrogenation catalyst in the presence or absence of a solvent and the light components are distilled off under reduced pressure while in contact with nitrogen gas.
  • a purified product is particularly preferably used in the case of use in topical applications where low odor and compatibility with other cosmetic components are required.
  • the solvents, reaction conditions, low pressure conditions, and so forth that are used in the purification of known organopolysiloxane copolymers can be used and selected without particular limitation in and for the hydrogenation reaction and stripping step under consideration.
  • the number-average molecular weight of the copolymer (A) used in the present invention is preferably from 3,000 to 2,000,000 and more preferably is from 5,000 to 800,000. Its state can be exemplified by liquid, gum, paste, bulk solid, and powder, and it is preferably a dispersion or solution provided by dilution with a solvent.
  • the coating agent additive according to the present invention can be any coating agent additive according to the present invention.
  • the main component of the coating agent is composed of a curing agent and an organic resin that can be used in a paint or coating agent and that can be cured by heating or can be cured at room temperature, while a curing catalyst may be added as necessary.
  • the organic resin can be exemplified by organic resins that do not correspond to the copolymer (A) used in the present invention and that are selected from alkyd resins, acrylic resins, polyester resins, polyurethane resins, and their mixtures.
  • the coating agent additive according to the present invention provides a particularly substantial improvement in compatibility and a particularly substantial improvement in the uniformity, transparency, solvent resistance, staining/soiling resistance, and water repellency of the cured coating layer.
  • the acryl ic resin that is the base of the coating agent is an acrylic resin that does not correspond to the copolymer (A) used in the present invention and that does not contain a carbosiloxane dendrimer structure in side chain position.
  • the coating agent according to the present invention favorably contains an acrylic resin, a curing agent, and the previously described coating agent additive containing the copolymer (A), and may also incorporate a curing catalyst on an optional basis. Two or more components may be used in combination for the copolymer (A), for the acrylic resin, and for the curing agent.
  • a favorable acrylic resin is obtained by the polymerization, among the unsaturated monomers described above, of primarily an acrylate ester or acrylate ester monomer and favorably contains at least two hydroxyl groups in each molecule.
  • Such an acrylic resin can be obtained by the polymerization, among the unsaturated monomers described above, of an acrylate ester or acrylate ester monomer and an unsaturated monomer that has the hydroxyl group in the molecule, for example, an acrylate ester that has the hydroxyl group in the molecule or a methacrylate ester that has the hydroxyl group in the molecule.
  • hydroxyl-functional acrylic resins are known as "acryl ic polyol resins" and are commercially available as, for example, “Burnock” (trademark) and “Acrydic” (trademark) from Dainippon Ink and Chemicals, Incorporated. A single species of such an acrylic resin may be used by itself or two or more species may also be used in combination.
  • the curing agent can be exempl ified by isocyanate compounds and melamine compounds.
  • the isocyanate compounds can be specifically exemplified by
  • polyisocyanate compounds e.g., aliphatic types such as xylene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate and their polyhydric alcohol adducts, biuret types, and trimer types, and aromatic types such as tolylene diisocyanate and diphenylmethane diisocyanate, and can be further exemplified by blocked isocyanate compounds.
  • isocyanate compound products can be exempl ified by "Burnock” (trademark) from Dainippon Ink and Chemicals, Incorporated, “Sumidur” (trademark) from Sumitomo Bayer Urethane, Ltd., "Takenate” (trademark) from Takeda Chemical Industries, Ltd., “Coronate” (trademark) from Nippon Polyurethane Industry Co., Ltd., and “Duranate” (trademark) from Asahi Kasei Chemicals.
  • a single species of isocyanate compound may be used by itself, or two or more species may also be used in combination.
  • the melamine compound can be specifical ly exempl ified by
  • melamine compound pentamethylolmelamine, hexamethylolmelamine, isobutyl ether-type melamine, n-butyl ether-type melamine, and so forth.
  • a single species of these melamine compounds can be used by itself or two or more species can be used in combination .
  • the amount of use of the melamine compound is preferably from 1 to 30 mass parts per 100 mass parts of the resin component in the coating agent.
  • the coating agent of the present invention particularly preferably contains an isocyanate group-containing compound as the aforementioned curing agent.
  • the reason for this is as follows : the copolymer (A), because it contains the hydroxyl group, exhibits an excellent reactivity with the isocyanate group and through its reaction with the curing agent is then efficiently incorporated into the cured coating agent system .
  • the isocyanate compounds described above are favorable curing agents.
  • the amount of use of the curing agent in the coating agent of the present invention can be selected as desired.
  • the molar equivalent for the isocyanate (-NCO) group in the isocyanate compound is preferably in the range from 0. 1 to 2.0 per 1 equivalent of the hydroxyl group (-OH) in the coating agent.
  • the hydroxyl group in the coating agent is primarily the sum of the hydroxyl groups present in the hydroxyl-functional acrylic resin and the hydroxyl groups present in copolymer (A), i.e., the coating agent additive according to the present invention.
  • the range of 1 /0.7 to 1 .2 for the equivalent ratio is more preferred .
  • the acryl ic resin-containing coating agent can undergo a stable cure without foaming or the generation of cure defects.
  • the isocyanate group is used at less than 0. 1 mole per 1 mole hydroxyl group, the cured coating layer may not exhibit a satisfactory staining/soiling resistance, water repellency, and non-stickiness.
  • the cured coating layer may have a poor workability when the isocyanate group is used at more than 2 moles per 1 mole hydroxyl group.
  • the respective amounts of use can be calculated by the usual methods from the hydroxyl value of the copolymer (A), the hydroxyl value of the acrylic resin, and the isocyanate group content of the isocyanate compound.
  • a curing catalyst may be incorporated on an optional basis, and the curing catalyst can be exemplified by organometal compounds, amine compounds, and acidic compounds.
  • the organometal compounds can be specifically exemplified by organotin compounds such as tin octylate, di-n-butyltin dioctate, di-n-butyltin dilaurate, di-n- octyltin bis(isooctyl thioglycolate), di-n-butyltin sulfide, and di-n-octyltin oxide;
  • organotitanium compounds such as tetraisopropoxytitanium, tetra-n-butoxytitanium, isopropyl triisostearoyltitanate, and isopropyl tris(dioctyl pyrophospate)titanate;
  • organoaluminum compounds such as aluminum isopropylate and aluminum
  • the amine compounds can be exemplified by triethylamine, ethylenediamine, diethylenetriamine, dimethylaminoethanol, and isophoronediamine.
  • the acidic compounds can be
  • curing catalysts exemplified by para-toluenesulfonic acid, dodecylbenzenesulfonic acid, phthalic acid, phthalic anhydride, phosphoric acid, monoalkyl phosphates, dialkyl phosphates, and organic amine blocked compounds of the preceding.
  • a single one or two or more of these curing catalysts may be used on an optional basis.
  • the amount of use for the curing catalyst is preferably from 0.001 to 5 mass parts per 100 mass parts of the resin component of the coating agent.
  • Additives can be exemplified by dehydrating agents, pigments, dispersing agents, defoamants, thickeners, settling inhibitors, sagging inhibitors, leveling agents, matting agents, anti-scratching agents, ultraviolet absorbers, photostabilizers, oxidation inhibitors, antimicrobials, and so forth; one or more of these can be used.
  • the dehydrating agent can be exemplified by dimethoxymethane, 1 , 1 - dimethoxyethane, 1 , 1 -dimethoxypropane, 1 , 1 -dimethoxybutane, and 1 , 1 - dimethoxycyclohexane and by hydrolyzable esters such as ethyl orthoformate, methyl orthoacetate, ethyl orthoacetate, dimethyldimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ - methacryloxypropyltrimethoxysilane, ⁇ -aminopropyltrimethoxysilane, ⁇ - aminopropyltriethoxysi lane, methyl silicate, ethyl si licate, and so forth.
  • hydrolyzable esters such as ethyl
  • the moisture fraction in the system can be removed by the addition of this dehydrating agent, which can bring about even further improvement in the storage stabil ity.
  • the amount of use of the dehydrating agent is preferably from 0. 1 to 50 mass parts per 100 mass parts of the resin component in the coating agent.
  • the quantity of use of the other additives is not particularly limited, and these additives can be added and used in the quantities of use known for the usual additives for curable resin coating agents in conformity with the particular application.
  • the usual coating methods known for curable resin coating agents can be selected without particular lim itation, in accordance with the shape of the substrate and the purpose of the coating, for the method of applying the coating agent of the present invention to a substrate.
  • any of the following may be used: bar coating methods, roll coating methods, blade coating methods, gravure coating methods, bead coating methods, curtain flow coating methods, immersion coating methods, and spray coating methods.
  • Coating can be carried out on only one side or on both sides of a substrate and can be carried out on a portion of a substrate or over the entire substrate.
  • curing can be performed at any temperature from ambient temperature to 300°C; however, drying is preferably performed for 5 seconds to 60 minutes by heating at a temperature of 60 to 250°C in order to promote solvent evaporation and accelerate the crosslinking reaction. Higher curing temperatures provide shorter curing times, and the curing time can be further shortened by the co-use of a curing catalyst.
  • the coating can also be aged or matured for 1 to 7 days at a temperature of 30 to 120°C.
  • the thickness of the coating film provided by application of the coating agent of the present invention can be selected without particular limitation in accordance with the shape of the substrate and the purpose of the coating, but is typically in the range from 0. 1 to 100 ⁇ and preferably is 0.5 to 50 ⁇ .
  • Materials that may be coated with the coating agent of the present invention can be exemplified by metals, inorganic materials, plastics, and composite materials.
  • the metals can be exemplified by stainless steel, aluminum, tin plate, galvanized plate, mild steel sheet and plate, copper, brass, various types of plated steel sheet and plate, titanium, and so forth.
  • the coating agent of the present invention can also be advantageously used on metal substrates that have been subjected to a surface treatment such as a conversion treatment or an alumite treatment.
  • the inorganic material can be exemplified by glass, mortar, slate, concrete, roof tile, and so forth.
  • the plastics can be exempl ified by moldings of, e.g., surface-treated polypropylene, polyethylene, acrylic, polycarbonate, polystyrene, polyethylene terephthalate, nylon, polyester, rubber, elastomers, and so forth and by products provided by processing the preceding into a film .
  • the composite materials can be exemplified by fiber-reinforced thermosetting plastics (FRP), fiber- reinforced thermoplastic plastics (FRTP), laminates, sandwich materials provided by the press bonding of a metal with an organic material, and plastics bearing a vapor-deposited metal film.
  • the coating layer provided by the cure of the coating agent of the present invention exhibits an excellent uniformity, transparency, solvent resistance,
  • staining/soiling resistance, and water repellency is therefore effective, for example, for blocking greasy contaminants, dust and dirt borne in the air, and the contaminants admixed in exhaust gas and rainwater; for blocking various types of il licit materials such as graffiti, posters, bills, and stickers; and for preventing snow accretion, icing, and the attachment of aquatic microorganisms.
  • Specific applications can be exemplified by blocking greasy contaminants, such as around kitchen stoves, on the doors of storage cabinets, at exhaust fans, on lighting covers, and so forth; preventing the soi ling of exterior walls, such as concrete and tile; preventing staining due to exhaust gases, e.g., of roadway tunnels and freeway sound-deadening wal ls; preventing the attachment of graffiti, posters, bi l ls, and stickers to exterior wal ls, public phone booths, utility poles, public toilets, and so forth; preventing snow accretion and icing on roofs and power lines; and preventing the attachment of barnacles that attach to the hulls of ships and vessels.
  • the present invention is specifical ly described by the practical examples and comparative examples given below, but the present invention is not limited to the following examples.
  • the viscosity is the value measured at 25 °C.
  • the properties of the copolymer (A) were measured using the following methods.
  • the kinematic viscosity of the copolymer was measured by a capi llary viscosity measurement procedure using a Ubbelohde vi scometer.
  • the molecular weight and dispersity of the copolymer were measured by gel permeation chromatography (GPC).
  • the molecular weight obtained for the copolymer is reported as the number-average molecular weight as polystyrene.
  • a reaction was run for 6 hours at 70°C to obtain a coating agent additive containing a sil icone-modified vinyl copolymer (A l ) with a number-average molecular weight as polystyrene of 8,200, a dispersity of
  • NCO/OH molar ratio 1 .5 was obtained by mixing the following by stirring: 16. 1 g, i .e., the amount that provided 1 mol% with reference to the total polyol, of the coating agent additive, which had an OH value of 43.2 and had been adjusted to a concentration of 3 wt% using butyl acetate; 78.3 g of the acryl ic polyol resin "Acryd ic (trademark) A-829" from Dainippon Ink and Chemicals, Incorporated, which had an OH value of 44 and a solids fraction concentration of 60 wt%; 25.0 g of the polyisocyanate compound
  • the coating agent was coated using a Mayer bar on an aluminum plate (JIS H 4000, 5 x 50 x 1 50 mm) and was cured by heating for 1 5 minutes at 1 50°C to yield a coated aluminum plate having a dry film thickness of 10 ⁇ for the coating layer, i .e., the coating film.
  • the thusly obtained coated aluminum plate was used to evaluate various properties according to the following criteria. The results are given in Table 1 .
  • the appearance of the resulting coating film was visually inspected and was evaluated using the fol lowing criteria.
  • the coating film is transparent.
  • the coating film presents a very slight cloudiness or unevenness.
  • a xylene-impregnated felt was installed in a rubbing tester from Taihei Rika Kogyo Kabushiki Kaisha; a 1 .2 kg load was applied; the surface of the coating film was subjected to 100 back-and-forth excursions; and the status of the coating film was then visually inspected and evaluated using the following criteria.
  • the cured coating film was marked with a Magic Ink blue ink pen from Pentel Co., Ltd., and was air-dried for 1 0 minutes and was then wiped with a KimWipe.
  • the status of crawl ing by the Magic Ink when marking was performed and the status of the wiping- off effort were visually inspected and evaluated using the following criteria.
  • a water droplet was placed on the cured coating film and the contact angle with the water was measured using a DM-700 contact angle meter from Kyowa Interface Science Co., Ltd.
  • the measurement was carried out under the following conditions using a Heid Type 14 friction tester from Shinto Scientific Co., Ltd. : 100 x 1 5 mm SUS cylinder, g load, and 100 mm/minute pull rate.
  • the conventional coating agent additive containing a strai ght chain polysiloxane results in a white cloudy appearance for the coating film and thus does not yield a uniform coating fi lm.
  • the coating agent additive of the present invention was characterized by an excellent compatibil ity with the curable resin component that was the base of the coating agent and thus characteristically yielded a uniform and transparent coating film .
  • sil icone-modified vinyl copolymer (A l ) which had the second generation carbosiloxane dendrimer structure shown in Practical Example 1 , not only provided these same properties, but was observed to provide a coating agent that also exhibited excellent coating layer properties such as staining/soiling resistance, water repellency, and so forth.
  • the coating agent additive of the present invention is a copolymer that has the hydroxyl group and a carbosiloxane dendrimer structure in side chain position and can provide a transparent resin solution.
  • a coating agent that incorporates the coating agent additive of the present invention provides, even at very small amounts of addition, a cured coating layer, i.e., a cured coating film, that is endowed with solvent resistance, staining/soiling resistance, water repellency, and so forth.
  • the coating agent of the present invention can function as a surface protectant and can impart staining/soiling resistance and thus can be used to counter a broad range of stains, dirt, and contaminants, such as oily or greasy contam inants and stains, the dust and dirt borne in the air, and the contaminants admixed in exhaust gas and rainwater.
  • the coating agent additive according to the present invention is also useful as a component for incorporation in paints and coating agents in general and is also effective when it is desired to restrain the smoothness of silicones while conferring their other properties, such as water repellency, for example, in the painting of gymnasium floors.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Cette invention concerne un additif pour agents de revêtement, ledit additif contenant (A) un copolymère qui contient un groupe hydroxyle et un groupe ayant une structure dendrimère carbosiloxane prédéfinie. En plus, un agent de revêtement qui contient cet additif pour agents de revêtement est décrit. Même à de très petites quantités d'ajout, l'additif selon la présente invention confère une excellente homogénéité, transparence, résistance aux solvants, résistance aux taches/à la saleté, et hydrophobicité à une couche de revêtement durcie.
PCT/JP2011/080604 2010-12-28 2011-12-26 Additif pour agent de revêtement et agent de revêtement le contenant WO2012091178A1 (fr)

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JP2010291659A JP5833821B2 (ja) 2010-12-28 2010-12-28 コーティング剤用添加剤およびそれを含有してなるコーティング剤

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Cited By (2)

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US10172779B2 (en) 2012-08-22 2019-01-08 Dow Corning Toray Co., Ltd. Copolymer having carbosiloxane dendrimer structure and composition and cosmetic containing the same
CN110684449A (zh) * 2018-07-04 2020-01-14 富士施乐株式会社 表面保护树脂部件形成用溶液、表面保护树脂部件形成用溶液组和表面保护树脂部件

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JP6092545B2 (ja) * 2012-08-22 2017-03-08 東レ・ダウコーニング株式会社 カルボシロキサンデンドリマー構造および親水性基を有する共重合体およびその用途
JP5976456B2 (ja) * 2012-08-22 2016-08-23 花王株式会社 化粧料
KR20220128612A (ko) * 2019-12-24 2022-09-21 미쓰이 가가쿠 가부시키가이샤 발수제 조성물, 발수제 조성물의 제조 방법, 및 섬유 제품

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JPS6178806A (ja) 1984-09-25 1986-04-22 Chisso Corp 被覆用熱硬化性アクリル樹脂組成物の製造法
JPH111530A (ja) 1997-06-12 1999-01-06 Toray Dow Corning Silicone Co Ltd シリコーン含有有機重合体およびその製造方法
JP2000019351A (ja) 1998-07-02 2000-01-21 Hamamatsu Photonics Kk 医療機器用光源装置
EP1006165A2 (fr) * 1998-11-30 2000-06-07 Dow Corning Toray Silicone Company, Ltd. Composition de revêtement
JP2000160025A (ja) 1998-11-26 2000-06-13 Dow Corning Toray Silicone Co Ltd 硬化性樹脂組成物および硬化樹脂
JP2000198939A (ja) 1998-10-27 2000-07-18 Dow Corning Toray Silicone Co Ltd 硬化性樹脂組成物
JP2001192424A (ja) 1999-10-29 2001-07-17 Dow Corning Toray Silicone Co Ltd シリコーングラフトビニル系共重合体エマルジョン組成物
JP2002256034A (ja) 2000-12-25 2002-09-11 Dow Corning Toray Silicone Co Ltd ビニル系共重合体エマルジョンおよび塗料添加剤
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JPS6178806A (ja) 1984-09-25 1986-04-22 Chisso Corp 被覆用熱硬化性アクリル樹脂組成物の製造法
JPH111530A (ja) 1997-06-12 1999-01-06 Toray Dow Corning Silicone Co Ltd シリコーン含有有機重合体およびその製造方法
JP2000019351A (ja) 1998-07-02 2000-01-21 Hamamatsu Photonics Kk 医療機器用光源装置
JP2000198939A (ja) 1998-10-27 2000-07-18 Dow Corning Toray Silicone Co Ltd 硬化性樹脂組成物
JP2000160025A (ja) 1998-11-26 2000-06-13 Dow Corning Toray Silicone Co Ltd 硬化性樹脂組成物および硬化樹脂
EP1006165A2 (fr) * 1998-11-30 2000-06-07 Dow Corning Toray Silicone Company, Ltd. Composition de revêtement
JP2001192424A (ja) 1999-10-29 2001-07-17 Dow Corning Toray Silicone Co Ltd シリコーングラフトビニル系共重合体エマルジョン組成物
JP2002256034A (ja) 2000-12-25 2002-09-11 Dow Corning Toray Silicone Co Ltd ビニル系共重合体エマルジョンおよび塗料添加剤
US20050008597A1 (en) * 2001-11-28 2005-01-13 Haruhiko Furukawa Cosmetic raw material cosmetic product and method for manufacturing a cosmetic product

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10172779B2 (en) 2012-08-22 2019-01-08 Dow Corning Toray Co., Ltd. Copolymer having carbosiloxane dendrimer structure and composition and cosmetic containing the same
CN110684449A (zh) * 2018-07-04 2020-01-14 富士施乐株式会社 表面保护树脂部件形成用溶液、表面保护树脂部件形成用溶液组和表面保护树脂部件

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