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WO2018168987A1 - Matériau de revêtement pour éléments d'intérieur de véhicule, élément d'intérieur de véhicule et procédé de production d'élément d'intérieur de véhicule - Google Patents

Matériau de revêtement pour éléments d'intérieur de véhicule, élément d'intérieur de véhicule et procédé de production d'élément d'intérieur de véhicule Download PDF

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Publication number
WO2018168987A1
WO2018168987A1 PCT/JP2018/010137 JP2018010137W WO2018168987A1 WO 2018168987 A1 WO2018168987 A1 WO 2018168987A1 JP 2018010137 W JP2018010137 W JP 2018010137W WO 2018168987 A1 WO2018168987 A1 WO 2018168987A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyrotaxane
vehicle interior
fluoropolymer
group
paint according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/010137
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English (en)
Japanese (ja)
Inventor
修平 尾知
ヤンシェン セドリックチン
俊 齋藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Inc
Original Assignee
Asahi Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Priority to JP2019506252A priority Critical patent/JP7031660B2/ja
Publication of WO2018168987A1 publication Critical patent/WO2018168987A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60K—ARRANGEMENT OR MOUNTING OF PROPULSION UNITS OR OF TRANSMISSIONS IN VEHICLES; ARRANGEMENT OR MOUNTING OF PLURAL DIVERSE PRIME-MOVERS IN VEHICLES; AUXILIARY DRIVES FOR VEHICLES; INSTRUMENTATION OR DASHBOARDS FOR VEHICLES; ARRANGEMENTS IN CONNECTION WITH COOLING, AIR INTAKE, GAS EXHAUST OR FUEL SUPPLY OF PROPULSION UNITS IN VEHICLES
    • B60K37/00—Dashboards
    • B60K37/20—Dashboard panels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
    • B60R13/02—Internal Trim mouldings ; Internal Ledges; Wall liners for passenger compartments; Roof liners
    • 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
    • C09D105/00—Coating compositions based on polysaccharides or on their derivatives, not provided for in groups C09D101/00 or C09D103/00
    • C09D105/16—Cyclodextrin; Derivatives thereof
    • 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
    • C09D127/00—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 a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/06—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms

Definitions

  • the present invention relates to a paint for a vehicle interior member, a vehicle interior member, and a method for manufacturing the vehicle interior member.
  • Vehicle interior components are hardened by curing the paint for the purpose of protecting the surface, decorating or improving the touch. May have a membrane.
  • a paint is used by painting directly on a vehicle interior base material constituting the vehicle interior member or by painting on a film used by being attached to the vehicle interior base material.
  • the contamination of the member due to the sunscreen agent adhering may be a problem, and the vehicle interior member is required to be resistant to contamination.
  • Patent Document 1 discloses a vehicle interior member film using a fluoropolymer.
  • the vehicle interior member is also required to have excellent scratch resistance.
  • the present inventors have found that it is impossible to achieve both the stain resistance and the scratch resistance for sunscreen agents.
  • the present invention has been made in view of the above problems, and is formed using a paint for a vehicle interior member capable of forming a vehicle interior member excellent in scratch resistance and anti-staining properties against sunscreen agents, and the same.
  • An object of the present invention is to provide a vehicle interior member having a cured film and a method for manufacturing the same.
  • the present inventors can obtain a desired effect when using a paint containing a fluorine-containing polymer having a crosslinkable group, a polyrotaxane having a crosslinkable group, and a curing agent. As a result, they have reached the present invention. That is, the present inventors have found that the above problem can be solved by the following configuration.
  • a fluoropolymer containing a unit based on a fluoroolefin and a unit based on a monomer having a first crosslinkable group, a polyrotaxane having two or more second crosslinkable groups, and the first crosslinkable property And a curing agent having two or more functional groups capable of reacting with at least one of the group and the second crosslinkable group.
  • a fluoropolymer has a glass transition temperature of 50 ° C. or higher.
  • the fluoropolymer further includes units based on a monomer having an alkyl group having a tertiary carbon atom having 3 to 9 carbon atoms or a cycloalkyl group having 4 to 10 carbon atoms in the side chain;
  • the content of the unit based on the monomer having the first crosslinkable group is 1 to 40 mol% with respect to the total units contained in the fluoropolymer, (1) to (3)
  • the coating material in any one of.
  • the polyrotaxane is a polyrotaxane having a cyclodextrin as a cyclic molecule and a polyethylene glycol having both ends blocked with blocking groups as an axis molecule, or a cyclic ester-modified product or a cyclic ether-modified product of the polyrotaxane, (1 ) To (7).
  • the first crosslinkable group and the second crosslinkable group are both hydroxy groups, and the curing agent is an isocyanate curing agent, according to any one of (1) to (12) paint.
  • a vehicle interior member having a vehicle interior base material and a cured film formed from the paint according to any one of (1) to (13) disposed on the vehicle interior base material.
  • the vehicle interior member coating material which can form the vehicle interior member excellent in damage resistance with respect to a scratch resistance and a sunscreen agent, and the vehicle interior member which has a cured film formed using this coating material, and The manufacturing method can be provided.
  • “Unit” is a general term for an atomic group derived from one monomer molecule formed directly by polymerization of a monomer and an atomic group obtained by chemical conversion of a part of the atomic group. is there. The content (mol%) of each unit with respect to all units contained in the polymer can be determined from the charged amount of each monomer.
  • “Acid value” and “hydroxyl value” are values measured according to the method of JIS K 0070-3 (1992), respectively.
  • “Glass transition temperature” is a value measured by the method defined in JIS K 6240 (2011). “Glass transition temperature” is also referred to as “Tg”.
  • “Number average molecular weight” and “weight average molecular weight” are values measured by gel permeation chromatography using polystyrene as a standard substance. “Number average molecular weight” is also referred to as “Mn”, and “weight average molecular weight” is also referred to as “Mw”. “Fluorine content” means the ratio (% by mass) of fluorine atoms to the total mass of the fluoropolymer. The fluorine content can be determined by analyzing the fluoropolymer by nuclear magnetic resonance spectroscopy.
  • the paint for vehicle interior members of the present invention includes a crosslinkable fluorine-containing heavy containing a unit based on a fluoroolefin and a unit based on a monomer having a first crosslinkable group.
  • a paint comprising a coalesced polymer, a crosslinkable polyrotaxane having two or more second crosslinkable groups, and a curing agent.
  • stain resistance refers to the resistance to contamination with sunscreens such as Copatone (registered trademark).
  • a vehicle interior member including a cured film formed from the paint containing a crosslinkable fluoropolymer and a crosslinkable polyrotaxane can achieve both scratch resistance and stain resistance at a high level. ing. Further, as shown in the examples described later, the vehicle interior member having a cured film of a paint containing a crosslinkable polymer other than the crosslinkable fluoropolymer and the crosslinkable polyrotaxane has deteriorated stain resistance. I also know that.
  • the fluoropolymer in the present invention is a monomer having a unit based on a fluoroolefin (hereinafter also referred to as “unit F”) and a first crosslinkable group (hereinafter also referred to as “monomer C”). It is a fluorine-containing polymer having a first crosslinkable group, which includes a unit based on (hereinafter also referred to as “unit C”).
  • a fluoroolefin is an olefin in which one or more hydrogen atoms are substituted with fluorine atoms.
  • one or more hydrogen atoms not substituted with fluorine atoms may be substituted with chlorine atoms.
  • the content of the unit F is preferably 20 to 70 mol%, particularly preferably 40 to 60 mol%, based on all units contained in the fluoropolymer, from the viewpoint of the weather resistance of the cured film.
  • the first crosslinkable group possessed by the monomer C is a functional group (hydroxy group, carboxy group, amino group, etc.) having active hydrogen or a hydrolyzable silyl group (alkoxysilyl) from the viewpoint of curability of the cured film.
  • Group, etc. are preferred, a hydroxy group or a carboxy group is more preferred, and a hydroxy group is particularly preferred.
  • Specific examples of the monomer C include hydroxyalkyl vinyl ether, hydroxycycloalkyl vinyl ether, hydroxyalkyl vinyl ester, hydroxycycloalkyl vinyl ester, hydroxyalkyl allyl ether, hydroxyalkyl allyl ester, hydroxyalkyl acrylate, hydroxyalkyl methacrylate.
  • esters examples include esters. Among these, from the viewpoint of curability of the cured film, hydroxyalkyl vinyl ether and hydroxyalkyl allyl ether are preferable, and 4-hydroxybutyl vinyl ether and 2-hydroxyethyl allyl ether are more preferable.
  • Monomer C may use 2 or more types together.
  • the content of unit C is preferably 1 to 40 mol%, more preferably 5 to 15 mol%, based on the total units contained in the fluoropolymer, from the viewpoint of scratch resistance and contamination resistance of the cured film.
  • the fluorine-containing polymer of the present invention has an alkyl group having a tertiary carbon atom of 3 to 9 carbon atoms or 4 to 10 carbon atoms from the viewpoint of forming a cured film having a high Tg and excellent impact resistance.
  • a unit (hereinafter also referred to as “unit T”) based on a monomer having a cycloalkyl group in the side chain (hereinafter also referred to as “monomer T”).
  • the monomer T contains neither a fluorine atom nor a crosslinkable group.
  • alkyl group and the cycloalkyl group include a tert-butyl group, a neononyl group, a cyclohexyl group, a cyclohexylmethyl group, a 4-cyclohexylcyclohexyl group, and a 1-decahydronaphthyl group.
  • the monomer T is vinyl ether, allyl ether, vinyl ester, allyl ester, acrylic acid ester or methacrylic acid ester, and is an alkyl group having 3 to 9 carbon atoms or a cyclocarbon having 4 to 10 carbon atoms. Monomers having an alkyl group in the side chain are preferred.
  • the monomer T examples include cyclohexyl vinyl ether, tert-butyl vinyl ether, tert-butyl vinyl ester, and neononanoic acid vinyl ester.
  • the monomer T may use 2 or more types together.
  • the content of the unit T is preferably 10 to 45 mol%, more preferably 12 to 40 mol%, more preferably 15 to 40 mol% with respect to the total units contained in the fluoropolymer, from the viewpoint of adjusting the Tg of the fluoropolymer. 35 mol% or 36 to 40 mol% is particularly preferred, and 36 to 40 mol% is particularly preferred.
  • the fluoropolymer further includes units other than the units F, C and T (units based on monomers other than the monomer F, the monomer C and the monomer T.
  • units H units based on monomers other than the monomer F, the monomer C and the monomer T.
  • monomers that can constitute the unit H include alkyl vinyl ethers (nonyl vinyl ether, hexyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, etc.), alkyl allyl ethers (ethyl allyl ether, hexyl allyl ether, etc.), carboxylic acids
  • Examples include vinyl esters (such as acetic acid, butyric acid, and propionic acid) and allyl esters of carboxylic acids (such as acetic acid, butyric acid, and propionic acid). Two or more of these monomers may be used in combination.
  • the content of the unit H is preferably 50 mol% or less,
  • the content of unit F, unit C, unit T, and unit H with respect to all units contained in the fluoropolymer In this order, 20 to 70 mol%, 1 to 40 mol%, 10 to 45 mol%, and 0 to 50 mol% are preferable.
  • the Mn of the fluoropolymer is preferably 3,000 to 50,000, more preferably 5,000 to 30,000, and particularly preferably 5,000 to 20,000.
  • the hydroxyl value of the fluorinated polymer is preferably from 1 to 150 mgKOH / g, more preferably from 1 to 100 mgKOH / g, particularly preferably from 15 to 50 mgKOH / g.
  • the fluorine content of the fluoropolymer is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, and particularly preferably 20 to 30% by mass from the viewpoint of the stain resistance and weather resistance of the cured film. When the fluorine content of the fluoropolymer is 10% by mass or more, the weather resistance of the cured film is more excellent.
  • the Tg of the fluoropolymer is preferably 35 ° C. or higher, more preferably 50 ° C. or higher, from the viewpoint of stain resistance of the cured film.
  • the Tg of the fluoropolymer is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and particularly preferably 100 ° C. or lower.
  • the content of the fluoropolymer in the present paint is 20 to 80 with respect to the total amount of the fluoropolymer, polyrotaxane and curing agent of the paint of the present invention from the viewpoint of stain resistance and weather resistance of the cured film. % By mass is preferable, and 25 to 75% by mass is more preferable.
  • the ratio of the mass of the fluoropolymer to the mass of the polyrotaxane in this paint (the mass of the fluoropolymer / the mass of the polyrotaxane) has both the stain resistance and the scratch resistance of the cured film, and is also stretchable. From the viewpoint of superiority, it is preferably 1.5 or more, more preferably 2.0 to 90, and particularly preferably 3.0 to 30.
  • the polyrotaxane in the present invention is a crosslinkable polyrotaxane having a second crosslinkable group.
  • the crosslinkable polyrotaxane may be directly cross-linked (bonded) with the fluoropolymer, or may be cross-linked with the fluoropolymer through a curing agent described later.
  • Polyrotaxane is a quasi-polyrotaxane in which openings of cyclic molecules such as cyclodextrin are skewered by linear shaft molecules, and multiple cyclic molecules enclose the shaft molecules (both ends of the shaft molecules). And a molecular complex in which a blocking group is arranged so that the cyclic molecule is not released.
  • the polyrotaxane has a cyclic molecule, a shaft molecule that includes the cyclic molecule in a skewered manner, and a blocking group that is disposed at both ends of the shaft molecule and prevents the removal of the cyclic molecule.
  • a polyrotaxane in addition to the said molecular complex, includes the crosslinked body by which the said molecular complex was bridge
  • an embodiment in which a cyclic molecule such as cyclodextrin is modified to improve compatibility and solubility is also included in the polyrotaxane.
  • the cyclic molecule can move freely on the axis molecule. Therefore, for example, when a cyclic molecule has a crosslinkable group, the crosslinkable group on the cyclic molecule moves with the free movement of the cyclic molecule, so that the cross-linked structure formed by the polyrotaxane is flexible against an applied impact. Can be dealt with. That is, the cross-linked structure can exhibit a force for correcting the disorder of the cross-linked structure caused by the impact without being destroyed by the impact (hereinafter, this effect is also referred to as “self-repairing”).
  • the cured film is excellent in scratch resistance due to the excellent self-healing property of the crosslinked structure formed by the polyrotaxane, as well as the improved curability of the cured film due to the crosslinking between the polyrotaxane and the fluoropolymer.
  • the axial molecule constituting the polyrotaxane is not particularly limited as long as it is a linear molecule that is included in the cyclic molecule and can be integrated non-covalently with the cyclic molecule.
  • “linear” of the axial molecule that is linear means substantially “linear”.
  • the axial molecule may have a branched chain as long as the cyclic molecule as a rotor is rotatable or the cyclic molecule is slidable on the axial molecule.
  • the length of the “straight chain” is not particularly limited as long as the cyclic molecule can slide or move on the axial molecule.
  • the Mw of the axial molecule is preferably 1,000 or more, more preferably 5,000 or more, and particularly preferably 10,000 or more. Further, the Mw of the axial molecule is preferably 100,000 or less, more preferably 50,000 or less, and particularly preferably 40,000 or less. If the Mw of the axial molecule contained in the polyrotaxane is 1,000 or more, the compatibility between the polyrotaxane and the fluoropolymer is excellent, and the curability of the cured film is improved, so that the scratch resistance of the cured film is further improved. Cheap. If the Mw of the axial molecule contained in the polyrotaxane is 100,000 or less, the fluoropolymers crosslinked via the polyrotaxane become dense, and the contamination resistance of the cured film is further improved.
  • the linear shaft molecules constituting the polyrotaxane include polycaprolactone, styrene-butadiene copolymer, isobutene-isoprene copolymer, polyisoprene, natural rubber, polyalkylene glycol, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran , Polydimethylsiloxane, polyethylene, polypropylene, ethylene-polypropylene copolymer, and the like.
  • the axial molecules are preferably polyethylene glycol, polypropylene glycol, polytetrahydrofuran, polyethylene glycol-polypropylene glycol copolymer, polyisoprene, polyisobutylene, polybutadiene, polydimethylsiloxane, polyethylene and polypropylene.
  • a particularly preferred axial molecule is polyethylene glycol.
  • Specific examples of the blocking group that blocks both ends of the axial molecule include dinitrophenyl group, adamantyl group, trityl group, fluorescein, and pyrene.
  • the terminal hydroxy group of polyethylene glycol can be converted to a carboxy group and reacted with 1-adamantanamine to block both ends of polyethylene glycol.
  • any cyclic molecule can be used as long as it is a cyclic molecule that can include the axial molecule.
  • Specific examples of the cyclic molecule include cyclodextrin ( ⁇ -cyclodextrin, ⁇ -cyclodextrin, ⁇ -cyclodextrin, dimethylcyclodextrin, glucosylcyclodextrin, etc.), crown ether, benzocrown, dibenzocrown, dicyclohexanocrown. And derivatives thereof.
  • cyclodextrin is particularly preferable.
  • the crosslinkable group possessed by the polyrotaxane may be possessed by a cyclic molecule, may be possessed by an axial molecule, or preferably possessed by a cyclic molecule.
  • the cyclic molecule is a cyclodextrin, it has a hydroxy group, and this hydroxy group can be converted into another crosslinkable group.
  • crown ether having a crosslinkable group or the like can also be used. Since a polyrotaxane usually includes a plurality of cyclic molecules in one axial molecule, when the cyclic molecule has a crosslinkable group, the polyrotaxane has two or more crosslinkable groups. Moreover, also when it has a crosslinkable group in the blocking group of an axial molecule, since the blocking group exists in both ends of an axial molecule, the polyrotaxane has two or more crosslinking groups.
  • an ester-modified product or an ether-modified product obtained by ring-opening addition of a cyclic ester or a cyclic ether to a polyrotaxane having a cyclic molecule having a functional group such as a hydroxy group can also be used.
  • a modified product obtained by ring-opening addition of a cyclic ester or a cyclic ether to the hydroxyl group of cyclodextrin, which is a cyclic molecule is known (see, for example, JP-A-2007-91938). It can be used as a polyrotaxane having a crosslinkable group.
  • generated by ring-opening addition of cyclic ester and cyclic ether to the hydroxy group of cyclodextrin is a group which has a hydroxyl group at the terminal.
  • the cyclic ether include alkylene oxides such as ethylene oxide and propylene oxide.
  • the cyclic ester include ⁇ -caprolactone, ⁇ -butyrolactone, and ⁇ -valerolactone.
  • the second crosslinkable group in the polyrotaxane is preferably a hydroxy group and a carboxy group, and is preferably a hydroxy group from the viewpoint of crosslinkability with a curing agent.
  • the hydroxyl value of the polyrotaxane is preferably 200 mgKOH / g or less, more preferably 10 to 200 mgKOH / g, and further preferably 50 to 150 mgKOH / g. 50 to 100 mgKOH / g is particularly preferable.
  • the hydroxyl value of the polyrotaxane is 10 mgKOH / g or more, the cured film has excellent scratch resistance, and when it is 200 mgKOH / g or less, the cured film has excellent water resistance.
  • the Tg of the polyrotaxane is preferably 0 ° C. or lower, more preferably 0 ° C. or lower and ⁇ 60 ° C. or higher from the viewpoint of compatibility with the fluoropolymer.
  • the content of the polyrotaxane in the present paint is preferably 0.1 to 30% by mass with respect to the total amount of the fluoropolymer, the polyrotaxane and the curing agent in the present paint, from the viewpoint of scratch resistance of the present cured film. 20% by mass is more preferable, and 5 to 15% by mass is particularly preferable.
  • the curing agent in the present invention is a compound having two or more functional groups capable of reacting with both the first crosslinkable group and the second crosslinkable group.
  • the number of functional groups in the curing agent is usually 30 or less.
  • curing agents include isocyanate curing agents, amine curing agents (melamine resins, guanamine resins, sulfoamide resins, urea resins, aniline resins, etc.), ⁇ -hydroxyalkylamide curing agents, epoxy curing agents ( Triglycidyl isocyanurate-based curing agents and the like) and carbodiimide-based curing agents. Two or more curing agents may be used in combination.
  • the curing agent is preferably an isocyanate curing agent from the viewpoint of adhesion between the cured film and the substrate and curability of the paint. .
  • isocyanate curing agent examples include a curing agent having two or more isocyanate groups and a curing agent having two or more blocked isocyanate groups (hereinafter, also referred to as “blocked isocyanate curing agent”). Is mentioned.
  • the former curing agent examples include alicyclic polyisocyanates such as isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (HMDI), methylcyclohexane diisocyanate, and bis (isocyanatomethyl) cyclohexane, hexa
  • aliphatic polyisocyanates such as methylene diisocyanate (HDI), dimer acid diisocyanate and lysine diisocyanate, and modified products (biuret, isocyanurate, adduct, etc.) of these compounds.
  • An adduct is a compound having an isocyanate group obtained by reacting a polyisocyanate with a low molecular weight compound having active hydrogen.
  • the low molecular weight compound having active hydrogen include water, polyhydric alcohol, polyamine, and alkanolamine. Specific examples include ethylene glycol, propylene glycol, trimethylolpropane, glycerin, sorbitol, ethylenediamine, ethanolamine, and diethanolamine.
  • a polyhydric alcohol is particularly preferable.
  • an adduct of the above compound is preferable, an adduct of aliphatic polyisocyanate is more preferable, and an adduct of HDI is particularly preferable.
  • the blocked isocyanate curing agent can be produced by reacting the polyisocyanate with a blocking agent.
  • blocking agents include alcohols (methanol, ethanol, benzyl alcohol, etc.), phenols (phenol, crezone, etc.), lactams (caprolactam, butyrolactam, etc.), oximes (cyclohexanone, oxime, methyl ethyl ketoxime, etc.) Can be mentioned.
  • the content of the curing agent is preferably 10 to 200 parts by mass, more preferably 30 to 170 parts by mass, and particularly preferably 50 to 150 parts by mass with respect to 100 parts by mass of the fluoropolymer in the paint. If content of a hardening
  • the paint may contain a curing catalyst.
  • the curing catalyst is a compound that accelerates the curing reaction when the above-described curing agent is used, and can be selected from known curing catalysts according to the type of the curing agent.
  • the content of the curing catalyst is preferably 0.00001 to 0.01 parts by mass with respect to 100 parts by mass of the curing agent.
  • This paint may contain components other than the above if necessary.
  • components other than the above include dispersion media and solvents (water, organic solvents, etc.), ultraviolet absorbers, light stabilizers (hindered amine light stabilizers, etc.), matting agents (ultrafine powder synthetic silica, etc.), leveling agents, Surface conditioner, surfactant, degassing agent, plasticizer, filler, heat stabilizer, thickener, dispersant, antistatic agent, rust inhibitor, silane coupling agent, antifouling agent, low contamination treatment Agents.
  • This paint can be used as a solution type (ie, a paint containing a solvent capable of dissolving a fluoropolymer), a water dispersion type, or a powder type (ie, a powder paint substantially free of a solvent).
  • a solution type is preferable, and a paint containing an organic solvent is more preferable.
  • the content of the solvent in the paint is 1% by mass or less, preferably 0.5% by mass or less, particularly preferably 0% by mass with respect to the total mass of the paint.
  • the solution-type paint is produced, for example, by dissolving the above-described components in a solvent using a stirrer such as a disper.
  • the powder-type paint is produced, for example, by melting and kneading a powdery mixture obtained by mixing each component in advance with an extruder, and crushing the extruded kneaded material after cooling.
  • the method for producing a vehicle interior member according to the present invention is a method in which a coating film is formed on a vehicle interior substrate by coating the coating material, and the coating film is cured to form a cured film.
  • a vehicle interior member having a vehicle interior base material and a fully cured film disposed on the vehicle interior base material is obtained. Since the vehicle interior member obtained in this way has a fully cured film, it is excellent in scratch resistance and contamination resistance.
  • Specific examples of the vehicle interior member include a dashboard (instrument panel), a center console, a door trim, a center cluster, a switch panel, and a shift knob.
  • the present paint may be applied directly to the vehicle interior base material, or may be applied to a film used by being attached to the vehicle interior base material.
  • the film in which the cured film was formed will be affixed on the said vehicle interior base material.
  • the material constituting the vehicle interior base material include polycarbonate resin, acrylic resin, methacrylic resin, acrylonitrile-butadiene-styrene copolymer, polystyrene, polypropylene, and polyester resin (polyethylene terephthalate, polybutylene terephthalate).
  • the material constituting the film include polycarbonate resin, acrylic resin, methacrylic resin, ABS resin, polyolefin resin (polyethylene, polypropylene, etc.), polyvinyl halide resin (polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, Polyvinylidene fluoride, etc.), polyester resins (polyethylene terephthalate, polybutylene terephthalate, etc.), polyamide resins (nylon 6, nylon 66, MXD nylon (metaxylenediamine-adipic acid copolymer), etc.), weight of olefin having substituents And EVA (ethylene-vinyl alcohol copolymer), ethylene-tetrafluoroethylene copolymer, etc.).
  • the film may use two or more of these materials in combination.
  • coating methods for this paint include sponge coating, spray coating, curtain coating (flow coating), roll coating, casting, dip coating, spin coating, die coating, electrostatic coating, static coating Examples thereof include an electrospraying method, an electrostatic dipping method, and a fluid dipping method.
  • the method for drying a coating film containing a solvent include natural drying, vacuum drying, centrifugal drying, heat drying, and the like, and heat drying is preferable from the viewpoint of serving also as a curing treatment described later.
  • the drying temperature of the coating film containing the solvent is preferably 15 to 45 ° C., more preferably 20 to 40 ° C. from the viewpoint of sufficiently volatilizing the solvent.
  • the drying time is preferably 15 minutes to 14 days, more preferably 30 minutes to 10 days.
  • the coating treatment method is a heat treatment.
  • the heating temperature is preferably 40 ° C. to 200 ° C., more preferably 45 ° C. to 150 ° C., from the viewpoint that bubbles or the like hardly occur in the cured film.
  • the heating time is preferably 1 minute to 3 hours, and more preferably 3 minutes to 2 hours.
  • the thickness of the cured film is preferably 5 to 150 ⁇ m, more preferably 10 to 100 ⁇ m. If the thickness of the cured film is 5 ⁇ m or more, the scratch resistance and stain resistance of the cured film are more exhibited, and if it is 150 ⁇ m or less, the vehicle interior member can be reduced in weight.
  • the vehicle interior member of the present invention has the vehicle interior base material and a cured film formed from the paint disposed on the vehicle interior base material. Since the vehicle interior member of the present invention has a cured film of the present paint, it is excellent in scratch resistance and contamination resistance.
  • the vehicle interior member of the present invention can be manufactured, for example, by the above-described method for manufacturing a vehicle interior member.
  • the fluoropolymer 1 contains 50 mol%, 39 mol%, and 11 mol% of units based on CTFE, units based on CHVE, and units based on HBVE in this order with respect to all units contained in the fluoropolymer 1. It was a polymer. Further, the fluoropolymer 1 had a Tg of 55 ° C., a fluorine content of 23.7% by mass, a hydroxyl value of 50 mgKOH / g, and Mn of 12,000.
  • Fluoropolymer 2 The monomer and ethyl vinyl ether (EVE) used in Production Example of Fluoropolymer 1 were used, and the amount of each monomer was adjusted to be similar to that in Production Example of Fluoropolymer 1 and contained. Fluoropolymer 2 was obtained.
  • the fluoropolymer 2 is composed of units based on CTFE, units based on CHVE, units based on HBVE, and units based on EVE in this order of 50 mol% and 15 mol% with respect to all units contained in the fluoropolymer 2.
  • the polymer contained 10 mol% and 25 mol%.
  • Fluoropolymer 2 had a Tg of 37 ° C., a fluorine content of 26.7% by mass, a hydroxyl value of 53 mgKOH / g, and Mn of 20,000.
  • the fluoropolymer solution 1 is a solution in which the fluoropolymer 1 is dissolved in butyl acetate.
  • the numerical value in the parenthesis in Table 1 indicates the amount (part by mass) of the fluoropolymer 1 contained in the fluoropolymer solution.
  • the fluoropolymer solution 2 is a solution in which the fluoropolymer 2 is dissolved in butyl acetate.
  • the numerical value in the parenthesis in Table 1 indicates the amount (part by mass) of the fluoropolymer 2 contained in the fluoropolymer solution.
  • Serum superpolymer SH2400P (manufactured by Advanced Soft Materials Co., Ltd., polyrotaxane having a hydroxyl group, axial molecular Mw: 20,000, hydroxyl value: 76 mgKOH / g, Tg: ⁇ 50 ° C.)
  • This polyrotaxane is a polyrotaxane obtained by modifying a polyrotaxane having a cyclodextrin as a cyclic molecule and a polyethylene glycol chain having an adamantyl group as a blocking group as an axis molecule with propylene oxide and ⁇ -caprolactone (Japanese Patent Laid-Open No.
  • A The elongation of the test piece is 100% or more and less than 150% with respect to the test piece before the tensile test.
  • B The elongation of the test piece is 50% or more and less than 100% with respect to the test piece before the tensile test.
  • C The elongation of the test piece is less than 50% with respect to the test piece before the tensile test.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Transportation (AREA)
  • Paints Or Removers (AREA)
  • Vehicle Interior And Exterior Ornaments, Soundproofing, And Insulation (AREA)

Abstract

L'invention concerne un matériau de revêtement pour des éléments d'intérieur de véhicule, qui est apte à former un élément d'intérieur de véhicule présentant une excellente résistance aux rayures et une excellente résistance à la contamination contre des agents d'écran solaire. Le matériau de revêtement pour des éléments d'intérieur de véhicule, est caractérisé en ce qu'il contient un polymère contenant du fluor qui a un motif basé sur une fluorooléfine et un motif basé sur un monomère ayant un premier groupe réticulable, un polyrotaxane qui a deux seconds groupes réticulables ou plus, et un agent de durcissement.
PCT/JP2018/010137 2017-03-15 2018-03-15 Matériau de revêtement pour éléments d'intérieur de véhicule, élément d'intérieur de véhicule et procédé de production d'élément d'intérieur de véhicule Ceased WO2018168987A1 (fr)

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JP2019506252A JP7031660B2 (ja) 2017-03-15 2018-03-15 車両内装部材用塗料、車両内装部材および車両内装部材の製造方法

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JP2017049467 2017-03-15

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WO2019124496A1 (fr) * 2017-12-20 2019-06-27 Ａｇｃ株式会社 Film décoratif, procédé de fabrication de film décoratif, procédé de fabrication d'article moulé en trois dimensions avec film décoratif, et composition de polymère fluoré
WO2019124495A1 (fr) * 2017-12-20 2019-06-27 Ａｇｃ株式会社 Film décoratif, et procédé de production d'un article moulé tridimensionnel ayant un film décoratif
EP3533845A4 (fr) * 2016-10-31 2020-04-15 Agc Inc. Composition de revêtement pour élément intérieur de véhicule, élément intérieur de véhicule et procédé de fabrication d'élément intérieur de véhicule
CN115027268A (zh) * 2021-03-05 2022-09-09 本田技研工业株式会社 车辆用内饰结构

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JPS58136662A (ja) * 1982-02-05 1983-08-13 Asahi Glass Co Ltd 被覆組成物
JP2004285107A (ja) * 2003-03-19 2004-10-14 Asahi Glass Co Ltd 非水分散液型塗料用組成物および塗料
JP2007099995A (ja) * 2005-10-06 2007-04-19 Nissan Motor Co Ltd 常温乾燥型溶剤系ソフトフィール塗料用材料、これを用いた塗料及び塗膜
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Publication number Priority date Publication date Assignee Title
EP3533845A4 (fr) * 2016-10-31 2020-04-15 Agc Inc. Composition de revêtement pour élément intérieur de véhicule, élément intérieur de véhicule et procédé de fabrication d'élément intérieur de véhicule
WO2019124496A1 (fr) * 2017-12-20 2019-06-27 Ａｇｃ株式会社 Film décoratif, procédé de fabrication de film décoratif, procédé de fabrication d'article moulé en trois dimensions avec film décoratif, et composition de polymère fluoré
WO2019124495A1 (fr) * 2017-12-20 2019-06-27 Ａｇｃ株式会社 Film décoratif, et procédé de production d'un article moulé tridimensionnel ayant un film décoratif
JPWO2019124496A1 (ja) * 2017-12-20 2021-01-14 Ａｇｃ株式会社 加飾フィルム、加飾フィルムの製造方法、加飾フィルム付き３次元成形品の製造方法および含フッ素重合体組成物
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JP7151721B2 (ja) 2017-12-20 2022-10-12 Ａｇｃ株式会社 加飾フィルム、加飾フィルムの製造方法、加飾フィルム付き３次元成形品の製造方法および含フッ素重合体組成物
CN115027268A (zh) * 2021-03-05 2022-09-09 本田技研工业株式会社 车辆用内饰结构

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