WO2010001773A1 - 塗料組成物及びこれを用いた塗膜形成方法 - Google Patents
塗料組成物及びこれを用いた塗膜形成方法 Download PDFInfo
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- WO2010001773A1 WO2010001773A1 PCT/JP2009/061447 JP2009061447W WO2010001773A1 WO 2010001773 A1 WO2010001773 A1 WO 2010001773A1 JP 2009061447 W JP2009061447 W JP 2009061447W WO 2010001773 A1 WO2010001773 A1 WO 2010001773A1
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/771—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur oxygen
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8108—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group
- C08G18/8116—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group esters of acrylic or alkylacrylic acid having only one isocyanate or isothiocyanate group
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8125—Unsaturated isocyanates or isothiocyanates having two or more isocyanate or isothiocyanate groups
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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
- 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
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/53—Base coat plus clear coat type
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
Definitions
- the present invention relates to a coating composition capable of imparting excellent scratch resistance and impact resistance to a coating film, and a multilayer coating film forming method and multilayer coating film using the same. Furthermore, it is related with the coating composition for forming a clear coating film.
- a clear coating is generally used for finishing automobiles.
- the clear coating is a transparent coating obtained by applying a transparent coating, which is formed as the outermost layer after an application step of a normally colored coating called base coating.
- the purpose of forming a clear coating is (1) By encapsulating fine irregularities due to the color pigment in the base layer in a transparent coating, it eliminates dullness due to irregular reflection and makes it appear more vivid and clear. (2) Improvement of durability such as high durability performance such as (2) UV resistance, acid rain resistance and chemical resistance, (3) Wear resistance and contamination resistance to reduce car washing scratches, etc. For example, the maintenance is improved.
- the scratch resistance and impact resistance of the clear coating are one of the important quality characteristics required for the final product.
- scratch resistance there is a problem that the coating film may be damaged when the product receives frictional force due to a car wash or the like, and with respect to impact resistance, when a strong external force is applied due to pebbles flying during driving.
- the scratch resistance of the clear coating film is improved by increasing the crosslinking density of the crosslinkable resin constituting the coating film. Therefore, as a paint capable of forming a highly scratch-resistant coating film, a fluorine-containing copolymer having an OH value in a specific range, an acrylic copolymer having an OH value in a specific range, and an isocyanate as a curing agent.
- a clear coating composition see Patent Document 1 containing a prepolymer and a specific ratio, a urethane compound having a specific structure, an acrylic photopolymerizable monomer having a specific structure, and a photopolymerization initiator.
- the photocurable resin composition (refer patent document 2) etc. which are formed are proposed.
- the coating composition described in Patent Document 1 is intended to increase the hardness of the coating film and improve the scratch resistance by introducing an acrylic copolymer.
- the photocurable resin composition described in Patent Document 2 attempts to increase the hardness of the coating film by increasing the crosslinking density by introducing a structure that promotes photopolymerization by ultraviolet irradiation, and to improve the scratch resistance. To do.
- the crosslinking density is too high, there is a problem that adhesion is lowered or cracks are generated due to an increase in strain during curing shrinkage. In either case, there is a limit to increasing the hardness, and it has been difficult to achieve a hardness that can withstand when the surface of the coating film is rubbed with a strong external force as described above.
- the coating compositions described in Patent Documents 3 and 4 alleviate the impact when dust or the like comes into contact with the coating film by introducing polycaprolactone, thereby improving the scratch resistance. I will try to let you. However, since the coating film obtained from this coating composition has insufficient hardness, if the coating film surface is rubbed with a strong external force as described above, the coating film may be scraped to the inside.
- the problem to be solved by the present invention is to provide a coating composition exhibiting excellent performance in terms of both scratch resistance and impact resistance, and a method for forming a multilayer coating film using the coating composition. It is to provide. Moreover, providing the coating composition which can be used suitably as a clear coating film for finish coatings, such as for motor vehicles, and also the coating composition in which high solidification is possible can also be mentioned as a problem to be solved.
- “high solidification” means that the solid content concentration in the paint is high.
- a compound having an isocyanate group is derived from a (meth) acrylate compound. That is, an isocyanate pendant type prepolymer can be obtained by homopolymerizing the (meth) acrylate moiety of the (meth) acrylate compound having an isocyanate group or copolymerizing it with another (meth) acrylate compound.
- the crosslinking density can be controlled, that is, the hardness of the coating film can be controlled.
- urethane By controlling the length between the isocyanate group of the (meth) acrylate compound having an isocyanate group and the (meth) acrylate moiety, and the length of the polyol reacted with the isocyanate group hanging from the prepolymer main chain, urethane is controlled. Based on the idea that the hardness of the coating film can be controlled by hydrogen bonding between the bonds, and the elasticity can also be controlled.
- a (meth) acrylic copolymer derived from a specific (meth) acrylate compound having an isocyanate group or a polyisocyanate prepolymer of a homopolymer is an essential component, a polyol is included as a crosslinking agent, and an average functional group equivalent is
- the present invention is as follows. [1] A paint comprising a polyisocyanate prepolymer (A) having a monomer unit represented by the following general formula (1) and a polyol (B) and having an average functional group equivalent of 160 to 400 g / eq Composition.
- R 1 represents a hydrogen atom or a methyl group
- n is an integer of 0 or 1
- the raw material monomer of the polyisocyanate prepolymer (A) is at least one selected from the group consisting of acryloyloxyethyl isocyanate, methacryloyloxyethyl isocyanate, and methacryloyloxyethoxyethyl isocyanate [1] or The coating composition according to [2].
- the polyol (B) contains at least one selected from the group consisting of a polylactone polyol (b1), a polyether polyol (b2), a polycarbonate diol (b3), and an aliphatic diol (b4).
- the coating composition according to any one of [1] to [3].
- a method for forming a multilayer coating film comprising forming a clear coating film comprising the coating composition according to any one of [1] to [4] on a base coating film.
- An automotive exterior part comprising the multilayer coating film obtained by the multilayer coating film forming method according to [5].
- the coating composition of the present invention By using the coating composition of the present invention, it is possible to form a coating film exhibiting excellent performance in both scratch resistance and impact resistance. According to the method for forming a multilayer coating film of the present invention, it is possible to form a coating film exhibiting excellent performance in both scratch resistance and impact resistance by using the coating composition.
- the coating composition and the multilayer coating film forming method of the present invention can be suitably applied to the formation of a clear coating film for finish coating such as for automobiles.
- the coating composition of the present invention can be made into a high solid such as a spray coating, and therefore, the amount of solvent can be reduced and VOC can be reduced.
- the coating composition of the present invention comprises, as an essential component, a polyisocyanate prepolymer (A) having a monomer unit represented by the following general formula (1) derived from a (meth) acrylate compound having an isocyanate group. To do. Moreover, a polyol (B) is included as a crosslinking agent.
- the “prepolymer” is a compound generated by a polymerization reaction, and having a curable functional group, can further perform a curing reaction.
- the weight average molecular weight of the polyisocyanate prepolymer (A) of the present invention is preferably 1000 to 30000, more preferably 2000 to 25000, and particularly preferably 2500 to 20000.
- a weight average molecular weight can be calculated
- the polyisocyanate prepolymer (A) of the present invention is a compound that forms the monomer unit represented by the general formula (1), that is, as the monomer, (a1) a (meth) acrylate compound having an isocyanate group is essential. If necessary, (a2) an unsaturated compound having a cyclic skeleton and / or (a3) another unsaturated carboxylic acid compound or unsaturated ester compound may be copolymerized.
- the (meth) acrylate compound having an isocyanate group is an unsaturated group-containing isocyanate compound represented by the following formula (2).
- the compound (a1) one kind of the unsaturated group-containing isocyanate compound may be used alone, or two or more kinds thereof may be used in combination.
- R 1 , m, n, l and p have the same meanings as R 1 , m, n, l and p in general formula (1), respectively.
- Specific examples of the compound (a1) include acryloyloxyethyl isocyanate (AOI) represented by the following formula (10), methacryloyloxyethyl isocyanate (MOI) represented by the following formula (11), and formula (12) below. Mention may be made of the methacryloyloxyethoxyethyl isocyanate (MOI-EG) shown. These can be used alone or in combination of two or more.
- the copolymerization ratio of the compound (a1) is not particularly limited, but the scratch resistance and From the viewpoint of achieving both impact resistance, it is preferably 50 mol% or more, and more preferably 80 mol% or more. When the total amount of the compounds is less than 50 mol%, a sufficient crosslinking density cannot be obtained and the strength may be insufficient.
- the unsaturated compound having a cyclic skeleton is a (meth) acrylic compound having no isocyanate group and having a cyclic skeleton.
- the compound (a2) include cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) ) Cycloalkyl (meth) acrylates such as acrylate and morpholinyl (meth) acrylate; ethylenically unsaturated aromatic compounds such as styrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, and p-methylstyrene These may be used, and these may be used alone, or two or more of these may be used in combination.
- isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, and morpholinyl (meth) acrylate are preferred because of their high glass transition point and high strength, and tricyclodecanyl (meth) acrylate is preferred. Most preferred.
- the following formulas (3) to (5) show monomer units obtained from isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate and morpholinyl (meth) acrylate, respectively.
- R 1 represents the same meaning as R 1 in the general formula (1), and one of R 6 and R 7 is always a methyl group, and the other side is always a hydrogen atom.
- R 1 represents the same meaning as R 1 in formula (1).
- R 1 represents the same meaning as R 1 in formula (1).
- the other unsaturated carboxylic acid compound or unsaturated ester compound is a (meth) acrylic compound having no isocyanate group and no cyclic skeleton.
- Examples of the compound (a3) include carboxyl group-containing compounds such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) Acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) Acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodec
- the total copolymerization ratio of the compound (a2) and the compound (a3) is not particularly limited, but may be 50% by mole or less from the viewpoint of achieving both scratch resistance and impact resistance. Preferably, it becomes 20 mol% or less. If the sum of the compounds of (a2) and (a3) exceeds 50 mol%, the crosslinking density may not be sufficiently obtained, and if the compound of (a2) exceeds 50 mol%, the solubility of the polymer May decrease or crystallinity may be improved, and handling may be reduced.
- the polyisocyanate prepolymer (A) is synthesized by polymerizing the compound (a1) or copolymerizing the compound (a1) with the compound (a2) and / or the compound (a3).
- a chain transfer agent may be used in combination for the synthesis of the polyisocyanate prepolymer (A).
- a chain transfer agent to be used, It is preferable to use the compound which has a mercapto group from a viewpoint of the reactivity or the characteristic of resin.
- Specific examples include monofunctional thiol compounds such as 2-mercaptoethanol, mercaptobenzene, and dodecyl mercaptan, and polyfunctional thiol compounds represented by the following general formula (6).
- X represents an alcohol residue of the polyfunctional alcohol compound
- R 8 and R 9 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or methyl
- X 3 and X 4 each independently represents a single bond or a linear or branched alkyl group having 1 to 3 carbon atoms
- x represents an integer of 2 to 10, preferably 2 to 4.
- Specific examples of the polyfunctional thiol compound include butanediol bis (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), tris-2- (3-mercaptobutyrate) ethyl isocyanurate, and the like. It can be illustrated.
- a copolymer having a branched structure can be obtained by using a tri- or higher functional chain transfer agent. Since the viscosity of the resin is reduced in the branched polymer, the handling property can be improved.
- a well-known solvent can be used.
- ester solvents such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and ethylene glycol monobutyl ether acetate, and aromatic hydrocarbon solvents such as toluene and xylene can be preferably used.
- the reaction temperature during the synthesis of the polyisocyanate prepolymer (A) is 60 ° C to 130 ° C, preferably 70 ° C to 125 ° C, more preferably 75 ° C to 120 ° C. If the reaction temperature is less than 60 ° C., the polymerization initiator may not sufficiently perform its function, and if it exceeds 130 ° C., the isocyanate group may be destroyed.
- a polymerization initiator used for the synthesis there is no restriction
- an azo initiator is preferably used. Specifically, azobisisobutyronitrile, 2,2-azobis- (2,4-dimethylvaleronitrile), dimethyl-2,2 -Azobis- (2-methylpropionate) and the like.
- Polyol (B) is a compound containing two or more —OH groups.
- polyol (B) polylactone polyol (b1), polyether polyol (b2), polycarbonate diol (b3) and aliphatic diol (b4) are preferable. These may contain 1 type, or 2 or more types.
- the polylactone polyol (b1) is not particularly limited.
- bifunctional polycaprolactone diols such as a compound represented by the following general formula (7), a compound represented by the following general formula (8) And trifunctional polycaprolactone triols, and other tetrafunctional polycaprolactone polyols.
- polylactone polyol (b1) only 1 type of these may be used and 2 or more types may be used.
- R 10 is any one of —C 2 H 4 —, —C 2 H 4 OC 2 H 4 —, —C (CH 2 ) 2 (CH 2 ) 2 —, q and r is an integer of 4 to 35.
- R 11 is any one of the following formulas (13) to (15), and s + t + u is an integer of 3 to 30)
- the polylactone polyol (b1) preferably has 2 to 5 —OH groups, more preferably 2 to 3. When the number of functional groups of the polylactone polyol (b1) exceeds 5, the scratch resistance may be lowered.
- the polyether polyol (b2) is not particularly limited. Examples include diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, polybutylene glycol, and polytetramethylene glycol. As polyether polyol (b2), only 1 type of these may be used and 2 or more types may be used.
- the polycarbonate diol (b3) is not particularly limited.
- polycarbonate diol soot produced by a known method can be used.
- polycarbonate diol soot obtained by reacting a carbonate component such as alkylene carbonate, diaryl carbonate, dialkyl carbonate or phosgene with an aliphatic diol component exemplified below can be mentioned.
- linear glycols such as 1,3-propanediol, 1,4-butanediol or 1,6-hexanediol, represented by the general formula (9)
- Examples include branched glycols.
- R 12 represents CH 3 — or CH 3 (CH 2 ) x — (wherein x represents an integer of 1 to 4), R 13 represents a hydrogen atom, CH 3 — or CH 3 (CH 2 ) y — (wherein y represents an integer of 1 to 4.)
- v and w are the same or different integers of 1 to 8, provided that 2 ⁇ v + w ⁇ 8.
- branched glycols such as 1,2-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, and ethylbutylpropanediol, or ether diols such as diethylene glycol and triethylene glycol are used as fat. Examples of the group diol component can be given.
- the aliphatic diol (b4) is not particularly limited, and examples thereof include ethylene glycol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 2-isopropyl-1,4-butanediol, , 5-pentanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,3-cyclohexanediol, 1,4-cyclo
- the polyisocyanate prepolymer (A) (main agent) and the polyol (B) component (curing agent) preferably have an NCO / OH (equivalent ratio) of 0.9 to 1.1, More preferably 0.95 to 1.05, and still more preferably 1.0.
- NCO / OH (equivalent ratio) means (number of moles of NCO / number of moles of OH).
- the NCO / OH (equivalent ratio) is less than 0.9, the crosslinking density may not be sufficiently obtained, and the weather resistance may be lowered.
- the NCO / OH (equivalent ratio) exceeds 1.1, the solvent resistance, water resistance and weather resistance may be deteriorated, or satisfactory results may not be obtained in terms of drying properties.
- the coating composition of the present invention has an average functional group equivalent of 160 to 400 g / eq, preferably 180 to 360 g / eq, and more preferably 200 to 250 g / eq.
- the average functional group equivalent is within the above range, the balance between the maximum pencil hardness that can be repaired by a scratch and the scratch resistance becomes good.
- average functional group equivalent means a value determined by the following formula (16).
- NCO equivalent is the molecular weight per NCO group of the polyisocyanate prepolymer (A),
- OH equivalent is the molecular weight per OH group of the polyol (B).
- the (NCO equivalent of the polyisocyanate prepolymer (A) ⁇ mixing mole fraction) is (NCO equivalent ⁇ mixing mole fraction) of each component. Summed up.
- (OH equivalent ⁇ blending mole fraction of polyol (B)) is the sum of (OH equivalent ⁇ blending mole fraction) of each component.
- the coating composition of the present invention preferably has a molecular weight between crosslink points after curing of 450 to 650 g / eq, and more preferably 500 to 600.
- the “molecular weight between cross-linking points” means that the NCO groups of the polyisocyanate prepolymer (A) and the OH groups of the polyol (B) are reacted at a blending ratio so as to be almost equal,
- the molecular weight of the crosslinking reaction product per crosslinking point that is, the molecular weight after crosslinking is determined by the number of NCO groups in the polyisocyanate prepolymer (A) (or It means a value divided by the number of OH groups in the polyol (B).
- (NCO equivalent ⁇ number of NCO groups) is the sum of (NCO equivalent ⁇ number of NCO groups) of each component.
- (OH equivalent ⁇ number of OH groups) is the sum of (OH equivalent ⁇ number of OH groups) of each component.
- the NCO equivalent and the OH equivalent are the same as in the case of the above formula (16).
- the number of moles of OH groups and the number of moles of NCO groups are determined by calculation from the functional group amounts of the polyol (B) and the polyisocyanate prepolymer (A) and the blending ratio thereof.
- the coating composition of the present invention comprises a curing accelerator (catalyst), a solvent, an ultraviolet absorber, a light stabilizer, an antioxidant, a yellowing inhibitor, a bluing agent, a dispersant, a flame retardant, and a dye as necessary.
- Fillers organic or inorganic pigments, mold release agents, fluidity modifiers, leveling agents, antifoaming agents, thickeners, antisettling agents, antistatic agents, antifogging agents, etc., without impairing the effects of the present invention It can mix
- the catalyst examples include monoamine triethylamine, N, N-dimethylcyclohexylamine, diamine tetramethylethylenediamine, other triamines, cyclic amines, alcohol amines such as dimethylethanolamine, ether amines, and metal catalysts such as potassium acetate, 2 Potassium ethylhexanoate, calcium acetate, lead octylate, di-n-butyltin dilaurate, tin octylate, tetra-n-butoxytitanium, bismuth neodecanoate, bismuth oxycarbonate, bismuth 2-ethylhexanoate, octyl Commonly used materials such as zinc acid, zinc neodecanoate, phosphine, and phospholine can be used.
- Solvents include dimethylformamide, diethylformamide, dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, acetone, methyl ethyl ketone, methyl isobutyl ketone, dioxane, cyclohexanone, benzene, toluene, xylene, ethyl cellosolve, ethyl acetate, butyl acetate, ethanol, isopropanol, n -Butanol can be used.
- Examples of the filler that increases the mechanical strength of the cured film include calcium carbonate, talc, mica, clay, silica (colloidal silica, Aerosil (registered trademark), etc.), barium sulfate, aluminum hydroxide, and zinc stearate.
- pigments for coloring include calcium carbonate, talc, mica, clay, silica (colloidal silica, Aerosil (registered trademark), etc.), barium sulfate, aluminum hydroxide, zinc stearate, zinc white, bengara, azo pigments, Examples include titanium oxide.
- silicone As the release agent, fluidity modifier, and leveling agent, silicone, silica fine particles, wax, stearate, polysiloxane and the like are used. Specifically, a trade name “BYK306” (leveling agent: manufactured by Big Chemie) or the like is preferably used.
- Tinuvin manufactured by Ciba Specialty Chemicals
- Irganox trade name
- Tinuvin 900 ultraviolet absorber; manufactured by Ciba Specialty Chemicals
- Tinubin 292 photoantioxidant: manufactured by Ciba Specialty Chemicals
- the coating composition of the present invention can be used as various coating materials such as plastic coating materials, automotive interior / exterior coating materials, and floor coating materials.
- the coating composition of the present invention is suitably used as a clear coating for coating, for example, automobile exterior parts and the like to improve scratch resistance and impact resistance.
- the multi-layer coating film forming method of the present invention is a multi-layer coating film forming method in which a clear coating film is formed by a clear coating material on a base coating film formed by a base coating material.
- a composition is used. Specifically, for example, after performing surface treatment, electrodeposition coating formation, intermediate coating formation, etc. on a metal substrate as necessary, a base coating is formed using a base coating as an overcoat. Further, there is a method of applying a clear coating comprising the coating composition of the present invention thereon to form a coating (curing), but is not limited thereto.
- the multilayer coating film forming method of the present invention can form a multilayer coating film on a plastic substrate. In that case, in order to remove the strain at the time of molding the substrate, if necessary. After applying heat treatment (annealing) and primer coating to the plastic substrate, a base coating is formed using the base coating as an overcoat, and a clear coating composed of the coating composition of the present invention is applied thereon.
- annealing heat treatment
- primer coating primer coating
- a base coating is formed using the base coating as an overcoat, and a clear coating composed of the coating composition of the present invention is applied thereon.
- the base paint that can be used in the method for forming a multilayer coating film of the present invention is not particularly limited.
- a solvent-type paint such as a lacquer paint, an acrylic-melamine baking paint, a two-component curable urethane paint, or a water-based paint. Etc. can be preferably used.
- the coating composition of the present invention is used as a clear coating, and a conventionally known coating film forming method can be applied.
- the method for applying the base paint or the clear paint is not particularly limited.
- known paints such as spray paint, dip paint, shower coat paint, roll coater paint, rotary bell paint, etc.
- the method should be adopted.
- electrostatic coating may be used.
- the film thickness at the time of coating may be set as appropriate. For example, it is usually applied so that the base paint has a dry film thickness of 10 to 20 ⁇ m and the clear paint has a dry film thickness of 20 to 40 ⁇ m. Is done.
- the base coating film and the clear coating film may be formed by coating each coating material and then drying and forming a coating film by an ordinary method.
- the method for drying and forming a coating film is not particularly limited, and examples thereof include room temperature drying, forced drying, room temperature curing, baking curing, and photocuring by ultraviolet irradiation. Drying and coating may be performed for each coating after each coating is applied, or may be performed at once after each coating is applied wet-on-wet.
- the multilayer coating film of the present invention is a multilayer coating film in which a clear coating film is formed by a clear coating on a base coating film formed by a base coating, and the coating composition of the present invention is used as the clear coating. Things are used.
- Such a multilayer coating film of the present invention has extremely high scratch resistance and impact resistance that could not be achieved so far. Specifically, it has scratch resistance that can withstand even if the surface of the coating is rubbed with a strong external force during car washing, and it can be applied even if it receives a strong impact force due to sand dust flying while traveling. It has impact resistance to the extent that cracks do not easily occur even when the film peels off or the base coating film.
- the multilayer coating film of the present invention can be easily obtained by, for example, the multilayer coating film forming method of the present invention described above.
- a polymerization reaction was performed. During the reaction, the liquid temperature was kept at 100 ° C. while constantly stirring the internal solution. Subsequently, a polymerization initiator solution consisting of 5 g of the azo polymerization initiator “V-601 (manufactured by Wako Pure Chemical Industries)” and 90 g of the mixed solvent (S 0 ) is kept at 100 ° C. while stirring.
- a solution (S1) containing a polyisocyanate prepolymer (A1) was obtained by adding dropwise into the reaction vessel over 1 hour, further raising the liquid temperature to 120 ° C. while stirring, and holding for 1 hour.
- the polyisocyanate prepolymer (A1) can be obtained as a residue by heat treatment at 200 ° C. for 3 hours, that is, a resin solid content (NV), and the solid content was 810 g at 54%.
- the resulting polyisocyanate prepolymer A1 had a weight average molecular weight of 8850. Moreover, since 2.5 mol of NCO groups were present in 810 g of resin solids, the NCO equivalent was 324 g / eq at 810 / 2.5. In addition, the weight average molecular weight was calculated
- the obtained polyisocyanate prepolymer (A2) can be obtained as a residue by heat treatment at 200 ° C. for 3 hours, that is, a resin solid content (NV), and the solid content was 835 g at 54%. .
- a polyisocyanate prepolymer A3 was obtained in the same manner as in the production of the polyisocyanate prepolymer A1.
- the obtained polyisocyanate prepolymer (A3) can be obtained as a residue by heat treatment at 200 ° C. for 3 hours, that is, a resin solid content (NV), and the solid content was 671 g at 49%. .
- the resulting polyisocyanate prepolymer A2 had a weight average molecular weight of 8,000. Moreover, since 2.5 mol of NCO groups were present in 671 g of resin solid content, the NCO equivalent was 268 g / eq at 671 / 2.5.
- tripropylene glycol (b2-1; solid content 100%, functional group number 2, hence OH equivalent is 96 g / eq , Wako Pure Chemicals Co., Ltd.) were sequentially charged with stirring and mixed well, and then the reaction vessel was charged with 4 g of the trade name “Tinuvin 900” (ultraviolet absorber; manufactured by Ciba Specialty Chemicals), and the trade name “Tinubin”.
- This coating composition had a resin solid content (NV) of 50%, a viscosity of 50 mPa ⁇ s, an average functional group equivalent of 219, and a molecular weight between crosslinking points of 517.
- the molecular weight between crosslinking points was determined as follows.
- the viscosity was measured at 25 ° C. according to a conventional method using a B-type viscometer DV-II + Pro (manufactured by BROOKFIELD).
- -Coating compositions of Examples 2 to 8 and Comparative Examples 1 to 4- The coating compositions of Examples 2 to 8 and the coating compositions of Comparative Examples 1 to 4 were produced in the same manner as described above by blending the resins shown in Table 1 below.
- polycaprolactone triol (b1-2), polycaprolactone diol (b1-3), (b1-4) and polycarbonate diol (b3-1), 1,6 as curing agents used in the above Examples and Comparative Examples were used.
- Resin solid content (NV ), Viscosity, average functional group equivalent, and molecular weight between crosslinking points are as shown in Table 1 below.
- Example of formation of multilayer coating film -Coating on metal material- ⁇ Examples 1 to 8, Comparative Examples 1 to 4>
- the coating thickness is reduced by spray coating “Presaf Gray 062-1940” (manufactured by Rock Paint Co., Ltd.) as an intermediate coating on a coated iron plate (ZB phosphate conversion coating PB-L3020 manufactured by Nippon Test Panel Co.). After coating to 30 ⁇ m, it was allowed to stand at room temperature for 10 minutes, and then dried and cured at 140 ° C. for 20 minutes using a dryer. The coated product was taken out and allowed to stand at room temperature.
- the dry film thickness is 15 ⁇ m.
- the coated product was taken out and brought to room temperature, and then the coating compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 4 were applied with a spray gun so that the dry film thickness was 30 ⁇ m, and 10 minutes at room temperature. After standing, it was placed in a dryer at 140 ° C. atmosphere temperature for 20 minutes to dry and harden to obtain a coated iron material and a test piece.
- Table 2 shows the results of the gloss retention obtained from the following formula and evaluated according to the following criteria. The higher the gloss retention value, the better the coating film.
- Table 2 shows the maximum brush hardness for repairing the scratches.
- a clear coating composition was applied to a quartz glass substrate (50 mm ⁇ 50 mm) so that the dry film thickness was 100 ⁇ m, left at room temperature for 10 minutes, and then dried and cured at 140 ° C. for 20 minutes.
- the obtained clear coating film is light having a wavelength of 400 nm using a spectrophotometer (manufactured by JASCO Corporation, UV3100) according to JIS-K7105.
- the transmittance (T%) was measured and shown in Table 2. The larger the transmittance value, the better the coating film.
- ⁇ Glass transition temperature Tg> A clear coating composition was applied to a quartz glass substrate (50 mm ⁇ 50 mm) so that the dry film thickness was 100 ⁇ m, left at room temperature for 10 minutes, and then dried and cured at 140 ° C. for 20 minutes.
- the obtained clear coating film is in a tensile mode, a temperature range of ⁇ 50 ° C. to 150 ° C., and a temperature rising rate. It calculated
- the present invention relates to a coating composition for forming a clear coating film capable of imparting excellent scratch resistance and impact resistance, and a multilayer coating film forming method and multilayer coating film using the same. Specifically, it is possible to form a coating film having scratch resistance that can withstand even if it receives frictional force such as a car wash, and receives a strong external force due to pebbles flying during driving. However, it is possible to form a coating film with impact resistance that does not cause peeling or cracking of the coating film. For example, it is suitable for molded products that are easily damaged on the surface, such as automobile exterior parts. Can be applied to.
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Abstract
Description
[1]下記一般式(1)で表されるモノマー単位を有するポリイソシアネートプレポリマー(A)及びポリオール(B)を含み、平均官能基当量が160~400g/eqであることを特徴とする塗料組成物。
n=0の場合は、l=0、p=1、及びmは1~8の整数を表し、
n=1の場合は、m=2、l=2、及びpは1~4の整数を表す。)
[2]平均官能基当量が、180~360g/eqであることを特徴とする[1]に記載の塗料組成物。
[3]ポリイソシアネートプレポリマー(A)の原料モノマーが、アクリロイルオキシエチルイソシアネート、メタクリロイルオキシエチルイソシアネート及びメタクリロイルオキシエトキシエチルイソシアネートからなる群より選ばれる少なくとも1種であることを特徴とする[1]または[2]に記載の塗料組成物。
[4]ポリオール(B)が、ポリラクトンポリオール(b1)、ポリエーテルポリオール(b2)、ポリカーボネートジオール(b3)、及び脂肪族ジオール(b4)からなる群より選ばれる少なくとも1種を含むことを特徴とする[1]~[3]のいずれかに記載の塗料組成物。
[5][1]~[4]のいずれかに記載の塗料組成物からなるクリヤー塗膜を、ベース塗膜の上に形成することを特徴とする複層塗膜形成方法。
[6][5]に記載の複層塗膜形成方法で得られることを特徴とする複層塗膜。
[7][5]に記載の複層塗膜形成方法で得られた複層塗膜を備えることを特徴とする自動車外装用部品。
〔塗料組成物〕
本発明の塗料組成物は、イソシアネート基を有する(メタ)アクリレート化合物に由来する下記一般式(1)で表されるモノマー単位を有することを特徴とするポリイソシアネートプレポリマー(A)を必須成分とする。また、架橋剤としてポリオール(B)を含む。ここで「プレポリマー」とは、重合反応によって生成した化合物であって、硬化性官能基を有していることによりさらに硬化反応を行うことができる化合物のことである。
n=0の場合は、l=0、p=1、及びmは1~8の整数を表し、
n=1の場合は、m=2、l=2、及びpは1~4の整数を表す。)
本発明のポリイソシアネートプレポリマー(A)の重量平均分子量は1000~30000であることが好ましく、さらに好ましくは2000~25000、特に好ましくは2500から20000である。重量平均分子量が1000より小さいと、本発明に特有の弾力性を十分に発揮することが困難であり、30000より大きいと粘度が高いために、塗料組成物のハンドリング性、塗工性を損ねる恐れがある。なお、重量平均分子量は、ゲルパーミエーションクロマトグラフィ(GPC)を使用し、常法により測定したポリスチレン換算の重量平均分子量によって求めることができる。
(a1)の化合物の具体例としては、下記(10)式で示されるアクリロイルオキシエチルイソシアネート(AOI)、下記(11)式で示されるメタクリロイルオキシエチルイソシアネート(MOI)、及び下記(12)式で示されるメタクリロイルオキシエトキシエチルイソシアネート(MOI-EG)を挙げることができる。これらは、単独で、あるいは2種以上を組み合わせて使用することができる。
(a2)の化合物としては例えば、シクロヘキシル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート、ジシクロペンテニル(メタ)アクリレート、ノルボルニル(メタ)アクリレート、イソボルニル(メタ)アクリレート、トリシクロデカニル(メタ)アクリレート、モルホリニル(メタ)アクリレートなどのシクロアルキル(メタ)アクリレート類;スチレン、α-メチルスチレン、o-メチルスチレン、m-メチルスチレン、p-メチルスチレンなどのエチレン性不飽和芳香族化合物などを挙げることができ、これらを単独で用いてもいいし、あるいはこれらの2種以上を併用することもできる。
(a3)他の不飽和カルボン酸化合物または不飽和エステル化合物とは、イソシアネート基を有さず環式骨格も有さない(メタ)アクリル化合物である。
前記多官能チオール化合物としては、具体的には ブタンジオールビス(3-メルカプトブチレート)、ペンタエリスリトールテトラキス(3-メルカプトブチレート)、トリス-2-(3-メルカプトブチレート)エチルイソシアヌレート等を例示することができる。
具体的には、1,2-プロパンジオール、ネオペンチルグリコール、3-メチル-1,5-ペンタンジオール、エチルブチルプロパンジオール等の分岐グリコール、あるいはジエチレングリコール、トリエチレングリコール等のエーテル系ジオール類を脂肪族ジオール成分の例として挙げることができる。
「OH当量」とは、ポリオール(B)のOH基1個当たりの分子量である。
なお、ポリイソシアネートプレポリマー(A)が複数の成分からなる場合は、(ポリイソシアネートプレポリマー(A)のNCO当量×配合モル分率)は、各成分の(NCO当量×配合モル分率)の総和となる。ポリオール(B)も同様に、複数の成分からなる場合は、(ポリオール(B)のOH当量×配合モル分率)は、各成分の(OH当量×配合モル分率)の総和となる。
ここで「架橋点間分子量」とは、ポリイソシアネートプレポリマー(A)のNCO基とポリオール(B)のOH基とがほぼ等量となる配合比で両者を反応させて、すべてのNCO基とすべてのOH基とが反応して架橋したと仮定した場合の、架橋点1個あたりの架橋反応生成物の分子量、つまり架橋後の分子量をポリイソシアネートプレポリマー(A)のNCO基の数(またはポリオール(B)のOH基の数)で割った値を意味する。ただし、ここでは簡易的に、原料であるポリイソシアネートプレポリマー(A)のNCO基1個当たりの分子量(NCO当量)とポリオール(B)のOH基1個当たりの分子量(OH当量)とから、下記式(17)により求められる数値を架橋点間分子量とする。
本発明の塗料組成物は、必要に応じて、硬化促進剤(触媒)、溶剤、紫外線吸収剤、光安定剤、酸化防止剤、黄変防止剤、ブルーイング剤、分散剤、難燃剤、染料、充填剤、有機または無機顔料、離型剤、流動性調整剤、レベリング剤、消泡剤、増粘剤、沈降防止剤、帯電防止剤、防曇剤等を、本発明の効果を損なわない範囲で適宜配合することができる。
本発明の塗料組成物は、例えば自動車外装用部品等に塗装して耐擦傷性及び耐衝撃性を向上させるためのクリヤー塗料として好適に用いられる。
〔複層塗膜形成方法〕
本発明の複層塗膜形成方法は、ベース塗料により形成されたベース塗膜の上にクリヤー塗料によりクリヤー塗膜を形成する複層塗膜の形成方法において、前記クリヤー塗料として前記本発明の塗料組成物を用いるものである。具体的には、例えば、金属基材に、必要に応じて、表面処理、電着塗膜形成、中塗り塗膜形成等を施したのち、上塗りとしてベース塗料を用いてベース塗膜を形成し、その上に本発明の塗料組成物からなるクリヤー塗料を塗装し、塗膜化(硬化)させる方法挙げられるが、これらに限定されるものではない。
本発明の複層塗膜形成方法において、ベース塗料やクリヤー塗料の塗装方法は、特に制限はなく、例えば、スプレー塗装、浸漬塗装、シャワーコート塗装、ロールコーター塗装、回転ベル塗装等の公知の塗装方法を採用すればよい。なお、スプレー塗装や回転ベル塗装の場合は、静電塗装であってもよい。塗装の際の膜厚は、適宜設定すればよいのであるが、例えば、通常、ベース塗料は乾燥膜厚10~20μmとなるように、クリヤー塗料は乾燥膜厚20~40μmとなるように、塗装される。
〔複層塗膜〕
本発明の複層塗膜は、ベース塗料により形成されたベース塗膜の上にクリヤー塗料によりクリヤー塗膜が形成されてなる複層塗膜であって、前記クリヤー塗料として前記本発明の塗料組成物が用いられてなるものである。このような本発明の複層塗膜は、これまで達成し得なかった極めて高い耐擦傷性と耐衝撃性を有する。具体的には、洗車の際に強い外力で塗膜表面がこすられても耐えうるだけの耐擦傷性を有し、且つ、走行中に飛んでくる砂塵等により強い衝撃力を受けても塗膜の剥れやベース塗膜にまではクラックが入りにくい程度の耐衝撃性を有する。本発明の複層塗膜は、例えば、前述した本発明の複層塗膜形成方法により容易に得ることができる。
[樹脂の製造例]
-ポリイソシアネートプレポリマーA1の製造-
攪拌機、温度計、還流管、滴下ロート、窒素導入管及びサーモスタット付き加熱装置を備えた反応容器に、酢酸ブチルとキシレンが質量比で1:3の混合溶剤(S0)を500g仕込み、攪拌しながら、内部溶剤温度を100℃まで昇温した。次いで、2-アクリロイルオキシエチルイソシアネート、商品名「Karenz AOI(昭和電工製)」352.5g(=2.5モル)、イソボロニルメタクリレート(商品名IBX;和光純薬製)245g、n-ブチルメタクリレート(商品名nBMA;和光純薬製)128.5gからなるモノマー混合溶液と、アゾ系重合開始剤であるジメチル―2,2―アゾビス-(2-メチルプロピオネート)、商品名「V-601(和光純薬製)」60gと上記混合溶剤(S0)120gとからなる重合開始剤溶液をそれぞれ別の滴下ロートに入れ、反応容器内部を攪拌しながら、それぞれ、3時間かけて滴下し、重合反応を行った。反応中は、常に内部溶液を攪拌しながら、液温度を100℃に保持した。次いで、上記アゾ系重合開始剤「V-601(和光純薬製)」5gと上記混合溶媒(S0)90gからなる重合開始剤溶液を、攪拌しながら液温を100℃に保持している反応容器内に、1時間かけて滴下し、さらに攪拌しながら液温を120℃に昇温した後1時間保持することでポリイソシアネートプレポリマー(A1)を含む溶液(S1)を得た。ポリイソシアネートプレポリマー(A1)は、当該溶液を200℃、3hrの加熱処理による残分、すなわち樹脂固形分(NV)として得ることができ、その固形分は54%で810gであった。
-ポリイソシアネートプレポリマーA2の製造-
ポリイソシアネートプレポリマーA1の製造において、2-アクリロイルオキシエチルイソシアネート352.5g(=2.5モル)を、2-(2-メタクリロイルオキシ)エトキシエチルイソシアネート352.5g(=2.5モル)に変更した以外は、ポリイソシアネートプレポリマーA1の製造と同様にして、ポリイソシアネートプレポリマーA2を得た。得られたポリイソシアネートプレポリマー(A2)は、当該溶液を200℃、3hrの加熱処理による残分、すなわち樹脂固形分(NV)として得ることができ、その固形分は54%で835gであった。
-ポリイソシアネートプレポリマーA3の製造-
ポリイソシアネートプレポリマーA1の製造において、8-メタクリロイルオキシオクチルイソシアネート625g(=2.5モル)のみを用い、イソボロニルメタクリレート、n-ブチルメタクリレートを用いず、重合開始剤V-601を30gとした以外は、ポリイソシアネートプレポリマーA1の製造と同様にして、ポリイソシアネートプレポリマーA3を得た。得られたポリイソシアネートプレポリマー(A3)は、当該溶液を200℃、3hrの加熱処理による残分、すなわち樹脂固形分(NV)として得ることができ、その固形分は49%で671gであった。
[塗料組成物の製造例]
-実施例1の塗料組成物-
攪拌機のついた反応容器に、主剤としての上記ポリイソシアネートプレポリマーA1の溶液(上記の溶液S1)を722g、硬化剤としてのポリカプロラクトンジオール、商品名「プラクセルL205AL」(b1-1;固形分100%、分子量500、官能基数2、よってOH当量が250g/eq、ダイセル化学工業社製)を201g、トリプロピレングリコール(b2-1;固形分100%、官能基数2、よってOH当量が96g/eq、和光純薬製)を33g、を攪拌しながら順次仕込み、十分混合させたのち、反応容器内に、商品名「チヌビン900」(紫外線吸収剤;チバスペシャリティケミカルズ社製)4g、商品名「チヌビン292」(光酸化防止剤;チバスペシャリティケミカルズ社製)2g、商品名「BYK306」(表面調整剤;ビックケミー社製)2g、キシレン/酢酸ブチル=3/1の混合溶媒(S0)305gを追加仕込みして十分に攪拌して、実施例1に用いる塗料組成物を製造した。
平均官能基当量は、以下のようにして求めた。すなわち、
平均官能基当量=(323×722×0.54/8850+250×201/500+96×33/192)/(722×0.54/8850+201/500+33/192)=219
架橋点間分子量は、以下のようにして求めた。すなわち、
上記の溶液S1中のポリイソシアネートプレポリマーA1のNCO当量 323g/eq、NCOモル数=722×0.54/323(p)、
ポリカプロラクトンジオールのOH当量 250g/eq、当該ポリカプロラクトンジオール由来のOH基モル数=201/250(q)、
トリプロピレングリコールのOH当量 96g/eq、当該トリプロピレングリコール由来のOH基モル数=33/96(r)、
架橋点間分子量=(323p+250q+96r)/p=517 となる。
-実施例2~8、比較例1~4の塗料組成物-
下記表1に示す樹脂配合により、上記と同様にして、実施例2~8の塗料組成物と比較例1~4の塗料組成物を製造した。
ポリカーボネートジオール(b3-1);商品名「プラクセルCD205PL」、固形分100%、分子量500、官能基数2、よってOH当量が250g/eq、ダイセル化学工業社製
1,6-ヘキサンジオール(b4-1);固形分100%、分子量118、官能基数2、よってOH当量が59g/eq、和光純薬製
上記塗料組成物における、樹脂固形分(NV)、粘度、平均官能基当量及び架橋点間分子量は下記表1に示すとおりである。
-金属素材への塗装-<実施例1~8、比較例1~4>
カチオン電着された塗装鉄板(リン酸亜鉛化成被膜処理PB-L3020 日本テストパネル社製)に、中塗り塗料として「プレサフグレー062-1940」(ロックペイント社製)をスプレー塗装にて乾燥膜厚が30μmになるように塗装した後、室温で10分間放置し、ついで、乾燥機を用いて140℃の雰囲気温度で20分間乾燥・硬化させた。塗装物を取り出し、室温放置した。次いで、ベース塗料として「ハイロックDX」(高耐光性ウレタン塗料 主剤/硬化剤/シンナー=4部/1部/2部 日本ペイント社製)をスプレーガンを用いて、乾燥膜厚が15μmになるように塗装した後、室温で10分間放置し、ついで、乾燥機を用いて140℃の雰囲気温度で20分間乾燥・硬化させた。ついで塗装物を取りだし室温にしてから、上記実施例1~8及び比較例1~4で得られた塗料組成物をスプレーガンにて乾燥膜厚が30μmになるように塗装し、室温で10分間放置後、140℃雰囲気温度の乾燥機に20分間入れて乾燥硬化して、鉄素材塗装物ならびに試験片を得た。
上述で作製した鉄素材複層塗膜試験片の各クリヤー塗膜の表面の光沢度をデジタル変角光沢度計(UGV-5D スガ試験機社製)にて測定角度60°で測定し、試験前の光沢度L0を求めた。そして、表面性状測定機(HEIDON-14DR 新東科学社製)の水平台上に、各試験片のクリヤー塗膜面を上にして置き、圧子としてスチールウール#0000を用い、175g/cm2の荷重をかけて、ストローク25mm、速度30mm/sec.で10往復摩擦した。そして、2時間放置後にL0測定に用いたのと同じ光沢度計で、クリヤー塗膜表面の光沢度L1を測定した。
B: 90%以上、95%未満
C: 70%以上、90%未満
D: 50%以上、70%未満
E: 50%未満
<耐衝撃性>
デュポン式衝撃試験機の水平台上に、上述で作製した鉄素材複層塗膜試験片の各クリヤー塗膜の表面を上にして、落錘重量100g、撃芯の尖端直径1/2インチの条件で行ない、塗膜に損傷を生じない最大落錘高さを評価して表2に示した。その最大落錘高さの値が大きいほど良好な塗膜であり、100cmを最大値とする。なお塗膜の損傷とは、塗膜の剥れ、及び下塗り層にまで達するクラックが生じることを意味する。
B: 90cm以上、100cm未満
C: 70cm以上、90cm未満
D: 50cm以上、70cm未満
E: 50cm未満
<鉛筆硬度>
上述で作製した鉄素材複層塗膜試験片の各クリヤー塗膜の表面対して、JIS-K5600に準拠し、三菱鉛筆(株)製ユニ(登録商標)を用いて鉛筆とクリヤー塗膜の角度が45度となるようにして引っ掻き、押傷を付け、2時間放置して再度表面の状態を観察した際に、押傷の修復(引っ掻いた際に生じた凹部が復元して元の表面状態に修復される)が認められたが、その押傷の修復する最大筆硬度を表2に示した。なお、その押傷の修復する最大鉛筆硬度以上では、塗膜の剥れが認められた。よって、その最大鉛筆硬度の値が大きいほど良好な塗膜である。
<密着性評価方法>
上述で作製した鉄素材複層塗膜試験片のクリヤー塗膜に2mm間隔で碁盤目状にカッターで切り込みを入れて、100個の桝目を作成し、その上に粘着テープを貼り付け、該テープを剥がし、塗膜の剥離状態を観察した。100枡中、剥離せず残存した升目数を数えて評価した結果を表2に示した。その剥離せず残存した升目数の値が大きいほど良好な塗膜である。
<透過率>
石英ガラス基板(50mm×50mm)に、乾燥膜厚が100μmになるようにクリヤー塗量組成物を塗布し、室温で10分間放置し、ついで140℃の雰囲気温度で20分間乾燥・硬化させた。
<ガラス転移温度 Tg>
石英ガラス基板(50mm×50mm)に、乾燥膜厚が100μmになるようにクリヤー塗量組成物を塗布し、室温で10分間放置し、ついで140℃の雰囲気温度で20分間乾燥・硬化させた。
Claims (7)
- 平均官能基当量が、180~360g/eqであることを特徴とする請求項1に記載の塗料組成物。
- ポリイソシアネートプレポリマー(A)の原料モノマーが、アクリロイルオキシエチルイソシアネート、メタクリロイルオキシエチルイソシアネート及びメタクリロイルオキシエトキシエチルイソシアネートからなる群より選ばれる少なくとも1種であることを特徴とする請求項1または2に記載の塗料組成物。
- ポリオール(B)が、ポリラクトンポリオール(b1)、ポリエーテルポリオール(b2)、ポリカーボネートジオール(b3)、及び脂肪族ジオール(b4)からなる群より選ばれる少なくとも1種を含むことを特徴とする請求項1~3のいずれかに記載の塗料組成物。
- 請求項1~4のいずれかに記載の塗料組成物からなるクリヤー塗膜を、ベース塗膜の上に形成することを特徴とする複層塗膜形成方法。
- 請求項5に記載の複層塗膜形成方法で得られることを特徴とする複層被膜。
- 請求項5に記載の複層塗膜形成方法で得られた複層塗膜を備えることを特徴とする自動車外装用部品。
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JP2013213207A (ja) * | 2012-03-09 | 2013-10-17 | Arakawa Chem Ind Co Ltd | 活性エネルギー線硬化型自己修復性塗料組成物 |
JP2013216854A (ja) * | 2012-03-14 | 2013-10-24 | Fuji Xerox Co Ltd | 表面保護膜 |
CN104254582A (zh) * | 2012-04-24 | 2014-12-31 | 昭和电工株式会社 | 透明粘合粘接片用组合物、其制造方法和透明粘合粘接片 |
JP2015038164A (ja) * | 2011-09-22 | 2015-02-26 | 富士ゼロックス株式会社 | 透明保護膜 |
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TWI426110B (zh) * | 2011-02-01 | 2014-02-11 | Hwa Pao Resins Chemical Co Ltd | 自修復塗料組成物及其製造方法 |
JP5877099B2 (ja) * | 2012-03-23 | 2016-03-02 | 昭和電工株式会社 | 透明粘着シート用組成物 |
DE102013204395A1 (de) | 2013-03-13 | 2014-09-18 | Evonik Industries Ag | Oberflächenvergütung auf Basis von vernetzbaren Fluorpolymeren |
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JP5615704B2 (ja) | 2014-10-29 |
CN102076797A (zh) | 2011-05-25 |
CN102076797B (zh) | 2014-03-12 |
EP2298842A4 (en) | 2015-04-22 |
KR20110019444A (ko) | 2011-02-25 |
JPWO2010001773A1 (ja) | 2011-12-22 |
TWI494388B (zh) | 2015-08-01 |
EP2298842B1 (en) | 2018-02-21 |
EP2298842A1 (en) | 2011-03-23 |
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