WO2021247342A1 - Article de cuir revêtu - Google Patents

Article de cuir revêtu Download PDF

Info

Publication number
WO2021247342A1
WO2021247342A1 PCT/US2021/034387 US2021034387W WO2021247342A1 WO 2021247342 A1 WO2021247342 A1 WO 2021247342A1 US 2021034387 W US2021034387 W US 2021034387W WO 2021247342 A1 WO2021247342 A1 WO 2021247342A1
Authority
WO
WIPO (PCT)
Prior art keywords
microspheres
acrylic
polymeric
basecoat
polymeric film
Prior art date
Application number
PCT/US2021/034387
Other languages
English (en)
Inventor
Ibrahim ERYAZICI
Joseph M. Hoefler
Nick Nicholas
Edwin A. NUNGESSER
Original Assignee
Rohm And Haas Company
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 Rohm And Haas Company filed Critical Rohm And Haas Company
Publication of WO2021247342A1 publication Critical patent/WO2021247342A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C11/00—Surface finishing of leather
    • C14C11/003—Surface finishing of leather using macromolecular compounds
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • 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
    • C08G18/08—Processes
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
    • C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/42—Gloss-reducing agents
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14B—MECHANICAL TREATMENT OR PROCESSING OF SKINS, HIDES OR LEATHER IN GENERAL; PELT-SHEARING MACHINES; INTESTINE-SPLITTING MACHINES
    • C14B7/00—Special leathers and their manufacture
    • C14B7/02—Composite leathers
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C11/00—Surface finishing of leather
    • C14C11/003—Surface finishing of leather using macromolecular compounds
    • C14C11/006—Surface finishing of leather using macromolecular compounds using polymeric products of isocyanates (or isothiocyanates) with compounds having active hydrogen
    • 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
    • B05D2203/00—Other substrates
    • B05D2203/24—Leather
    • 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
    • B05D7/56—Three layers or more
    • B05D7/57—Three layers or more the last layer being a clear coat
    • B05D7/574—Three layers or more the last layer being a clear coat at least some layers being let to dry at least partially before applying the next layer

Definitions

  • the present invention relates to a leather article coated with a basecoat and a topcoat.
  • Leather is routinely finished by a multistep process that includes applying a basecoat to the leather surface followed by applying a topcoat.
  • the basecoat is routinely applied in the first step of treating leather to provide color, softening, and embossing, as well as protection from damage over years of extended use.
  • leather Under normal conditions of use, leather is subject to flexing, stretching, and contorting, any of which may lead to cracking and further deterioration from added stresses over time.
  • the topcoat gives feel and ease of cleaning without damaging the leather.
  • Basecoat compositions contain matting agents to provide a dull finish.
  • Inorganic matting agents such as silica based materials and calcium carbonate are disfavored because they are known to disrupt film integrity by inducing cracking and causing losses in water and abrasion resistance as well as flexibility.
  • Advances in matting agents that overcome some of the problems associated with inorganic matting agents include multistaged polymeric microspheres, as described by Chiou et al. in US 7,829,626. Nevertheless, these microspheres, while more robust than their inorganic counterparts, do not provide the desired flexibility in the leather substrate.
  • compositions comprising an aqueous dispersion of a) film- forming polymer particles comprising polyurethane polymer particles having a z-average particle size in the range of from 50 nm to 500 nm, as determined by dynamic light scattering, and a T g of less than 10 °C; and b) non-film-forming single phase crosslinked polymeric microspheres having a median weight average particle size in the range of from 2 pm to 30 pm and a T g of not greater than 10 °C.
  • the present invention is a multilayered article comprising a) a leather substrate; b) a basecoat layer superposing the leather substrate and having a dry film thickness in the range of from 10 pm to 100 pm; and c) a topcoat layer superposing the basecoat layer and having a dry film thickness in the range of from 2 mhi to 30 mhi; wherein the basecoat layer comprises non-film-forming single phase crosslinked polymeric microspheres embedded in a first polymeric film, wherein the polymeric microspheres have a median weight average particle size in the range of from 2 pm to 30 pm and T g of not greater than 10 °C, and the first polymeric film has a T g of less than 10 °C; and wherein the topcoat layer comprises a second polymeric film.
  • composition of the present invention addresses a need in the art by providing a flexible matte finish to a leather substrate to retain flexibility without significant cracking under accelerating stress testing conditions.
  • the present invention is a composition
  • the weight-to-weight ratio of crosslinked single phase microspheres to the film- forming polymer particles having a T g of less than 10 °C is preferably in the range of 1:1, more preferably from 1:2 to 1:10, more preferably to 1:8.
  • the aqueous composition comprises film-forming polyurethane particles having a T g of less than 10 °C, preferably less than 0 °C, and preferably greater than -60 °C.
  • particles or “polymer particles” are synonymous with binder or latex particles.
  • Aqueous dispersions of polyurethane particles suitable for use in the composition are well known in the art - see, for example, US 5,569,707, US 5,959,027, and US 2004/0242765 A1 - and are commercially available, for example as Bayderm Polyurethane Binders and PRIMALTM Polyurethane Binders (a Trademark of The Dow Chemical Company or its affiliates).
  • the aqueous composition further comprises non- film- forming single phase crosslinked polymeric microspheres having a particle size in the range of from 2 pm, preferably from 4 pm, to 30 pm, preferably to 20 pm, more preferably to 15 pm, and most preferably to 10 pm.
  • the polymeric microspheres have a T g of not greater than 10 °C, preferably less than 0 °C, and preferably greater than -60 °C as calculated by the Fox equation.
  • single phase refers to microspheres that are neither covered by a shell nor occluded with domains having a T g of greater than 25 °C as calculated by the Fox equation.
  • the composition comprises a substantial absence of multiphase microspheres, that is, a substantial absence of low T g microspheres clad with a high T g shell or occluded with high T g domains.
  • substantial absence refers to less than 10, preferably less than 5, and most preferably 0 weight percent, based on the weight of the single phase microspheres in the composition, of multiphase microspheres.
  • the single phase crosslinked microspheres comprise structural units of one or more monoethylenically unsaturated monomers whose homopolymers have a T g of not greater than 10 °C (low T g monomers) such as methyl acrylate, ethyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate.
  • the single phase crosslinked microspheres comprise from 50, more preferably from 70, more preferably from 80 weight percent, and most preferably from 90, to preferably 99, and more preferably to 97.5 weight percent structural units of a low T g monomer.
  • structural unit of a named monomer refers to the remnant of the monomer after polymerization.
  • a structural unit of n-hutyl acrylate is as illustrated: structural unit of «-butyl acrylate where the dotted lines represent the points of attachment of the structural unit to the polymer backbone.
  • the crosslinked single phase microspheres also comprise structural units of a multiethylenically unsaturated monomer, examples of which include allyl methacrylate, allyl acrylate, divinyl benzene, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, butylene glycol (1,3) dimethacrylate, butylene glycol (1,3) diacrylate, ethylene glycol dimethacrylate, and ethylene glycol diacrylate.
  • a multiethylenically unsaturated monomer examples of which include allyl methacrylate, allyl acrylate, divinyl benzene, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, butylene glycol (1,3) dimethacrylate, butylene glycol (1,3) diacrylate, ethylene glycol dimethacrylate, and ethylene glycol diacrylate.
  • the concentration of structural units of the multiethylenically unsaturated monomer in the crosslinked microspheres is preferably in the range of from 1, more preferably from 2 weight percent, to 10, more preferably to 8, and most preferably to 6 weight percent, based on the weight of the polymeric microspheres.
  • the polymeric microspheres may further comprise, based on the weight of the microspheres, from 0.05 to 5 percent structural units of a polymerizable organic phosphate represented by the structure of Formula I:
  • n is 0, x is 1, and y is 2, the polymerizable organic phosphate or salt thereof is represented by the structure of Formula II:
  • each R 1 is H, and each R 2 is H or CFp; m is preferably from 3, and more preferably from 4; to preferably to 8, and more preferably to 7.
  • Sipomer PAM- 100, Sipomer PAM-200 and Sipomer PAM-600 phosphate esters are examples of commercially available compounds within the scope of the compound of Formula II.
  • a commercially available compound within the scope of Formula III is Kayamer PM-21 phosphate ester.
  • the polymeric microspheres may also comprise 0.05 to 5 weight percent, based on the weight of the microspheres, of an ethylene oxide salt of a distyryl or a tristyryl phenol represented by the structure of Formula IV :
  • the single phase crosslinked microspheres may also comprise structural units of monomers whose homopolymers have a T g greater than 25 °C (high T g monomers), such as methyl methacrylate, styrene, or z-butyl methacrylate, provided the concentration of structural units of these high T g monomers is sufficiently low to ensure that the T g of the microspheres is not greater than 10 °C.
  • high T g monomers such as methyl methacrylate, styrene, or z-butyl methacrylate
  • the single phase crosslinked microspheres can be prepared as described by suspension polymerization methods known in the art, such as EP 3 502 196 Al, para [0059] to para [0061].
  • the method may also include growing out microspheres in the presence of a nonionic polyalkylene oxide of a distyryl or tristyryl phenol or an anionic polyalkylene oxide salt of a distyryl or tristyryl phenol, as described in US 2019/0177554, para [0054] to para [0060].
  • the film- forming polymer particles may also comprise non-polyurethane particles having a z-average particle size, as determined by dynamic light scattering, in the range of 50 nm and 500 nm and having a T g of less than 10 °C.
  • examples of other polymer particles include acrylic, styrene- acrylic, and vinyl acetate polymer particles.
  • the acrylic polymer particles preferably comprise at least 30, more preferably at least 50, and most preferably at least 80 percent structural units of acrylate or methacrylate monomers, such as methyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, and combinations thereof.
  • the acrylic polymer particles may also include structural units of acid monomers such as carboxylic acid, sulfur acid, and phosphorus acid monomers.
  • the polyurethane particles comprise at least 30 weight percent of the film-forming polymer particles, more preferably at least 50 weight percent of the film-forming polymer particles in the composition.
  • composition advantageously includes a number of other components including rheology modifiers, pigments, surfactants, softening agents, and waxes.
  • the present invention is a multilayered article comprising a) a leather substrate; b) a basecoat layer superposing the leather substrate and having a thickness in the range of from 10 pm to 100 pm; and c) a topcoat layer superposing the basecoat layer and having a thickness in the range of from 2 pm to 30 pm; wherein the basecoat layer comprises non-film-forming single phase crosslinked polymeric microspheres embedded in a first polymeric film, wherein the polymeric microspheres have a median weight average particle size in the range of from 2 pm to 30 pm and T g of not greater than 10 °C, and the first polymeric film has a T g of less than 10 °C; and wherein the topcoat layer comprises a second polymeric film.
  • the basecoat layer preferably has a thickness in the range of from 20 pm to 60 pm and comprises the non-film-forming single phase crosslinked polymeric microspheres embedded in a polymeric film. Both the film and the microspheres have a T g of less than 10 °C, and preferably less than 0 °C.
  • the polymeric film is preferably an acrylic, styrene- acrylic, poly(vinyl acrylate), or polyurethane film or a combination thereof.
  • a more preferred polymeric film comprises a combination of acrylic and polyurethane polymers.
  • the polymeric microspheres are preferably acrylic, styrene- acrylic, vinyl acrylate, silicone, or urethane polymers, preferably acrylic or styrene- acrylic polymers, and have a median weight average particle size (D50) in the range of from 2 pm, more preferably from 4 pm, to 30 pm, preferably to 20 pm, more preferably 15 pm, more preferably to 13 pm, and most preferably to 10 pm, as measured using Disc Centrifuge Photosedimentometer, as described herein.
  • the basecoat preferably further comprises less than 10, more preferably less than 5, and most preferably 0 weight percent microspheres clad with a high T g shell, based on the weight of total microspheres in the basecoat layer.
  • the weight-to- weight ratio of crosslinked polymeric microspheres to the first polymeric film is in the range of from 1:1, more preferably from 1:2, to 1:10, more preferably to 1:8.
  • the basecoat layer advantageously further comprises additional components including rheology modifiers, pigments, surfactants, softening agents, matting agents, and waxes.
  • the topcoat preferably has a thickness in the range of 5 pm to 25 pm and comprises a second polymeric film having a T g of less than 10 °C, preferably less than 0 °C, as calculated by the Fox equation.
  • the second polymeric film is preferably an acrylic, styrene- acrylic, vinyl acetate, or polyurethane based polymeric film.
  • the topcoat advantageously further comprises additional components including dullers, pigments, feel modifiers, wetting agents, rheology modifiers, and crosslinking agents.
  • the thickness of the basecoat is greater than the thickness of the topcoat.
  • the multilayered article is advantageously prepared as follows: A basecoat comprising the composition of the present invention along with a rheology modifier, a pigment, a surfactant, a softening agent, and a matting agent is sprayed or roll coated onto the leather substrate, and dried at high temperature (generally ⁇ 90 °C). After being allowed to cure, the basecoated substrate is embossed with a patterned embossing plate or smooth rolled, then either milled or mechanically staked. A second basecoat, which is a color coat, is preferentially spray or roll coated to the coated substrate and dried as described above. A topcoat is then spray or roll coated to the base/color coated leather and cured, generally for 3 days.
  • a basecoat comprising the composition of the present invention along with a rheology modifier, a pigment, a surfactant, a softening agent, and a matting agent is sprayed or roll coated onto the leather substrate, and dried at high temperature (generally ⁇ 90 °C). After being
  • the article of the present invention provides robust protection for a variety of embossed coatings under accelerated flex testing. Examples
  • D50 Median weight average particle sizes were measured using Disc Centrifuge Photosedimentometer (DCP, CPS Instruments, Inc., Prairieville, LA) that separates modes by centrifugation and sedimentation through a sucrose gradient.
  • the samples were prepared by adding 1 to 2 drops of the oligomer seed dispersion or the microsphere dispersion into 10 mL of deionized (DI) water containing 0.1% sodium lauryl sulfate, followed by injection of 0.1 mL of the sample into a spinning disc filled with 15 g/mL of sucrose gradient.
  • DI deionized
  • An aqueous dispersion of acrylic oligomer seed (33% solids, 67 butyl acrylate/18 n-dodecyl mercaptan/14.8 methyl methacrylate/ 0.2 methacrylic acid) with a weight average median particle size (D50) of 885 nm, and a weight average molecular weight of 2532 g/mole was prepared substantially as described in US 8,686,096, Examples 1 and 5 (col. 19 and 20). This seed was used to prepare the microspheres of all the Intermediate Examples and Intermediate Comparative Examples described herein.
  • Initiator emulsion was prepared by combining in a separate vial deionized water (1.0 g), Rhodacal DS-4 branched alkylbenzene sulfonate (DS-4, 0.7 g, 22.5% aq. solution), 4-hydroxy 2,2,6,6-tetramethylpiperidine (4-hydroxy TEMPO, 0.4 g, 5% aq. solution), z-butyl peroxy-2- ethylhexanoate (TBPEH, 5.6 g, 98% active), then emulsified using a stir bar for 10 min.
  • a shot monomer emulsion was prepared in a separate flask by combining deionized water (162.5 g), Solvay Sipomer PAM-600 phosphate esters of PPG monomethacrylate (PAM-600, 3.0 g, 60% active), DS-4 (5.6 g, 22.5% solution), 4-hydroxy TEMPO (0.3 g, 5% aq. solution), n-butyl acrylate (BA, 339.5 g) and allyl methacrylate (ALMA, 14.2 g).
  • Deionized water (1800 g) was added to a 5-L round bottom flask (reactor) fitted with a stirrer, condenser, and a temperature probe. The reactor was heated to 70 °C, after which time the initiator and oligomer seed mixture was added to the reactor, and Shot ME was fed into the reactor over 15 min. After an induction period of 30 min, the resultant exotherm caused the reactor temperature to rise to 80 °C.
  • a first monomer emulsion (ME1, prepared by combining deionized water (487.5 g), PAM-600 (9.0 g, 60% active), DS-4 (16.7 g, 22.5% aq. solution), 4-hydroxy TEMPO (0.8 g, 5% aq. solution), BA (1018.6 g) and ALMA (42.5 g) was then fed into the reactor over 63 min. After a 20-min hold, reactor temperature was increased to 95 °C then held for 60 minutes to chase residual monomers. The reactor was allowed to cool, after which time the consequent dispersion was filtered through a 45 -pm screen. The filtrate was analyzed for percent solids (33.8%) and D50 particle size (8.5 pm, as measured by DCP).
  • Initiator emulsion was prepared by combining deionized water (1.0 g), DS-4 (0.7 g, 22.5% aq. solution), 4-hydroxy TEMPO (0.4 g, 5% aq. solution), and TBPEH (5.8 g, 98% active) in a vial and stirring for 10 min. The initiator emulsion was then added to the dispersion of the acrylic oligomer seed (4.4 g, 32% solids) in a separate vial and mixed for 60 min. A shot monomer emulsion (shot ME) was prepared in a separate flask by combining deionized water (125.0 g), PAM-600 (2.3 g, 60% active), DS-4 (4.3 g, 22.5% aq.
  • a first monomer emulsion (ME1, prepared by combining deionized water (375.0 g), PAM-600 (6.9 g, 60% active), DS-4 (12.9 g, 22.5% aq. solution), 4-hydroxy TEMPO (0.6 g, 5% aq. solution), BA (783.5 g) and ALMA (32.7 g), was then fed into the reactor over 63 min. After a 20-min hold, NH 4 OH (0.8 g, 28% aq.) was fed into the reactor over 3 min.
  • the reactor temperature was cooled to and maintained at 75 °C, after which time FeSO ⁇ hEO (11.4 g, 0.15% aq.) and EDTA tetrasodium salt (2.1 g, 1.0% aqueous solution) were mixed and added to reactor.
  • a second monomer emulsion (ME2) was prepared in a separate flask by combining deionized water (115.0 g), DS-4 (3.3 g, 22.5% aq. solution), PAM-600 (2.3 g), methyl methacrylate (MMA, 261.2 g), and ethyl acrylate (EA, 10.8 g).
  • ME2 z-butyl hydroperoxide solution (z-BHP, 1.5 g (70% aq.
  • Comparative Intermediate Example 2 Preparation of a Dispersion of Crosslinked Acrylic Microspheres with a High T g Shell
  • the dispersion was prepared substantially as described to make the dispersion of high T g clad microspheres of Comparative Intermediate Example 1 except that the initiator emulsion was added to 13.3 g of acrylic oligomer seed (32% solids) instead of 4.4 g.
  • the filtrate was analyzed for percent solids (33.0%) and D50 particle size (5.8 pm, as measured by DCP).
  • Table 1 illustrates the basecoat and comparative basecoat formulations. All amounts are in grams.
  • Table 2 illustrates the topcoat formulation for all samples.
  • Basecoat Example and Comparative Basecoat Examples were separately added to a 500-mL paint container and mixed with an overhead agitator for 5 min.
  • Basecoat Example and Comparative Basecoat Examples were spray applied to commercial grade automotive corrected leather substrates (6-8 separate substrates used for each basecoat application) and dried for approximately 4 minutes in a 90 °C oven. After curing for 1 d the base coated leather was either embossed with a patterned embossing plate or was subject to a Finiflex smooth roller. The embossed basecoated leather was subjected to either milling (4 h) or mechanical staking. Then, a color coat using the same ingredients as used for the basecoat was applied to the base and dried for approximately 4 min in a 90 °C oven. A topcoat (see Table 2) was then applied to the base and color coated leather and cured for 3 days before testing.
  • the fully finished articles were subjected to flexibility stress tests using a bally flexometer for either 150,000 cycles at 25 °C or 30,000 cycles at -10 °C. After flexing, the samples were visually evaluated for cracking using a 10X stereoscope. The coatings were assessed a relative rating of 1 to 10 where 1 indicated severe cracking 10 indicated no observable cracking of the coating.
  • Application results for leather coated with the basecoat formulations prepared from Example 1 and Comparative Examples 1 to 3 (illustrated in Table 1), and the topcoat formulation (illustrated in Table 2), are reported in Table 3.
  • the reported average 60° gloss reflect the averages of Finiflex, embossed stake, and embossed milled treatments, with the number of treatments for each illustrated in parentheses.
  • Average 60° basecoat gloss refers to the gloss measured after application of the basecoat; similarly, average 60° topcoat gloss refers to the gloss measured after application of the topcoat. Standard deviations for all measurements are shown parenthetically.
  • Coating failure rating 25 °C refers to the failure rating at 25 °C and 150,000 flex cycles; coating failure rating -10 °C refers to the failure rating at -10 °C and 30,000 flex cycles.
  • Table 3 shows the results of gloss measurements and flex testing. 60° gloss of all basecoats were comparable independent of the type matting bead used in the basecoat. The average results of bally flex show that the articles that contained the basecoat with the single phase crosslinked polymer particles were showed superior resistance to cracking in accelerated flex testing and with greater consistency across multiple treatments - as evidenced by a lower standard deviation - in contrast with each of the comparative coated leather articles.

Abstract

La présente invention concerne un article multicouche comprenant a) un substrat en cuir ; b) une couche de revêtement de base superposée sur le substrat en cuir et c) une couche de revêtement de finition superposée sur la couche de revêtement de base ; la couche de revêtement de base comprenant des microsphères polymères réticulées à phase unique non filmogènes incorporées dans un premier film polymère, les microsphères polymères présentant une Tg qui n'est pas supérieure à 10°C et le premier film polymère présentant une Tg inférieure à 10°C ; et la couche de revêtement de finition comprenant un deuxième film polymère. L'article de la présente invention permet d'obtenir un cuir fini mat qui présente une résistance à la fissuration sous des conditions de test de flexion accélérée.
PCT/US2021/034387 2020-06-04 2021-05-27 Article de cuir revêtu WO2021247342A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202063034664P 2020-06-04 2020-06-04
US63/034,664 2020-06-04

Publications (1)

Publication Number Publication Date
WO2021247342A1 true WO2021247342A1 (fr) 2021-12-09

Family

ID=76808130

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2021/034387 WO2021247342A1 (fr) 2020-06-04 2021-05-27 Article de cuir revêtu

Country Status (1)

Country Link
WO (1) WO2021247342A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114181602A (zh) * 2021-12-27 2022-03-15 濮阳展辰新材料有限公司 水性双组分清面漆及其制备方法

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5569707A (en) 1994-02-25 1996-10-29 Bayer Aktiengesellschaft Aqueous polyester-polyurethane dispersions and their use in coating compositions
US5959027A (en) 1997-03-17 1999-09-28 The Dow Chemical Company Continuous process for preparing a polyurethane latex
US20040242765A1 (en) 2003-05-30 2004-12-02 Thomas Munzmay Aqueous polyurethane dispersions for producing coatings with soft feel effect
US7829626B2 (en) 2006-03-15 2010-11-09 Rohm And Haas Company Aqueous compositions comprising polymeric duller particle
US8686096B2 (en) 2005-09-16 2014-04-01 Rohm And Haas Company Swellable particles
US20170058371A1 (en) * 2015-08-31 2017-03-02 Rohm And Haas Company Aqueous multi-stage copolymer compositions for use in leather topcoats
US20180327562A1 (en) * 2017-05-10 2018-11-15 Rohm And Haas Company Process for preparing an aqueous dispersion of polymeric microspheres
US20190177554A1 (en) 2017-12-13 2019-06-13 Rohm And Haas Company Aqueous dispersion of microspheres p-acid functionalized polymer particles
EP3502196A1 (fr) 2017-12-19 2019-06-26 Rohm and Haas Company Dispersion aqueuse de particules de polymère, de microsphères et de cire de polyéthylène
CN110408313A (zh) * 2019-06-21 2019-11-05 安徽大学 一种聚丙烯腈中空微球改性的水性聚氨酯消光树脂及制备方法

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5569707A (en) 1994-02-25 1996-10-29 Bayer Aktiengesellschaft Aqueous polyester-polyurethane dispersions and their use in coating compositions
US5959027A (en) 1997-03-17 1999-09-28 The Dow Chemical Company Continuous process for preparing a polyurethane latex
US20040242765A1 (en) 2003-05-30 2004-12-02 Thomas Munzmay Aqueous polyurethane dispersions for producing coatings with soft feel effect
US8686096B2 (en) 2005-09-16 2014-04-01 Rohm And Haas Company Swellable particles
US7829626B2 (en) 2006-03-15 2010-11-09 Rohm And Haas Company Aqueous compositions comprising polymeric duller particle
US20170058371A1 (en) * 2015-08-31 2017-03-02 Rohm And Haas Company Aqueous multi-stage copolymer compositions for use in leather topcoats
US20180327562A1 (en) * 2017-05-10 2018-11-15 Rohm And Haas Company Process for preparing an aqueous dispersion of polymeric microspheres
US20190177554A1 (en) 2017-12-13 2019-06-13 Rohm And Haas Company Aqueous dispersion of microspheres p-acid functionalized polymer particles
EP3502196A1 (fr) 2017-12-19 2019-06-26 Rohm and Haas Company Dispersion aqueuse de particules de polymère, de microsphères et de cire de polyéthylène
CN110408313A (zh) * 2019-06-21 2019-11-05 安徽大学 一种聚丙烯腈中空微球改性的水性聚氨酯消光树脂及制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 201990, Derwent World Patents Index; AN 2019-94284R, XP002803785 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114181602A (zh) * 2021-12-27 2022-03-15 濮阳展辰新材料有限公司 水性双组分清面漆及其制备方法

Similar Documents

Publication Publication Date Title
CN102574936B (zh) 由硬核、软壳结构的聚合物颗粒制得的含水可自交联的聚合物分散体、及涂料或处理组合物
US9458347B2 (en) Aqueous coating composition and coating formed therefrom having a particular gloss profile
US9221992B2 (en) Aqueous coating compositions
US20130052454A1 (en) Basecoat/clearcoat coating
AU5207500A (en) Polymer
JPH03140306A (ja) 合成樹脂エマルション及びその製造方法
EP1421145A1 (fr) Compositions de revetement aqueuses reticulables, a base de fluoropolymeres vinyliques
RU2763432C2 (ru) Водная композиция для матирования поверхности
EP0266152B1 (fr) Procédé de peinture
WO2021247342A1 (fr) Article de cuir revêtu
CA3022470C (fr) Compositions architecturales resistantes a l'abrasion
WO2021247341A1 (fr) Dispersion aqueuse de microsphères réticulées à phase unique et de particules de polyuréthane filmogènes
CA3090503A1 (fr) Compositions architecturales resistantes a l'ecornure
WO2018087710A1 (fr) Procédé de fabrication de particules cœur-enveloppe par gonflement osmotique
PT1554323E (pt) Dispersão de microgel com ácido fosfónico modificado
JPS6166710A (ja) 非造膜性ビニル系樹脂エマルジヨンの製造法及びその粉末化法
WO2017101093A1 (fr) Retannage de cuir sans chrome
WO2023153189A1 (fr) Composition pour matériau de revêtement
CA3185914A1 (fr) Dispersion aqueuse de particules polymeres et de microspheres
JP2004130238A (ja) 塗装方法
JP2002003558A (ja) 水性架橋型樹脂組成物
MXPA99007403A (en) Water-based emulsion polymers which resist blocking
WO2014169413A1 (fr) Particules encapsulees de dioxyde de titane traitees au sulfate
BRPI0700629B1 (pt) Aquosa composition, method of manufacture of a coating, and, coated substrate

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21739199

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21739199

Country of ref document: EP

Kind code of ref document: A1