CN113801554A - Composition and preparation method and application thereof - Google Patents

Composition and preparation method and application thereof Download PDF

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Publication number
CN113801554A
CN113801554A CN202010551197.3A CN202010551197A CN113801554A CN 113801554 A CN113801554 A CN 113801554A CN 202010551197 A CN202010551197 A CN 202010551197A CN 113801554 A CN113801554 A CN 113801554A
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China
Prior art keywords
composition
aqueous
dispersion
weight
substrate
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CN202010551197.3A
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Chinese (zh)
Inventor
赵东波
张晨曦
李芳�
谭淼
覃元昊
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Covestro Deutschland AG
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Covestro Deutschland AG
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Priority to CN202010551197.3A priority Critical patent/CN113801554A/en
Priority to PCT/EP2021/065747 priority patent/WO2021254895A1/en
Priority to TW110121374A priority patent/TW202206486A/en
Priority to CN202180043027.7A priority patent/CN115698179A/en
Publication of CN113801554A publication Critical patent/CN113801554A/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/06—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J111/00—Adhesives based on homopolymers or copolymers of chloroprene
    • C09J111/02—Latex
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention relates to a composition comprising: A) 70-99.6% by weight of an aqueous polyurethane dispersion; and B) 0.4% to 2% by weight of an aqueous nanosilica dispersion containing hydroxyl groups; the above weights are all based on 100% by weight of the composition; the aqueous polyurethane dispersion is prepared by a reaction comprising a polyester polyol; the particle size of the hydroxyl-containing aqueous nano silicon dioxide dispersoid is 5nm-18 nm; the weight ratio of the hydroxyl-containing aqueous nano silicon dioxide dispersion to the aqueous polyurethane dispersion is 1: 249-1: 49. The compositions of the present invention have the advantages of low VOC and low odor.

Description

Composition and preparation method and application thereof
Technical Field
The present invention relates to a composition, the preparation and use of the composition, a two-component system comprising the composition and its use, and articles coated or bonded using the composition or the two-component system.
Background
Along with the improvement of living standard of people and the popularization of automobile domestication, people pay more and more attention to the quality of air in the automobile. The evaluation of the air quality in the vehicle is mainly two aspects, namely the content of volatile organic compounds (VOC for short) in the vehicle and the odor in the vehicle. According to statistics, the problem that the VOC content exceeds the standard exists in nearly 90% of automobiles according to the indoor air quality standard. The excessive content of VOC can cause the immune level disorder of human body, affect the function of nervous system, cause symptoms such as dizziness, headache, somnolence, weakness and the like, affect the digestive system, cause inappetence, nausea and the like, seriously damage liver and hematopoietic system and threaten the health of human. In the PP100 (problem per hundred vehicles) list of new vehicle quality research (IQS), "unpleasant odors/odors" have been high in recent years, and although these odors are not necessarily threatening human health, consumers often do not want odors present in vehicles. Sources of VOC and odor in vehicles are various, such as seat foam, fabric coating, plastic upholstery, adhesives, and the like.
The aqueous dispersion system has very low VOC content, and can effectively solve the problem that the VOC content in the vehicle exceeds the standard. And the aqueous dispersion system has low odor, and can solve the problem of unpleasant odor in the vehicle.
CN 104151540A discloses a preparation method of polyether polyol with low VOC content and high resilience for polyurethane foam, which is characterized in that a polyol compound is adopted as an initiator, and an alkali metal hydroxide is adopted as a catalyst to react under the pressure of 0-0.6MPa and the temperature of 60-140 ℃, so that the polyether polyol is polymerized with an epoxy compound step by step and then is obtained through special post-treatment; wherein, the mass of the polyalcohol compounds accounts for 10 to 19.5 percent of the total feeding amount, the mass of the epoxy compounds accounts for 80 to 89.5 percent of the total feeding amount, and the mass of the alkali metal hydroxide accounts for 0.2 to 0.5 percent of the total feeding amount.
CN 104592878B discloses an environment-friendly water-based paint and a preparation method thereof, wherein the preparation method comprises the following steps: the water-based resin coating comprises a water-based resin dispersion, water, composite anion powder, an anion additive, a film forming auxiliary agent, a defoaming agent, a thickening agent, a dispersing agent and a pH regulator. The composite anion powder consists of crystal salt, nano silicon dioxide, nano titanium dioxide phosphate and nano zinc dioxide. The nanometer silicon dioxide, the nanometer titanium dioxide phosphate and the nanometer zinc dioxide are used as photocatalyst materials, and can effectively degrade harmful gases such as formaldehyde and the like in the air under illumination to produce bovine superoxide anion free radicals and associated negative oxygen ions.
CN 103980814A discloses a polyurethane odorless matte wear-resistant clear finish and a preparation method thereof, which is prepared by a main agent, a curing agent and a diluent according to the weight ratio of 1-1.4: 0.5-0.7: 0.7-1.2; the specific ratio of the main agent to the curing agent is 1-1.4: 0.5-0.7, so that hydroxyl in the main agent and isocyanate in the curing agent are fully and completely reacted, the optimal molar ratio of the hydroxyl to the isocyanate is 2: 1, the hydroxyl and the isocyanate are optimally matched in the construction process, and the hydroxyl and the isocyanate are completely reacted to generate stable polyurethane bonds, so that the odor purification effect is achieved, and the pungent odor brought by the raw materials is eliminated.
CN 106009271 a discloses a modified polypropylene composition, which comprises the following blended components: polypropylene, ethylene propylene grafted maleic anhydride copolymer, reinforcing filler, deodorant, antioxidant and processing aid. Wherein the deodorant is an organic salt and/or silicate with micropores, and the silicate with micropores is at least one of sodium silicate salt, aluminum silicate salt, magnesium silicate salt and calcium silicate salt; the specific surface area of the silicate with micropores is 200-600m2/g, preferably 300-2(ii)/g; the pores of the microporous silicate have an average pore diameter of 0.2 to 2nm, preferably 0.1 to 1 nm.
CN 101379157 a discloses the use of nanoparticles, especially finely dispersed barium sulfate, which may or may not be used with chemical modification, for the preparation of adhesives such as aqueous dispersion polyacrylates, polyurethanes and epoxy resins. By the incorporation of nanoparticles, the properties of such adhesives are improved, such as cohesion and heat resistance, while maintaining comparable adhesion.
CN 103608361B discloses a process for the preparation of a concentrated aqueous dispersion comprising organic polymer particles and silica particles, as well as the aqueous dispersion obtained by this process and its use as a binder and the use of such a dispersion as a binder, the preparation step of the aqueous dispersion comprising: a) providing an aqueous dispersion comprising organic polymer particles and silica particles, said dispersion having an initial content of organic polymer and an initial content of silica; b) contacting the dispersion of step a) with a creaming agent to produce an aqueous clear phase and an aqueous concentrated phase, and c) separating the clear phase from the concentrated phase.
However, the demand of low odor in the vehicle is becoming more severe for consumers, and the existing aqueous dispersion systems are difficult to satisfy.
It is desirable to develop a new low VOC, low odor composition that further reduces odor over existing products to meet the demanding odor applications, such as automotive interior coatings or automotive interior binders.
Disclosure of Invention
The object of the present invention is to provide a composition, in particular a composition not comprising a chelating agent, the preparation and use of the composition, a two-component system comprising the composition and its use, and articles coated or bonded using the composition or the two-component system.
The composition according to the invention comprises:
A) 70-99.6% by weight of an aqueous polyurethane dispersion; and
B) 0.4-2 wt% of an aqueous nanosilica dispersion containing hydroxyl groups;
the above weight percentages all relative to the total weight of the composition;
the aqueous polyurethane dispersion is prepared by a reaction comprising a polyester polyol; the particle size of the hydroxyl-containing aqueous nano silicon dioxide dispersoid is 5nm-18 nm; the weight ratio of the hydroxyl-containing aqueous nano silicon dioxide dispersion to the aqueous polyurethane dispersion is 1: 249-1: 49.
According to one aspect of the present invention, there is provided a method of preparing a composition provided herein, comprising the steps of: mixing the aqueous polyurethane dispersion and the hydroxyl-containing aqueous nanosilica dispersion in any manner.
According to a further aspect of the present invention there is provided the use of a composition provided according to the present invention for the preparation of an article.
According to a further aspect of the present invention, there is provided an article comprising a substrate and a coating formed by applying a composition provided according to the present invention to the substrate.
According to yet another aspect of the present invention, there is provided a method of manufacturing a coated article comprising the steps of: the compositions provided according to the present invention are applied to a substrate surface and subsequently cured.
According to yet another aspect of the present invention, there is provided a method of manufacturing a bonded article comprising the steps of:
i. applying a composition provided according to the present invention to at least one surface of a substrate; and
ii contacting the substrate surface treated in step i with the substrate itself or a surface of an additional substrate to obtain the bonded article.
According to a further aspect of the present invention there is provided a two-component system comprising an a-component which is a composition provided according to the present invention and a B-component which is a cross-linking agent.
According to a further aspect of the present invention there is provided the use of a two-component system provided according to the present invention for the preparation of an article.
According to yet another aspect of the present invention, there is provided an article comprising a substrate and a coating formed by applying the two-component system provided according to the present invention to the substrate.
The composition is an aqueous composition, is suitable for industrial application, has the characteristic of low VOC, has the advantage of low odor, and can meet the application fields with strict requirements on VOC and odor, such as automobile interiors, indoor houses and the like.
Detailed Description
The present invention provides a composition comprising: A) 70-99.6% by weight of an aqueous polyurethane dispersion; and B) 0.4% to 2% by weight of an aqueous nanosilica dispersion containing hydroxyl groups; the above weight percentages all relative to the total weight of the composition; the aqueous polyurethane dispersion is prepared by a reaction comprising a polyester polyol; the particle size of the hydroxyl-containing aqueous nano silicon dioxide dispersoid is 5nm-18 nm; the weight ratio of the hydroxyl-containing aqueous nano silicon dioxide dispersion to the aqueous polyurethane dispersion is 1: 249-1: 49. The invention also provides a preparation method and application of the composition, in particular application in the fields of coatings and adhesives, a two-component system of the composition and application thereof, and an article coated or bonded by using the composition or the two-component system.
The term "cure" as used herein refers to the process of a composition or two-component system containing a composition from a liquid to a solid.
As used herein, the term "coating" refers to a chemical substance that can be applied to the surface of an object by various application processes to form a strong, continuous solid coating.
As used herein, the term "adhesive" refers to a chemical substance that can be applied to the surface of an object by different application processes, form a coating on the object itself or the surface of one object to another, and bond the object itself or the surface of one object to another, and is also used as a synonym for adhesive and/or sealant and/or adhesive.
The term "polyurethane polymer" as used herein refers to polyurethaneurea polymers and/or polyurethane polyureas polymers and/or polyurea polymers and/or polythiourethane polymers.
The term "aqueous polyurethane dispersion" as used herein refers to an aqueous polyurethaneurea dispersion and/or an aqueous polyurethane polyurea dispersion and/or an aqueous polythiourethane dispersion.
The term "emulsifier" as used herein refers to a compound comprising emulsifying groups or latent emulsifying groups.
The term "isocyanate-reactive group" as used herein refers to a group containing Zerewitinov-active hydrogen, which is defined with reference to Rompp's Chemical Dictionary (Rommp Chemie Lexikon), 10th ed., Georg Thieme Verlag Stuttgart, 1996. In general, zerewitinov-active hydrogen-containing radicals are understood in the art to mean hydroxyl (OH), amino (NH)x) And a thiol group (SH).
The term "chelating agent" as used herein refers to a compound capable of forming a stable complex with metal ions, in particular heavy metal ions or transition metal ions.
The term "not comprising a chelating agent" as used herein means that the amount of chelating agent in the composition is less than 0.05 wt%.
Composition comprising a metal oxide and a metal oxide
The composition preferably does not comprise a chelating agent, most preferably the chelating agent of the composition is in an amount of 0.
The amount of organic solvent in the composition preferably does not exceed 5 wt.%, most preferably does not exceed 0.5 wt.%, relative to the total weight of the composition.
The weight ratio of the hydroxyl-containing aqueous nanosilica dispersion to the aqueous polyurethane dispersion is preferably from 1: 200 to 1: 50.
The composition is aqueous, and the composition has the characteristic of low VOC.
The composition is preferably a coating or a binder, most preferably an interior coating or an interior binder.
Aqueous polyurethane dispersions
The amount of the aqueous polyurethane dispersion is preferably from 90% to 99% by weight, most preferably from 98% to 99.6% by weight, relative to the total weight of the composition.
The solids content of the aqueous polyurethane dispersion is preferably from 40% to 60% by weight, relative to the total weight of the aqueous polyurethane dispersion.
The amount of residual organic solvent in the aqueous polyurethane dispersion is preferably less than 1.0% by weight, relative to the total weight of the solids of the aqueous polyurethane dispersion.
The aqueous polyurethane dispersion may be added to the composition directly as a dispersion or may be added to the composition as a polyurethane polymer and water and mixed to form a dispersion.
The aqueous polyurethane dispersion comprises a polyurethane polymer and water, wherein the polyurethane polymer is preferably obtained by reacting a system comprising a polyisocyanate, a polyester polyol and an emulsifier.
Polyisocyanates
The functionality of the polyisocyanate is preferably not less than 2, and further preferably 2 to 4.
The amount of the polyisocyanate is preferably 5% to 70% by weight, further preferably 5% to 40% by weight, still further preferably 5% to 35% by weight, most preferably 10% to 30% by weight, relative to the total weight of the system for preparing the polyurethane polymer.
The polyisocyanate is preferably one or more of the following: aliphatic polyisocyanates, cycloaliphatic polyisocyanates, aromatic polyisocyanates, and their derivatives with iminooxadiazinedione, isocyanurate, uretdione, urethane, allophanate, biuret, urea, oxadiazinetrione, oxazolidinone, acylurea and/or carbodiimide groups.
The aliphatic polyisocyanate is preferably one or more of the following: 1, 6-hexamethylene diisocyanate, 2-dimethylpentanedione diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, butene diisocyanate, 1, 3-butadiene-1, 4-diisocyanate, 2, 4, 4-trimethyl-1, 6-hexamethylene diisocyanate, 1, 6, 11-undecane triisocyanate, 1, 3, 6-hexamethylene triisocyanate, 1, 8-diisocyanato-4-isocyanatomethyloctane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, lysine methyl diisocyanate, lysine triisocyanate, bis (isocyanatomethyl) sulfide, bis (isocyanatoethyl) sulfide, bis (isocyanatopropyl) sulfide, bis (isocyanatohexyl) sulfide, butene diisocyanate, 2, 4-dimethylbutene diisocyanate, 2, 4-hexamethylene diisocyanate, 2-dimethylene diisocyanate, 2-diisocyanate, 4-hexamethylene diisocyanate, 1, 6-hexamethylene triisocyanate, 6-hexamethylene diisocyanate, 1, 8-diisocyanate, 4-hexamethylene diisocyanate, 6-hexamethylene diisocyanate, 1, 6-hexamethylene diisocyanate, 4-hexamethylene diisocyanate, 1, 6-diisocyanate, 6-hexamethylene diisocyanate, 1, 4-diisocyanato, 4-diisocyanat, bis (diisocyanato, bis (isocyanato-bis (isocyanato) carbonate), bis (isocyanato) carbonate), bis (isocyanate), bis (isocyanate), bis (diisocyanate, bis (isocyanato) ether, bis (isocyanate), bis (isocyanato-bis (isocyanate), bis (isocyanato) ether, bis (isocyanate), bis (isocyanate), bis (isocyanato) sulfide, bis (isocyanate, bis (isocyanato) ether, bis (isocyanate), bis (isocyanate), bis (isocyanato) sulfide, bis (isocyanate, Bis (isocyanatomethyl) sulfone, bis (isocyanatomethyl) disulfide, bis (isocyanatoethyl) disulfide, bis (isocyanatopropyl) disulfide, bis (isocyanatomethylthio) methane, bis (isocyanatoethylthio) methane, bis (isocyanatomethylthio) ethane, bis (isocyanatoethylthio) ethane, 1, 5-diisocyanato-2-isocyanatomethyl-3-thiapentane, 1, 2, 3-tris (isocyanatomethylthio) propane, 1, 2, 3-tris (isocyanatoethylthio) propane, 3, 5-dithia-1, 2, 6, 7-heptanediisocyanate, 2, 6-diisocyanatomethyl-3, 5-dithia-1, 7-heptanediisocyanate, bis (isocyanatomethyl) disulfide, bis (isocyanatoethyl) disulfide, bis (isocyanatoethylthio) ethane, bis (isocyanatopropyl) disulfide, bis (isocyanatomethylthio) methane, bis (isocyanatoethylthio) methane, bis (isocyanatomethylthio) methane, bis (isocyanatoethylthio) ethane, 1, 5-dithia-1, 2, 6, 7-heptanediisocyanate, 2, 6-diisocyanatomethyl-3, 5-dithio-1, 7-heptane, 2, 5-diisocyanatomethylthiophene, isocyanatoethylthio-2, 6-dithia-1, 8-octane diisocyanate, thiobis (3-isothiocyanatopropane), thiobis (2-isothiocyanatoethane), dithiobis (2-isothiocyanatoethane), hexamethylene diisocyanate, and isophorone diisocyanate, most preferably one or more of the following: 1, 6-hexamethylene diisocyanate and hexamethylene diisocyanate.
The cycloaliphatic polyisocyanate is preferably one or more of the following: 2, 5-bis (isocyanatomethyl) -bicyclo [2.2.1]Heptane, 2, 6-bis (isocyanatomethyl) -bicyclo [2.2.1]Heptane, bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, 2, 5-diisocyanato tetrahydrothiophene, 2, 5-diisocyanatomethyltetrahydrothiophene, 3, 4-diisocyanatomethyltetrahydrothiophene, 2, 5-diisocyanato-1, 4-dithiane, 2, 5-diisocyanatomethyl-1, 4-dithiane, 4, 5-diisocyanato-1, 3-dithiolane, 4, 5-bis (isocyanatomethyl) -1, 3-dithiolane, 4, 5-diisocyanatomethyl-2-methyl-1, 3-dithiolane, norbornane diisocyanate (NBDI), Xylylene Diisocyanate (XDI), hydrogenated xylylene diisocyanate (H).6XDI), 1, 4-cyclohexyl diisocyanate (H)6PPDI), 1, 5-Pentamethylene Diisocyanate (PDI), m-tetramethylxylylene diisocyanate (m-TM)XDI) and cyclohexane diisothiocyanate, most preferably one or more of the following: isophorone diisocyanate and dicyclohexyl diisocyanate.
The aromatic polyisocyanate is preferably one or more of the following: 1, 2-diisocyanatobenzene, 1, 3-diisocyanatobenzene, 1, 4-diisocyanatobenzene, 2, 4-diisocyanatotoluene, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, toluene diisocyanate, diethylbenzene diisocyanate, diisopropylbenzene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, biphenyl diisocyanate, toluidine diisocyanate, 4 ' -methylenebis (phenyl isocyanate), 4 ' -methylenebis (2-methylphenyl isocyanate), bibenzyl-4, 4 ' -diisocyanate, bis (isocyanatophenyl) ethylene, bis (isocyanatomethyl) benzene, bis (isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene, α, α, α ', α ' -tetramethylxylylene diisocyanate, Bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanatomethyl phenyl) ether, bis (isocyanatoethyl) phthalate, 2, 6-bis (isocyanatomethyl) furan, 2-isocyanatophenyl-4-isocyanatophenyl sulfide, bis (4-isocyanatophenyl) sulfide, bis (4-isocyanatomethyl) sulfide, bis (4-isocyanatophenyl) disulfide, bis (2-methyl-5-isocyanatophenyl) disulfide, bis (3-methyl-6-isocyanatophenyl) disulfide, bis (4-methyl-5-isocyanatophenyl) disulfide, bis (4-methoxy-3-isocyanatophenyl) disulfide, 1, 2-diisothiocyanatobenzene, 1, 3-diisothiocyanatobenzene, 1, 4-diisothiocyanatobenzene, 2, 4-diisothiocyanatotoluene, 2, 5-diisothiocyanato-m-xylene, 4' -methylenebis (phenylisothiocyanate), 4, 4 ' -methylenebis (2-methylphenyl isothiocyanate), 4 ' -methylenebis (3-methylphenyl isothiocyanate), 4 ' -diisothiocyanatobenzophenone, 4 ' -diisothiocyanato-3, 3 ' -dimethylbenzophenone, bis (4-isothiocyanatophenyl) ether, 1-isothiocyanato-4- [ (2-isothiocyanato) sulfonyl.]Benzene, thiobis (4-isothiocyanatobenzene)) Sulfonyl (4-isothiocyanatobenzene), hydrogenated toluene diisocyanate (H)6TDI), diphenylmethane diisocyanate and dithiobis (4-isothiocyanatobenzene), most preferably one or more of the following: 1, 2-diisocyanatobenzene, 1, 3-diisocyanatobenzene, 1, 4-diisocyanatobenzene, diphenylmethane diisocyanate, and 2, 4-diisocyanatotoluene.
The polyisocyanate may also have isocyanate groups and isothiocyanate groups such as 1-isocyanato-6-isothiocyanatohexane, 1-isocyanato-4-isothiocyanatocyclohexane, 1-isocyanato-4-isothiocyanatobenzene, 4-methyl-3-isocyanato-1-isothiocyanatobenzene, 2-isocyanato-4, 6-diisothiocyanato-1, 3, 5-triazine, 4-isocyanato-4-isothiocyanatophenylthioether and 2-isocyanato-2-isothiocyanatoethyldisulfide.
The polyisocyanate may also be a halogen substituent of the above polyisocyanates, for example a chlorine substituent, a bromine substituent, an alkyl substituent, an alkoxy substituent, a nitro substituent or a silane substituent such as isocyanatopropyltriethoxysilane or isocyanatopropyltrimethoxysilane.
Polyester polyols
The amount of the polyester polyol is preferably 5% to 95% by weight, preferably 10% to 90% by weight, relative to the total weight of the system for preparing the polyurethane polymer.
The hydroxyl value of the polyester polyol is preferably 20 to 80.
The polyester polyol is preferably a linear polyester polyol.
The linear polyester polyol or the lightly branched polyester polyol is prepared by comprising the following components: aliphatic, alicyclic or aromatic di-or polycarboxylic acids, such as succinic acid, methylsuccinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, azelaic acid, decanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, maleic acid, fumaric acid, malonic acid or trimellitic acid; anhydrides, such as phthalic anhydride, trimellitic anhydride or succinic anhydride or mixtures thereof; and low molecular weight polyols, and optionally higher functional polyols, such as trimethylolpropane, glycerol or pentaerythritol, cycloaliphatic and/or aromatic di-and poly-hydroxy compounds.
Emulsifier
The amount of said emulsifier is preferably comprised between 0.1% and 20% by weight with respect to the total weight of the system for preparing said polyurethane polymer.
The emulsifier preferably comprises at least one isocyanate-reactive group and at least one emulsifying group or latent emulsifying group.
The isocyanate-reactive groups are preferably one or more of the following: hydroxyl, thiol and amino groups.
The emulsifying groups or potential emulsifying groups are preferably one or more of the following: sulfonic acid groups, carboxylic acid groups, tertiary amino groups, and hydrophilic polyethers.
The emulsifier comprising sulfonic acid groups and/or carboxylic acid groups is preferably one or more of the following: diamino compounds comprising sulfonic acid groups and/or carboxylic acid groups and dihydroxy compounds comprising sulfonic acid groups and/or carboxylic acid groups, further preferably one or more of the following: sodium, potassium, lithium, tertiary amine salts of N- (2-aminoethyl) -2-aminoethanesulfonic acid, N- (3-aminopropyl) -3-aminopropanesulfonic acid, N- (2-aminoethyl) -3-aminopropanesulfonic acid, like carboxylic acids, dimethylolpropionic acid or dimethylolbutyric acid, most preferably one or more of the following: n- (2-aminoethyl) -2-aminoethanesulfonate and dimethylolpropionic acid.
The sulfonic acid groups or carboxylic acid groups can be used directly in the form of their salts, such as sulfonates or carboxylates.
The sulfonic acid or carboxylic acid groups can also be obtained by partial or complete addition of neutralizing agents during or after the preparation of the polyurethane polymer.
The neutralizing agent for salt formation is preferably one or more of the following: triethylamine, dimethylcyclohexylamine, ethyldiisopropylamine, ammonia, diethanolamine, triethanolamine, dimethylethanolamine, sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, methyldiethanolamine, and aminomethylpropanol, most preferably one or more of the following: triethylamine, dimethylcyclohexylamine and ethyldiisopropylamine.
Organic solvent
The system for preparing the polyurethane polymer may further comprise an organic solvent that is miscible with water but inert to isocyanate groups.
The amount of said organic solvent is preferably comprised between 0.001% and 20% by weight with respect to the total weight of the system for preparing said polyurethane polymer.
The organic solvent is preferably one or more of the following: acetone, 2-butanone, tetrahydrofuran, xylene, toluene, cyclohexane, butyl acetate, dioxane acetate, methoxypropyl acetate, N-methylpyrrolidone, N-ethylpyrrolidone, acetonitrile, dipropylene glycol dimethyl ether, and solvents containing ether or ester units, most preferably one or more of the following: acetone and 2-butanone.
The organic solvent may be added only at the beginning of the preparation, or may be added in part during the preparation as needed.
Reactive diluent
The system for preparing the polyurethane polymer may further comprise a reactive diluent.
The amount of the reactive diluent is preferably from 0.001% to 90% by weight, relative to the total weight of the system for preparing the polyurethane polymer.
The reaction diluent is preferably one or more of the following: acrylic acid and acrylic esters.
The aqueous polyurethane dispersion is preferably an anionic aqueous polyurethane dispersion, most preferably one or more of the following: dispercoll U56 and Dispercoll U54.
Aqueous nanosilica dispersions containing hydroxyl groups
The amount of the aqueous nanosilica dispersion containing hydroxyl groups is preferably from 0.4 wt% to 1.8 wt%, most preferably from 0.7 wt% to 1.8 wt%, relative to the total weight of the composition.
The particle size of the aqueous nanosilica dispersion containing hydroxyl groups is preferably from 8nm to 15nm, most preferably from 9nm to 15 nm.
The pH of the aqueous nanosilica dispersion containing hydroxyl groups is preferably equal to or greater than 7, most preferably from 8 to 10.
The hydroxyl-containing aqueous nanosilica dispersion preferably has a specific surface area of 100m2/g-400m2Per g, further preferably 120m2/g-350m2In g, most preferably 200m2/g-300m2/g。
The hydroxyl group-containing aqueous nanosilica dispersion preferably has a density of 1.1g/cm3-1.3g/cm3。
When the composition comprises two or more hydroxyl group-containing aqueous nanosilica dispersions, the particle size refers to the average of the particle sizes of all hydroxyl group-containing aqueous nanosilica dispersions, preferably the particle size of each hydroxyl group-containing aqueous nanosilica dispersion in the composition is in the range of from 5nm to 18 nm.
Stabilizer
The composition may further comprise a stabilizer which is beneficial to reduce hydrolysis of the composition and prolong the pot life of the composition.
The stabilizer is preferably one or more of the following: carbodiimide compounds, epoxy compounds, oxazoline compounds and aziridine compounds.
The content of the stabilizer is preferably 0 to 10% by weight, more preferably 0.5% by weight to 10% by weight, most preferably 0.5 to 2% by weight, relative to the total weight of the solid portion of the composition.
Additive agent
The composition may further comprise an additive.
The additive is preferably one or more of the following: co-binders, thickeners, adhesion promoters, lubricants, wetting additives, dyes, light stabilizers, aging inhibitors, pigments, flow control agents, antistatic agents, UV absorbers, film-forming aids, defoamers and plasticizers.
The amount of the additive may be an amount well known to those skilled in the art.
Aqueous dispersion
The composition may further comprise an aqueous dispersion different from the aqueous polyurethane dispersion, preferably one or more of the following: aqueous polyester dispersions, aqueous polyurethane-polyacrylate dispersions, aqueous polyester-polyacrylate dispersions, alkyd resins, aqueous polyamide/imide dispersions and aqueous polyepoxide dispersions.
The weight ratio of the aqueous dispersion different from the aqueous polyurethane dispersion to the aqueous polyurethane dispersion is preferably between 0 and 0.42: 1.
Method for preparing composition
The aqueous polyurethane dispersion is preferably obtained from a reaction comprising the following steps:
a. reacting some or all of the polyisocyanate and the polyester polyol to obtain a prepolymer, the reaction being carried out in the presence of or after the optional water-miscible organic solvent which is inert to isocyanate groups to dissolve the prepolymer;
b. reacting the prepolymer, an emulsifier, an optional reaction diluent, a polyisocyanate that is not added in step a, and a polyester polyol that is not added in step a to obtain the polyurethane polymer; and
c. introducing water and optionally an emulsifier before, during or after step b to obtain the aqueous polyurethane dispersion.
The aqueous polyurethane polymer is preferably prepared using a prepolymer mixing process, an acetone process or a melt dispersion process, most preferably using the acetone process.
The order of mixing of the components of the system for preparing the aqueous polyurethane dispersion can be carried out in a conventional manner.
The polyisocyanate and polyester polyol may be added in one portion or in multiple portions, either of the same or different composition as previously added.
The organic solvent present in the aqueous polyurethane dispersion can be removed by distillation. The organic solvent may be removed during or after the polyurethane polymer is formed.
When the composition further comprises a stabilizer, additive or aqueous dispersion different from said aqueous polyurethane dispersion, the process for preparing the composition of the invention preferably comprises the steps of: mixing the aqueous polyurethane dispersion, the hydroxyl-containing aqueous nanosilica dispersion, the optional stabilizer, the optional additives and the optional aqueous dispersion different from the aqueous polyurethane dispersion in any manner.
The article is preferably selected from automotive interiors and interior furnishings.
The substrate is preferably one or more of the following: wood, plastic, metal, glass, textile, alloy, fabric, artificial leather, paper, cardboard, EVA, rubber, leather, glass fiber, ethylene vinyl acetate copolymer, polyolefin, thermoplastic polyurethane, polyurethane foam, polymer fiber, and graphite fiber, most preferably one or more of the following: EVA, rubber, genuine leather, artificial leather, ethylene vinyl acetate copolymer, polyolefin, thermoplastic polyurethane, and polyurethane foam.
The application may be the application of the composition to the entire surface of the substrate or only to one or more portions of the surface of the substrate.
The application may be brushing, dipping, spraying, rolling, knife coating, flow coating, pouring, printing or transferring, preferably brushing, dipping or spraying.
In the method of manufacturing a bonded article, a step iii between the step i and the step ii may be further comprised of heating and drying the surface of the substrate to which the composition is applied. When the method of making a bonded article further comprises a step iii, step ii is contacting the substrate surface treated in step iii with the substrate itself or a surface of an additional substrate to obtain the bonded article.
The step iii of heating and drying the surface of the substrate to which the adhesive is applied may refer to heating and drying only the surface of the substrate, or may refer to heating and drying a part of the substrate including the surface of the substrate to which the adhesive is applied or the entire substrate.
The heating and drying may remove volatile components. The volatile component may be water.
The heating and drying is preferably one or more of: infrared thermal radiation, near infrared thermal radiation, microwaves and the use of convection ovens or spray dryers at elevated temperatures.
The higher the temperature of the heating, the better, but should not be above the temperature limit at which the substrate deforms in an uncontrolled manner or suffers other damage.
The contacting is preferably performed before the temperature of the substrate surface is reduced below the temperature at which the adhesive can bond.
The additional substrate may be any substrate that requires adhesion.
The additional substrate and the base material may be the same or different.
The further substrate is preferably coated and heat treated as the substrate.
Two-component system
The amount of organic solvent of the two-component system is preferably not more than 5 wt.%, most preferably not more than 0.5 wt.%, relative to the total weight of the two-component system.
The two-component system preferably does not comprise a chelating agent.
The two-component system is aqueous, and the VOC content of the two-component system is low.
The a and B components are preferably stored separately and mixed prior to use.
The weight ratio of the component A to the component B is preferably 1: 1 to 100: 1, most preferably 15: 1 to 25: 1.
The crosslinking agent is preferably an isocyanate group-containing compound.
The two-component system is preferably a coating or a binder, most preferably an interior coating or an interior binder.
The article is preferably selected from automotive interiors and interior furnishings.
The substrate is preferably one or more of the following: wood, plastic, metal, glass, textile, alloy, fabric, artificial leather, paper, cardboard, EVA, rubber, leather, glass fiber, ethylene vinyl acetate copolymer, polyolefin, thermoplastic polyurethane, polyurethane foam, polymer fiber, and graphite fiber, most preferably one or more of the following: EVA, rubber, genuine leather, artificial leather, ethylene vinyl acetate copolymer, polyolefin, thermoplastic polyurethane, and polyurethane foam.
The application may be the application of the composition to the entire surface of the substrate or only to one or more portions of the surface of the substrate.
The application may be brushing, dipping, spraying, rolling, knife coating, flow coating, pouring, printing or transferring, preferably brushing, dipping or spraying.
Examples
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In the event that a definition of a term in this specification conflicts with a meaning commonly understood by those skilled in the art to which the invention pertains, the definition set forth herein shall govern.
Unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth herein are approximations that can vary depending upon the desired properties to be obtained.
As used herein, "and/or" means one or all of the referenced elements.
As used herein, "comprising" and "comprises" encompass the presence of only the recited elements as well as the presence of other, non-recited elements in addition to the recited elements.
All percentages in the present invention are by weight unless otherwise indicated.
The analytical measurements according to the invention were carried out at 23 ℃ unless otherwise stated.
As used in this specification, the terms "a", "an" and "the" are intended to include "at least one" or "one or more" unless otherwise indicated. For example, "a component" refers to one or more components, and thus more than one component may be considered and may be employed or used in the practice of the described embodiments.
The solids content of the aqueous polyurethane dispersions was determined using a HS153 moisture meter from Mettler Toledo according to DIN-EN ISO 3251.
The isocyanate group (NCO) content is determined volumetrically according to DIN-EN ISO 11909 and the data determined include the free and potentially free NCO content.
The pH was measured at 20 ℃ using a PB-10pH meter from Sartorius, Germany.
The specific surface area (BET) is determined in accordance with DIN ISO 9277 standard test methods.
Raw materials and reagents
Dispercoll U56: anionic aqueous polyurethane dispersions having a solids content of 50. + -. 1% are available from Kostew Innovation, Germany.
Dispercoll U54: anionic aqueous polyurethane dispersions having a solids content of 50. + -. 1% are available from Kostew Innovation, Germany.
Dispercoll U53: anionic aqueous polyurethane dispersions having a solids content of 50. + -. 1% are available from Kostew Innovation, Germany.
Dispercoll S4020: hydrophilic fumed nanosilica dispersion with a solids content of 40 wt.%, a particle size of 15nm, BET 200m2G, density 1.29g/cm3pH 9, available from Kossi Industrie GmbH, Germany.
Dispercoll S5005: hydrophilic gas phase nano-dioxideSilicon dispersion with a solids content of 50 wt.%, particle size 55nm, BET 50m2G, density 1.39g/cm3pH 9, available from Kossi Industrie GmbH, Germany.
Dispercoll S4510: hydrophilic fumed nanosilica dispersion with a solids content of 45 wt.%, a particle size of 30nm, BET 100m2G, density 1.34g/cm3pH 9, available from Kossi Industrie GmbH, Germany.
Dispercoll S3030: hydrophilic fumed nanosilica dispersion with a solids content of 30% by weight, a particle size of 9nm, BET 300m2G, density 1.21g/cm3pH 9, available from Kossi Industrie GmbH, Germany.
Dispercoll S2020 XP: hydrophilic fumed nanosilica dispersion with a solids content of 20% by weight, a particle size of 15nm, BET 200m2G, density 1.13g/cm3pH 9, available from Kossi Industrie GmbH, Germany.
Borchigel L75N: solids content 25% by weight, thickener, commercially available from OMG.
Table 1 is the evaluation criteria and rating of the odor test. Table 2 shows the composition of the compositions of examples and comparative examples, the odor test of the compositions, and the viscosity test results after thickening the compositions.
Method for preparing compositions of examples 1 to 9 and comparative examples 1 to 9
The aqueous polyurethane dispersion was weighed out to be stirred in a vessel at a speed of 800rpm according to the amounts shown in Table 2; adding a small amount of aqueous nano silicon dioxide dispersoid, and stirring at the speed of 800rpm to disperse the aqueous nano silicon dioxide dispersoid in the aqueous polyurethane dispersoid; the remaining aqueous nanosilica dispersion was added and stirring was continued at 900rpm to 1000rpm for about 30min until a homogeneously dispersed composition was obtained. Of these, the compositions of comparative examples 1-3 comprise only aqueous polyurethane dispersions.
Odor test
1. Uniformly coating the composition sample on a matt surface of aluminum foil paper, and standing at room temperature until the composition sample is completely dried;
2. the aluminum foil paper coated with the sample to be detected is made into 50 +/-5 cm by cutting, stacking and other modes3The volume is small, and the mixture is placed for 7 days at room temperature;
3. putting the aluminum foil paper obtained in the step 2 into a transparent glass bottle with the capacity of about 1L and no special odor per se, and sealing;
4. putting the glass bottle into an oven, heating for 2h at 80 ℃, then cooling to 60 ℃ and preserving heat for more than half an hour;
5. the vials were removed from the oven and after opening the lids 5 persons each smelled and given an odor rating according to the table 1 standard. If the difference in the results given by 5 persons is larger than 1, the results are invalid and the test is needed again.
If the result differences are less than or equal to 1, the average value of 5 results is taken as the final result, and the final result can be accurate to 0.1. The results are shown in Table 2.
Table 1 odor test standards and ratings
Figure BDA0002541913020000161
Figure BDA0002541913020000171
Thickening of compositions
Samples of the composition were mechanically stirred using an IKA machine at 700-800rpm for 10 minutes, the stirring was stopped and Borchigel L75N (0.8 parts of Borchigel L75N per 100 parts of the composition) was added, stirring was continued at 300-400rpm until Borchigel L75N was mixed with the composition, and finally stirring was continued at 700-800rpm for 30 minutes to obtain a thickened composition. The thickened compositions were tested for initial viscosity and viscosity after 2 weeks of aging at 50 ℃ and are shown in Table 2. In actual industrial application, the composition is often required to be thickened for use. When the viscosity of the thickened composition is less than 1000mpa.s, it cannot meet the industrial requirements. Viscosity test method: the samples were tested using a Brook Field viscometer with a speed set at 30RPM with rotor S62 being selected for measurement if the sample viscosity is less than 900mPas and rotor S63 being used if the sample viscosity is greater than 900 mPas.
Test results
The compositions of comparative examples 1 to 3 comprise only aqueous polyurethane dispersions and no aqueous nanosilica dispersions containing hydroxyl groups, and the odor test readings of the compositions of the comparative examples are significantly higher than those of examples 1 to 9.
The compositions of comparative examples 4, 6, 9 comprise aqueous nanosilica dispersions containing hydroxyl groups with particle sizes of 55nm and 30nm, respectively, the compositions of comparative examples 4, 6 having odor test readings significantly higher than those of examples 1-4 and the composition of comparative example 9 having odor test readings significantly higher than those of examples 5-8.
The composition of comparative example 5 comprises the hydroxyl group-containing aqueous nano-silica dispersion having a particle size of 30nm and an amount of the hydroxyl group-containing aqueous nano-silica dispersion of 2.4% by weight of the composition, and the viscosity of the composition of comparative example 5 after thickening and aging for 2 weeks decreases rapidly to be much less than 1000mpa.s, i.e., the thickened composition cannot meet the use requirements of the industry.
The composition of comparative example 7 comprised an amount of the hydroxyl group-containing aqueous nanosilica dispersion of 0.3% of the amount of the composition, and the composition of comparative example 7 had an odor test reading value significantly higher than the odor test readings values of examples 1-9.
The composition of comparative example 8 comprises an amount of the hydroxyl-containing aqueous nanosilica dispersion of 2.2% of the amount of the composition, and the viscosity of the composition of comparative example 8 after thickening after aging for 2 weeks at 50 ℃ decreases very rapidly, much less than 1000mpa.s, i.e. the thickened composition has not been able to meet the use requirements of the industry.
Figure BDA0002541913020000191
The invention also provides an adhesive, which comprises the following components: 79.20g Dispercoll C84 (waterborne Neoprene latex), 1.74g TSR-1068, 1.45g Dnano-233W-30WS, 8.71g Revacryl X9045 (tackifying resin emulsion), 8.89g PRIML AS-2010 (tackifying resin emulsion), 2.00g Eastman TXIB and 2.50g glycine. The above adhesive compositions were mixed homogeneously and had a viscosity (using Brookfield/LV/Sp3/60rpm/23 ℃) of 263.0 mPas and a pH of 8.00. The adhesive is uniformly sprayed on the surface of the sponge base material to be tested, then manual bonding is carried out, the shortest time that the sponge can be completely bonded is recorded as the initial bonding time, the sponge can be completely bonded, and the longest time that the sponge material can be finally broken is the opening time. The tack time of the test adhesive was 10s-20s at 23 ℃ and 60% RH, and the open time was 20min-25 min.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing description, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description; and therefore any changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.

Claims (20)

1. A composition, comprising:
A) 70-99.6% by weight of an aqueous polyurethane dispersion; and
B) 0.4-2 wt% of an aqueous nanosilica dispersion containing hydroxyl groups;
the above weight percentages all relative to the total weight of the composition;
the aqueous polyurethane dispersion is prepared by a reaction comprising a polyester polyol; the particle size of the hydroxyl-containing aqueous nano silicon dioxide dispersoid is 5nm-18 nm; the weight ratio of the hydroxyl-containing aqueous nano silicon dioxide dispersion to the aqueous polyurethane dispersion is 1: 249-1: 49.
2. The composition of claim 1, wherein the composition does not comprise a chelating agent.
3. The composition according to claim 1 or 2, characterized in that the amount of the aqueous nanosilica dispersion containing hydroxyl groups is from 0.4% to 1.8% by weight, most preferably from 0.7% to 1.8% by weight, relative to the total weight of the composition.
4. The composition according to any one of claims 1 to 3, wherein the hydroxyl group-containing aqueous nanosilica dispersion has a particle size of from 8nm to 15 nm.
5. The composition according to any one of claims 1 to 4, wherein the hydroxyl-containing aqueous nanosilica dispersion has a pH of 7 or more.
6. The composition according to one of claims 1 to 5, wherein the weight ratio of the hydroxyl-containing aqueous nanosilica dispersion to the aqueous polyurethane dispersion is from 1: 200 to 1: 50.
7. The composition according to any one of claims 1 to 6, wherein the amount of the aqueous polyurethane dispersion is from 98% to 99.6% by weight, relative to the total weight of the composition.
8. The composition of any one of claims 1 to 7, wherein the composition is a coating or an adhesive.
9. A process for preparing a composition as claimed in any one of claims 1 to 8, comprising the steps of: mixing the aqueous polyurethane dispersion and the hydroxyl-containing aqueous nanosilica dispersion in any manner.
10. Use of a composition according to any one of claims 1 to 8 for the preparation of an article.
11. Use according to claim 10, wherein the article is selected from automotive interiors and interior furnishings.
12. An article comprising a substrate and a coating formed by applying the composition of any one of claims 1-8 to the substrate.
13. A method of making a coated article comprising the steps of: applying a composition according to any one of claims 1 to 8 to a substrate surface followed by curing.
14. A method of making a bonded article comprising the steps of:
i. applying a composition according to any one of claims 1 to 8 to at least one surface of a substrate; and
contacting the surface of the substrate treated in step i with the surface of the substrate itself or of an additional substrate to obtain the bonded article.
15. A two-component system comprising an a-component which is a composition according to any one of claims 1 to 8 and a B-component which is a cross-linking agent.
16. The two-component system according to claim 15, wherein the crosslinking agent is an isocyanate group-containing compound.
17. Two-component system according to claim 15 or 16, wherein the two-component system is a coating or a binder.
18. Use of the two-component system according to any of claims 15-17 for the preparation of an article.
19. Use according to claim 18, wherein the article is selected from automotive interiors and interior furnishings.
20. An article comprising a substrate and a coating formed by applying the two-component system of any of claims 15-17 to the substrate.
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