Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
• • 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
• • 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
• • 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
• • 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
• • 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
  • C09D175/08—Polyurethanes from polyethers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D201/00—Coating compositions based on unspecified macromolecular compounds

Definitions

• the present invention relates to a coated body having a plastic substrate and a coating film formed on the surface thereof, and more particularly to a self-repairing painted body for automobile interior.
• Plastic molded products are molded products of polymer materials with plasticity, and are used in mobile phones, home appliances, OA equipment, automobile interior parts, etc.
• the surface of these plastic molded products is decorated, It may be painted to add functionality. Paints for coating plastic moldings (plastic coatings) are used for decoration purposes, and depending on the application of the plastic moldings, the coating film is resistant to scratches, abrasion resistance, anti-fading, It may be required to provide functions such as sebum, high gloss, high weather resistance, and electrical insulation.
• Patent Document 1 discloses a self-polymer obtained by reacting polyisocyanate, acrylic polyol, and polycarbonate polyol. A restorative coating composition is disclosed.
• the self-healing coating composition described in Patent Document 1 is excellent in self-healing properties against scratches on the coating film, and is excellent in transparency, smoothness, and repair limit strength of the coating film.
• Patent Document 2 discloses a coating material for a soft coating film containing fine particles having a particle diameter of 1 nm to 300 nm.
• the coating material for a fine coating film containing fine particles described in Patent Document 2 has excellent anti-fouling and anti-resistance properties while maintaining the original properties of a soft coating material having excellent scratch resistance and being resistant to cracking. It is also said to have chemical properties.
• an object of the present invention is to provide a coated body having a coating film with good scratch resistance and chemical resistance.
• the inventors of the present invention have conducted extensive research in view of the above problems. As a result, it was found that the above problems can be solved by adjusting the coating composition so that the glass transition temperature of the coating film and the Young's modulus of the coating film satisfy predetermined numerical conditions, and the present invention is completed. It came. Specifically, the present invention provides the following.
• the glass transition temperature of the coating film is 30 ° C. or higher.
• the Young's modulus of the coating film is 1000 N / mm 2 or less, and the elongation percentage of the coating film is 80% or more.
• the coating film is formed from a main agent containing at least the following (A) and (B) as a hydroxyl group-containing component and a self-repairing paint containing the following (C): [3]
• the painted body according to any one of the above.
• (C) Isocyanate-based curing agent is Isocyanate-based curing agent.
• the ratio (B) / (A) of the hydroxyl value of the component (A) to the hydroxyl value of the component (B) is 0.5 or more and 1.5 or less. Painted body.
• the mass average molecular weight of the component (A) is 500 or more and 2000 or less, and the mass average molecular weight of the component (B) is 5000 or more and 100,000 or less, [4] to [6] The painted body in any one.
• the coating composition of the present invention has been adjusted so that the glass transition temperature of the coating film and the Young's modulus of the coating film satisfy predetermined numerical conditions, the coating film formed on the coating body is resistant to Scratch resistance and chemical resistance are compatible.
• the coated body of the present invention has a plastic substrate and a coating film formed on the surface thereof.
• this coating film satisfies the following conditions (1) and (2).
• the glass transition temperature of the coating film is 30 ° C. or higher.
• the Young's modulus of the coating film is 1000 N / mm 2 or less, and the elongation percentage of the coating film is 80% or more.
• the coated body of the present invention has a glass transition temperature of 30 ° C. or higher.
• the glass transition temperature of the coating film is 30 ° C. or higher, the chemical resistance of the coating film becomes good.
• the glass transition temperature of a coating film may be observed in multiple numbers, in such a case, what is necessary is just to let the addition average of several glass transition temperature be the glass transition temperature of a coating film.
• the coating film preferably has a plurality of glass transition temperatures.
• the glass transition temperature of the coating film is preferably 30 ° C. or more and 60 ° C. or less, and more preferably 30 ° C. or more and 50 ° C. or less. When the glass transition temperature of the coating film is within the above range, the chemical resistance and the scratch resistance of the coating film can be satisfactorily achieved.
• the Young's modulus of the coating film of the coated body of the present invention is 1000 N / mm 2 or less.
• the Young's modulus of the coating film satisfies this condition, the coating film has excellent flexibility, the self-repairing property of the scratches on the coating film is good, and the scratch resistance of the coating film is good.
• Young's modulus of a coating film it measured at 23 degreeC based on the measuring method of the static Young's modulus of JISZ2280.
• Young's modulus of the coating film is preferably 50 N / mm 2 or more 500 N / mm 2 or less, more preferably 85N / mm 2 or more 255N / mm 2 or less.
• the elongation percentage of the coating film of the coated body of the present invention is 80% or more.
• the coating film has excellent flexibility, the self-repairing property of the scratches on the coating film is good, and the scratch resistance of the coating film is good.
• about the elongation rate of the coating film it measured at 23 degreeC based on the measuring method of the elongation at the time of cutting
• the elongation percentage of the coating film is preferably 85% or more and 150% or less, and more preferably 95% or more and 125% or less. When the elongation percentage of the coating film is within the above range, the chemical resistance and the scratch resistance of the coating film can be satisfactorily achieved.
• the coating film of the coated body of the present invention preferably has a molecular weight between crosslinks of 700 or more and 1200 or less, and more preferably 750 or more and 1000 or less.
• crosslinking is what divided the number average molecular weight of the polymer which comprises a coating film by the number of crosslinkable functional groups.
• the dry film thickness of the coating film formed on the coated body of the present invention is not particularly limited as long as the chemical resistance and scratch resistance of the coating film can be satisfactorily achieved, but adhesion to the base material From the point of achieving both good compatibility and paintability, it is preferably 10 ⁇ m or more and 50 ⁇ m or less, and more preferably 20 ⁇ m or more and 40 ⁇ m or less.
• the coating film of the coated body of the present invention has a predetermined glass transition temperature, Young's modulus, and elongation, but such a coating film is generally a resin component used when forming a coating film. It can be obtained by adjusting the glass transition temperature and the crosslinking density.
• the self-healing paint for forming the coating film of the present invention it is preferable to use a urethane-based paint.
• the main ingredient includes at least the following (A) and (B) as a hydroxyl group-containing component.
• a self-healing paint containing (C) can be used.
• the component (A) is a polycarbonate diol having a hydroxyl value of 80 mgKOH / g or more and 200 mgKOH / g or less, and preferably has a glass transition temperature of ⁇ 100 ° C. or more and 0 ° C. or less.
• a coating film using such a polycarbonate diol is excellent in elasticity, and by using this, it is possible to form a coating film excellent in self-healing properties.
• Examples of the polycarbonate diol used in the present invention include compounds obtained by polycondensation reaction of a known diol and a carbonylating agent. Specifically, for example, “Plaxel CD205PL”, “Plaxel CD210”, “Plaxel CD220”, “Plaxel CD220PL” manufactured by Daicel Chemical Industries, Ltd.
• These polycarbonate diols may be used alone or in combination of two or more.
• the mass average molecular weight of the polycarbonate diol is preferably 500 or more and 2000 or less.
• the hydroxyl value of the polycarbonate diol is preferably 90 mgKOH / g or more and 200 mgKOH / g or less, and more preferably 100 mgKOH / g or more and 160 mgKOH / g or less.
• the component (B) is a resin component (polyol) having a hydroxyl value of 80 mgKOH / g or more and 200 mgKOH / g or less, and preferably has a glass transition temperature of 50 ° C or more and 120 ° C or less.
• This resin component is a compound having two or more hydroxyl groups in one molecule and, like the component (A), forms a urethane bond by reacting with an isocyanate group of polyisocyanate, but has a glass transition temperature of Since it is 50 degreeC or more and 120 degrees C or less, it contributes to the improvement of the glass transition temperature of the whole coating film, and contributes to a chemical-resistant improvement as a result.
• Examples of the resin component used in the present invention include acrylic polyol, polyester polyol, polyether polyol, hydroxyl group-containing acrylic silicone resin, and hydroxyl group-containing fluorine resin.
• acrylic polyol, polyester polyol are particularly preferable.
• a polyether polyol is preferable.
• commercially available products can be suitably used. For example, they can be easily obtained by using a monomer having a hydroxyl group when synthesizing an acrylic resin, a polyester resin, a polyether resin, an acrylic silicone resin, or a fluorine resin. Can do.
• (B) component is resin components other than polycarbonate diol.
• the resin component as the component (B) preferably has a mass average molecular weight of 5,000 or more and 100,000 or less. By setting the mass average molecular weight of the resin component within the above range, the coating film formability can be improved, and the workability of the self-repairing paint can be improved.
• the hydroxyl value of the resin component (B) is preferably 85 mgKOH / g or more and 160 mgKOH / g or less, and more preferably 100 mgKOH / g or more and 150 mgKOH / g or less.
• the ratio (B) / (A) of the hydroxyl value of the component (A) to the hydroxyl value of the component (B) is preferably 0.5 or more and 1.5 or less, More preferably, it is 1.2 or less.
• the blending amount of the resin component of the component (B) in the self-healing coating composition is preferably 40 parts by mass or more and 150 parts by mass or less, and 50 parts by mass or more and 120 parts by mass or less per 100 parts by mass of the component (A). It is more preferable that By making the blending amount of the resin component of the component (B) within the above range, the chemical resistance and the scratch resistance of the coating film can be made well compatible.
• hydroxyl-containing component although it may contain hydroxyl-containing resin ((G) component) other than (A) component and (B) component, (A) component and (B) with respect to the total amount of a hydroxyl-containing component.
• the total amount of the components is preferably 70% by mass or more.
• the ratio (NCO mol% / OH mol%) of the hydroxyl group concentration (OH mol%) derived from the component (A) and the component (B) to the isocyanate group concentration (NCO mol%) is 0.9. It is preferable to adjust the blending amount of the component (C) so as to be 1.3 or more. When adjusted to this range, unreacted hydroxyl groups and isocyanate groups are reduced, so that a coating film having good water resistance and film hardness can be obtained.
• the organic solvent is mainly used for dissolving the hydroxyl group-containing component.
• the organic solvent those generally used in the paint field can be used. More specifically, aromatic hydrocarbons such as toluene, xylene, Solvesso 100 and Solvesso 150, esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and isophorone, Examples include aliphatic solvents such as alcohols, glycols, acetates, and mineral spirits. These are appropriately selected in consideration of solubility, evaporation rate, safety, and the like.
• the organic solvent mentioned above may be used independently, and 2 or more types may be mixed and used for it.
• the self-healing coating composition used for forming the coated body of the present invention includes conventional crosslinking catalysts, colorants, various pigments, slip agents, surface conditioners, ultraviolet absorbers and the like. You may mix
• [(A) component] (A1) “Duranol G3450J” (manufactured by Asahi Kasei Corporation, resin component 100%, hydroxyl value 140 mgKOH / g) (A2) “Desmophen (registered trademark) C1100” (manufactured by Covestro, resin component 100%, hydroxyl value 110 mg KOH / g)
• Component (B)] (B1) “Acridic A859B” (manufactured by DIC, acrylic polyol, resin component 70% by weight, hydroxyl value of resin 143 mgKOH / g) (B2) “Acridic WFU-580” (manufactured by DIC, acrylic polyol, 62% by weight of resin component, hydroxyl value of resin 87 mgKOH / g) (B3) “Dianar JR-6642” (manufactured by Mitsubishi Chemical Corporation, acrylic polyol, resin component 57 wt%, resin hydroxyl value 144 mg KOH / g)
• Component (C) (C1) “Desmodur N3300” (manufactured by Sumika Covestro Urethane Co., Ltd., isocyanurate-modified hexamethylene diisocyanate, NCO concentration 21.8 wt%, nonvolatile content 100 wt%) (C2) “Duranate MHG-80B” (manufactured by Asahi Kasei Corporation, isocyanurate-modified hexamethylene diisocyanate, NCO concentration of 15.1% by weight, nonvolatile content of 100% by weight) (C3) “Desmodur N3580” (manufactured by Sumika Covestro Urethane Co., Ltd., butyl acetate solution of isocyanurate-modified hexamethylene diisocyanate, NCO concentration 15.4 wt%, nonvolatile content 80 wt%)
• [Pigment dispersion] (E1) Carbon black dispersion (manufactured by Nichihiro Bix, 23% by weight of active ingredient) [Other additives] (F1) “BYK306” (silicon-based surface conditioner, manufactured by Big Chemie) (F2) “TINUVIN400” (UV absorber, hydroxyphenyltriazine (HPT) UV absorber, manufactured by BASF) (F3) “TINUVIN123” (light stabilizer, hindered amine light stabilizer, manufactured by BASF)
• Glass transition temperature of coating film Tg (m)
• the coating films of the coated bodies of Examples 1 to 4 and Comparative Examples 1 to 3 were peeled from the polypropylene resin plate, and then cut into a sample length of 50 mm and a width of 8 mm to prepare a measurement sample.
• RSA G2 dynamic viscoelasticity measuring device
• the glass transition temperature was defined as the dynamic glass transition temperature measured as the temperature indicating the maximum value of the modulus / storage modulus.
• the molecular weight of the resin between crosslinks is referred to as the molecular weight between crosslinks, and is represented by the reciprocal of the crosslink density.
• the molecular weight between crosslinks of the cured coating film of the present invention is a theoretical calculation value obtained by applying the minimum value of the storage elastic modulus obtained at the time of measuring the glass transition temperature of the cured coating film to the following rubber viscoelasticity theoretical formula. .
• n E ′ / 3RT here, n: Crosslink density (mol / cc) 1 / n: Molecular weight between crosslinks (cc / mol) R: Gas constant (8.314 J / K / mol) T: Absolute temperature (K) when the storage elastic modulus is E ′ E ′: Minimum value of storage elastic modulus (Pa)
• Young's modulus Young's modulus was measured by the following method. First, the coating films of the coated bodies of Examples 1 to 4 and Comparative Examples 1 to 3 were peeled from the polypropylene plate and cut into strips having a length of 50 mm and a width of 10 mm to obtain measurement samples. Next, using a precision universal testing machine Autograph AG-1 100 kN (manufactured by Shimadzu Corporation), measurement was performed under the conditions of load cell: 100 N, measuring temperature: 23 ° C., pulling speed: 20 mm / min, and distance between chucks: 30 mm. The sample was pulled in the longitudinal direction until the sample was broken to obtain a stress strain curve. Subsequently, the Young's modulus was calculated from the tangent of the rising portion of the obtained stress strain curve.
• the coating films of the coated bodies of Examples 1 to 4 and Comparative Examples 1 to 3 were peeled off from the polypropylene plate and cut into 50 mm length ⁇ 10 mm width to obtain a measurement sample.
• the sample for measurement was subjected to a tensile test at 23 ° C. using a precision universal testing machine Autograph AG-1 100 kN manufactured by Shimadzu Corporation at a load cell of 100 N, a measurement temperature of 23 ° C., and a tensile speed of 20 mm / min.
• the elongation percentage of the coating film was calculated using the following formula.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Laminated Bodies (AREA)
• Paints Or Removers (AREA)
• Application Of Or Painting With Fluid Materials (AREA)
• Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
• Polyurethanes Or Polyureas (AREA)

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• 2018
  • 2018-03-30 JP JP2018067613A patent/JP6701582B2/ja active Active
• 2019
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  • 2019-03-19 CN CN201980023663.6A patent/CN111936565B/zh active Active
  • 2019-03-19 WO PCT/JP2019/011396 patent/WO2019188574A1/ja active Application Filing

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