阅读说明：本技术 一种组合物及其制备方法和应用 (Composition and preparation method and application thereof ) 是由 金晨 朱英丹 安锦年 于 2018-08-24 设计创作，主要内容包括：本发明涉及一种组合物、组合物的制备和应用,以及使用该组合物涂覆得到的产品。该组合物包含(a)一聚氨酯聚合物,所述聚氨酯聚合物是包含下列组分的反应产物：(a1)一多异氰酸酯,(a2)一含异氰酸酯反应性基团的化合物,所述含异氰酸酯反应性基团的化合物包含一聚酯多元醇,所述聚酯多元醇的量大于10重量％,以所述含异氰酸酯反应性基团的化合物的量为100重量％计,(a3)可选的一乳化剂,(a4)可选的一溶剂,和(a5)可选的一反应性稀释剂；(b)一有机抗氧化剂,所述抗氧化剂的量为0.001重量％-1重量％,以所述组合物的固体组分的量为100重量％计；(c)一螯合剂；和(d)水。本发明的组合物具有良好的耐黄变性能。(The present invention relates to a composition, the preparation and use of the composition, and the products coated with the composition. The composition comprises (a) a polyurethane polymer that is the reaction product of: (a1) a polyisocyanate, (a2) an isocyanate-reactive group containing compound comprising a polyester polyol in an amount greater than 10% by weight based on 100% by weight of the isocyanate-reactive group containing compound, (a3) optionally an emulsifier, (a4) optionally a solvent, and (a5) optionally a reactive diluent; (b) an organic antioxidant in an amount of 0.001 wt% to 1 wt%, based on 100 wt% of the solid components of the composition; (c) a chelating agent; and (d) water. The compositions of the present invention have good yellowing resistance.)

1. A composition, comprising:

(a) a polyurethane polymer, said polyurethane polymer being the reaction product of:

(a1) a polyisocyanate, and a polyisocyanate,

(a2) an isocyanate-reactive group-containing compound comprising a polyester polyol in an amount of more than 10% by weight based on 100% by weight of the isocyanate-reactive group-containing compound,

(a3) optionally an emulsifier, which is a mixture of at least one of the above-mentioned compounds,

(a4) optionally a solvent, and

(a5) optionally a reactive diluent;

(b) an organic antioxidant in an amount of 0.001 wt% to 1 wt%, based on 100 wt% of the solid components of the composition;

(c) a chelating agent;

(d) water;

(e) optionally a stabilizer;

(f) optionally a cross-linking agent; and

(g) optionally an additive.

2. The composition according to claim 1, wherein said polyurethane polymer (a) has a first temperature rise curve with a melting enthalpy of more than 15J/g between 20 ℃ and 100 ℃ measured by DSC according to DIN65467, or a first temperature rise curve with a melting enthalpy of more than 15J/g between 20 ℃ and 100 ℃ measured by DSC according to DIN65467 after said composition has dried to a film.

3. The composition according to claim 1, wherein the compound containing isocyanate reactive groups (a2) has a first temperature rise curve with a melting enthalpy of more than 15J/g between 20 ℃ and 100 ℃ measured by DSC according to DIN 65467.

4. The composition of claim 1, wherein the amount of the organic antioxidant (b) is 50ppm to 5000ppm, based on 100% by weight of the solid components of the composition.

5. The composition of claim 1, wherein the amount of the organic antioxidant (b) is from 0.01 wt% to 0.5 wt%, based on 100 wt% of the solid components of the composition.

6. The composition of claim 1, wherein the chelating agent (c) is present in an amount of from 0.01 wt% to 1.95 wt%, based on 100 wt% of the solid components of the composition.

7. The composition of claim 1, wherein the chelating agent (c) is present as a water soluble salt of a chelating agent, wherein the water soluble salt of a chelating agent satisfies the following condition: the content of the water-soluble salt of the chelating agent in the aqueous solution of the water-soluble salt of the chelating agent is 4.3 x 10^-7At mol/g, the pH is greater than 5, preferably greater than 6, most preferably greater than 9.

8. The composition of claim 7, wherein the water soluble salt of a chelating agent is one or more of: ethylenediaminetetraacetate, tartrate, citrate, pyrophosphate, tripolyphosphate, hexametaphosphate and gluconate, most preferably one or more of the following: tetrasodium ethylenediaminetetraacetate, tetrapotassium ethylenediaminetetraacetate, and tetrasodium pyrophosphate.

9. The composition of claim 1, wherein the stabilizer (e) is one or more of the following: carbodiimide-based compounds, epoxy-based compounds, oxazoline-based compounds and aziridine-based compounds, the amount of the stabilizer being 0.5 to 10% by weight, based on 100% by weight of the solid components of the composition.

10. The composition of any one of claims 1-9, wherein the composition is a coating or an adhesive.

11. A process for the preparation of a composition as claimed in any one of claims 1 to 10, comprising the steps of: mixing the polyurethane polymer (a) or the components for preparing the polyurethane polymer, the organic antioxidant (b), the chelating agent (c), water (d), optionally a stabilizer (e), optionally a crosslinking agent (f) and optionally an additive (g) in any desired manner.

12. The method of claim 11, wherein the polyurethane polymer (a) and water (d) are formed into an aqueous polyurethane dispersion, and the organic antioxidant (b), the chelating agent (c), optionally a stabilizer (e), optionally a crosslinking agent (f), and optionally an additive (g) are introduced to form the composition.

13. The process according to any one of claims 11 to 12, wherein the chelating agent (c) is added in the form of an aqueous solution.

14. Use of a composition according to any one of claims 1 to 10 for the preparation of a coated product.

15. A coating method comprising the steps of: applying a composition according to any one of claims 1 to 10 to a substrate surface followed by curing.

16. A coated product comprising a substrate and a coating formed by applying the composition of any one of claims 1-10 to the substrate.

17. A method of making a bonded product comprising the steps of:

i. applying a composition according to any one of claims 1 to 10 to at least one surface of a substrate;

ii heating and drying the substrate surface to which the composition is applied; and

contacting the surface of the substrate treated in step ii with the surface of the substrate itself or of a further substrate to obtain the bonded product.

18. The method of claim 17, further comprising a step iv between step ii and step iii of irradiating the surface of the substrate treated in step ii with actinic radiation.

19. The method of claim 17, wherein 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.

20. A bonded product made according to the method of any one of claims 17-19.

Technical Field

The invention relates to a composition, to the preparation and use of the composition, in particular in the field of coatings, adhesives, and to the products coated with the composition.

Background

The polyurethane polymer and water are mixed to form an aqueous polyurethane dispersion. The aqueous polyurethane dispersion can be applied to the fields of coatings and adhesives. In the field of adhesives, it is common to apply an aqueous polyurethane dispersion to a substrate surface, heat and evaporate the water from the dispersion to form a coating, then heat activate (e.g., infrared heat) the coating, and finally contact and bond the substrate surface to which the dispersion is applied to other substrate surfaces to obtain a product. In practical applications, if the temperature required for thermal activation is high, not only is more energy consuming, but also manual application and bonding difficulties are increased, and therefore, the industry desires to find an adhesive suitable for low thermal activation temperatures.

US 4870129A discloses an adhesive comprising a crosslinking agent containing isocyanate functional groups and an aqueous polyurethane dispersion containing hydroxyl groups, the composition forming a coating requiring a thermal activation temperature of 40 to 80 ℃. The adhesive has the defects of easy yellowing and unattractive appearance.

Yellowing of adhesives is often due to the tendency of the polymer to oxidize, which is exacerbated when the adhesive is exposed to heat or UV light, resulting in increased yellowing. Yellowing of the adhesive not only leads to an aesthetically unpleasing appearance of the product to which it is bonded, but also means that the adhesive ages and the mechanical properties of the bonded product resulting from adhesive bonding deteriorate. In practical applications, the coating and the adhesive are often applied in high temperature environment. For example: the adhesive is applied to the glass fiber during sizing and forming, and is firstly applied to the glass fiber, and then dried and formed at high temperature to obtain the plastic plate.

EP0356655B1 discloses a composition for reinforcing materials comprising at least one crosslinkable polyurethaneAn ester, a silicone coupling agent, a copolymer of an acrylic monomer and a polymerizable monomer, a crosslinking agent, a metal chelating agent, and water, wherein the metal chelating agent is a polydentate compound or has the formula (RH)_2nC_n)₂N(CH₂)_xN(C_nH_2nR)₂The compound of (1). The glass fiber reinforced polymer treated by the composition has good mechanical properties under long-term exposure to solvents, high temperature or UV.

EP0381125B1 discloses a composition which is not prone to oxidation and which can be applied to fibre sizing. The composition comprises: component A is a thermoplastic polyester, a polyoxyalkylene, ethylene glycol, polyvinyl alcohol, polyolefin latex, polyvinyl acetate, epoxy resin, starch, a combination of epoxy polymer and polyvinyl alcohol, a combination of epoxy polymer and polyurethane; component B is a metal chelator selected from a polydentate compound or of the formula (RH)_2nC_n)₂N(CH₂)_xN(C_nH_2nR)₂A compound of (1); both components C and D are antioxidants. The products obtained by treating the fibers with the above compositions have good mechanical properties even after long-term exposure to high temperatures.

AU a 60777/94 discloses an aqueous polymer dispersion for use as a sticker comprising a polyurethane and a chelating agent, the chelating agent comprising a polyvalent metal and a polydentate compound. The adhesive has high strength at high temperatures.

The technology solves the problems of aging and mechanical property reduction of the coating and the adhesive at high temperature, but does not solve the problem that the coating and the adhesive are easy to yellow when heated.

CN104387548 discloses a polyurethane resin not prone to yellowing, which is prepared from aliphatic polyether polyol, aliphatic polyester polyol, aliphatic isocyanate, aliphatic chain extender and antioxidant.

JP2009143765 discloses an adhesive for sizing and forming glass fibers, which is not easily yellowed at high temperature. The adhesive comprises pyrophosphate and polyurethane, the amount of pyrophosphate being 10% to 75% by weight of the amount of polyurethane solids.

CN106928422 discloses a preparation method of yellowing-resistant polyurethane, comprising: (1) reacting diisocyanate and diol in the presence of a catalyst to obtain a reactant; (2) reacting the reactant with a chain extender to obtain a chain-extended product; (3) and reacting the chain-extended product with epoxy resin to obtain the yellowing-resistant polyurethane product.

US7091280 discloses an adhesive comprising an aqueous polyurethane dispersion and a stabilizer. The adhesive has yellowing resistance.

Therefore, it is desirable to develop a composition that forms a coating having good yellowing resistance.

Disclosure of Invention

The invention aims to provide a composition, in particular a yellowing-resistant coating and adhesive, preparation and application of the composition, and a product coated by the composition.

The composition according to the invention comprises: (a) a polyurethane polymer, said polyurethane polymer being the reaction product of:

(a1) a polyisocyanate, and a polyisocyanate,

(a2) an isocyanate-reactive group-containing compound comprising a polyester polyol in an amount of more than 10% by weight based on 100% by weight of the isocyanate-reactive group-containing compound,

(a3) optionally an emulsifier, which is a mixture of at least one of the above-mentioned compounds,

(a4) optionally a solvent, and

(a5) optionally a reactive diluent;

(b) an organic antioxidant in an amount of 0.001 wt% to 1 wt%, based on 100 wt% of the solid components of the composition;

(c) a chelating agent; and

(d) water;

(e) optionally a stabilizer;

(f) optionally a cross-linking agent; and

(g) optionally an additive.

According to one aspect of the present invention, there is provided a process for the preparation of a composition provided herein, comprising the steps of: mixing the polyurethane polymer (a) or the components for preparing the polyurethane polymer, the organic antioxidant (b), the chelating agent (c), water (d), optionally a stabilizer (e), optionally a crosslinking agent (f) and optionally an additive (g) in any desired manner.

According to yet another aspect of the invention, the use of the composition provided by the invention for the preparation of a coated product.

According to still another aspect of the present invention, there is provided a coating method 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 coated product comprising a substrate and a coating layer formed by applying the composition provided according to the present invention to the substrate.

According to still another aspect of the present invention, there is provided a method of manufacturing a bonded product, comprising the steps of:

i. applying a composition provided according to the present invention to at least one surface of a substrate;

ii heating and drying the substrate surface to which the composition is applied; and

contacting the surface of the substrate treated in step ii with the surface of the substrate itself or of a further substrate to obtain the bonded product.

According to yet another aspect of the invention, there is provided a bonded product manufactured according to the method provided by the invention.

The compositions of the present invention have good yellowing resistance.

Detailed Description

The present invention provides a composition comprising:

(a) a polyurethane polymer, said polyurethane polymer being the reaction product of:

(a1) a polyisocyanate, and a polyisocyanate,

(a2) an isocyanate-reactive group-containing compound comprising a polyester polyol in an amount of more than 10% by weight based on 100% by weight of the isocyanate-reactive group-containing compound,

(a3) optionally an emulsifier, which is a mixture of at least one of the above-mentioned compounds,

(a4) optionally a solvent, and

(a5) optionally a reactive diluent;

(b) an organic antioxidant in an amount of 0.001 wt% to 1 wt%, based on 100 wt% of the solid components of the composition;

(c) a chelating agent;

(d) water;

(e) optionally a stabilizer;

(f) optionally a cross-linking agent; and

(g) optionally an additive. The invention also provides a preparation method and application of the composition, in particular to the application in the fields of coatings and adhesives, and a product coated by the composition.

The term "curing" as used herein refers to the process of a liquid composition from a liquid state to a cured state.

The term "composition" as used herein refers to a mixture of chemical components that will cure upon application and form a coating, and herein the composition may be a coating or an adhesive.

As used herein, the term "coating" refers to a composition that can be applied to the surface of an object by various application processes to form a strong, continuous solid coating.

The term "adhesive" as used herein means a composition that can be applied to the surface of an object by different application processes, forms a coating on the object itself or on the surface of an object and bonds the object itself or an object to the surface of another object, and is also used as a synonym for adhesive and/or sealant and/or adhesive.

Polyurethane Polymer (a)

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 polyurethane polymer (a) preferably has a melting enthalpy at 20 ℃ to 100 ℃ of the first temperature rise curve of more than 15J/g, measured by DSC according to DIN65467, or preferably has a melting enthalpy at 20 ℃ to 100 ℃ of more than 15J/g, measured by DSC according to DIN65467 after the composition has dried to a film.

The polyurethane polymer (a) has a first temperature rise curve with a melting enthalpy of 20 ℃ to 100 ℃ measured by DSC according to DIN65467, most preferably 25J/g to 100J/g, or the composition, after drying to a film, has a first temperature rise curve with a melting enthalpy of 20 ℃ to 100 ℃ measured by DSC according to DIN65467, most preferably 25J/g to 100J/g.

The amount of the polyurethane polymer is preferably from 10% to 99.98% by weight, based on 100% by weight of the solid components of the composition.

The amount of the polyurethane polymer is most preferably from 95 wt% to 99.98 wt%, based on 100 wt% of the solid components of the composition.

The polyurethane polymer may be added as a solid or may be added as a dispersion after first being mixed with water in the composition to form an aqueous polyurethane dispersion, most preferably directly as a dispersion.

Polyisocyanate (a1)

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, based on 100% by weight of the amount of the component 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, 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-heptane tetraisocyanate, 2, 6-diisocyanatomethyl-3, 5-dithia-1, 7-heptane diisocyanate, 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, N-diisocyanatomethyl-tetrahydrothiophene, 2, 5-diisocyanatomethyl-1, 3-dithiolane, 4, 5-diisocyanato-1₆XDI), 1, 4-cyclohexyl diisocyanate (H)₆PPDI), 1, 5-Pentanediisocyanate (PDI), m-tetramethylxylylene diisocyanate (m-TMXDI), 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 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 ' -tetramethylxylylene diisocyanate, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanatomethyl phenyl) ether, bis (isocyanatoethyl) phthalate, 2, 6-bis (isocyanatomethyl) furan, 2-4-dithiophenyl) benzene, bis (isocyanatomethyl) sulfide, bis (isocyanatomethyl) 3-dithiophenyl) sulfide, 5-dithiophenyl) 3-diisocyanatomethyl (3-dithiophenyl) sulfide, bis (isocyanatomethyl) phenyl) sulfide, bis (isocyanatoethyl) phenyl sulfide, bis (isocyanatomethyl) phenyl) sulfide, bis (isocyanatomethyl) 3-dithiophenyl sulfide, bis (isocyanatomethyl) sulfide, 2, 5-dithiophenyl sulfide, 3-dithiophenyl sulfide, 5-dithiophenyl) sulfide, bis (isocyanatomethyl) sulfide, 3-dithiophenyl sulfide, 5-dithiophenyl sulfide, bis (isocyanatomethyl) ether, 3-dithiophenyl sulfide, 5-dithiophenyl sulfide3-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.

Compound containing isocyanate reactive group (a2)

As used herein, the term "isocyanate-reactive group" refers to a group containing Zerewitinov-active hydrogens, which are defined with reference to Romp's Chemical Dictionary (Romp Chemie Lexikon), 10^thed., 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 compound containing isocyanate-reactive groups (a2) preferably has a melting enthalpy at 20 ℃ to 100 ℃ of the first temperature rise curve of more than 15J/g, measured by DSC according to DIN 65467.

The compound containing isocyanate-reactive groups (a2) has a melting enthalpy of the first temperature rise curve at 20 ℃ to 100 ℃ most preferably from 25J/g to 100J/g, measured by DSC according to DIN 65467.

The amount of the isocyanate reactive group containing compound is preferably 5% to 95% by weight, preferably 10% to 90% by weight, based on 100% by weight of the amount of the components for preparing the polyurethane polymer.

The amount of the polyester polyol is preferably 15% by weight to 100% by weight, more preferably 50% by weight to 100% by weight, most preferably 99% by weight to 100% by weight, based on 100% by weight of the isocyanate reactive group-containing compound.

The hydroxyl value of the polyester polyol is preferably 20 to 80.

The polyester polyol is preferably one or more of the following: linear polyester polyols, lightly branched polyester polyols and lactones.

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.

The homopolymers or mixed polymers of lactones are preferably obtained by addition of lactones or lactone mixtures, such as butyrolactone,. epsilon. -caprolactone and/or methyl-. epsilon. -caprolactone, to suitable di-and/or higher-functional starter molecules. The epsilon-caprolactone is preferably a polymer of epsilon-caprolactone.

The isocyanate reactive group-containing compound preferably further comprises a compound selected from one or more of the following: the amount of the hydroxyl group-containing compound, thiol group-containing compound and amino group-containing compound is preferably 10% to 90% by weight, based on 100% by weight of the isocyanate-reactive group-containing compound.

The hydroxyl-containing compound is preferably one or more of the following: polyacrylate polyols, polyurethane polyols, polycarbonate polyols, polyether polyols, polyester polyacrylate polyols, polyurethane polyester polyols, polyurethane polyether polyols, polycarbonate polyether polyols, polyurethane polycarbonate polyols, polyester polycarbonate polyols and hydroxy-functional compounds having a molecular weight of 32 to 400g/mol, most preferably polycarbonate polyols.

The number average molecular weight of the polycarbonate polyol may be 400-8000g/mol, preferably 600-3000 g/mol.

The polycarbonate polyols may be selected from hydroxyl-containing polycarbonates, preferably polycarbonate diols.

The polycarbonate diol may be obtained from a carbonic acid derivative such as diphenyl carbonate or dimethyl carbonate and a polyol, preferably a diol.

The diol may be ethylene glycol, 1, 2-and 1, 3-propanediol, 1, 3-and 1, 4-butanediol, 1, 6-hexanediol, 1, 8-octanediol, neopentyl glycol, 1, 4-bis-hydroxymethylcyclohexane, 2-methyl-1, 3-propanediol, 2, 4-trimethyl-1, 3-pentanediol, dipropylene glycol, polypropylene glycols, dibutylene glycol, polybutylene glycols, bisphenol A or lactone-modified diols of the type mentioned above.

The diol preferably comprises 40 wt% to 100 wt% of hexylene glycol. The hexanediol is preferably 1, 6-hexanediol and/or hexanediol derivatives. The 1, 6-hexanediol derivatives contain ester or ether groups in addition to the OH end groups and can be obtained by reacting hexanediol with an equal amount or excess of caprolactone or by self-etherification of hexanediol to give di-or trihexylene glycol.

The polycarbonate polyether polyol may be a polyol based on dimethyl carbonate and hexanediol and/or butanediol and/or epsilon-caprolactone, preferably a polyol based on dimethyl carbonate and hexanediol and/or epsilon-caprolactone.

The hydroxy-functional compound having a molecular weight of 32g/mol to 400g/mol is preferably one or more of the following: polyols having up to 20 carbon atoms, ester diols and monofunctional or isocyanate-reactive hydroxy-functional compounds.

The polyol having up to 20 carbon atoms is preferably one or more of the following: ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 3-butanediol, cyclohexanediol, 1, 4-cyclohexanedimethanol, 1, 6-hexanediol, neopentyl glycol, hydroquinone dihydroxyethyl ether, bisphenol A (2, 2-bis (4-hydroxyphenyl) propane), hydrogenated bisphenol A (2, 2-bis (4-hydroxycyclohexyl) propane), trimethylolpropane, glycerol and pentaerythritol.

The ester diol is preferably one or more of a-hydroxybutyl-e-hydroxyhexanoate, ω -hydroxyhexyl- γ -hydroxybutyrate, adipic acid- β -hydroxyethyl ester and terephthalic acid- β -hydroxyethyl ester.

The monofunctional or isocyanate-reactive hydroxyl-functional compound is preferably one or more of the following: ethanol, n-butanol, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, 2-ethylhexanol, 1-octanol, 1-dodecanol, 1-hexadecanol, 1, 6-hexanediol, 1, 4-butanediol, neopentyl glycol, and trimethylolpropane, most preferably one or more of the following: 1, 6-hexanediol, 1, 4-butanediol, neopentyl glycol and trimethylolpropane.

The thiol group-containing compound is preferably one or more of the following: compounds comprising at least one thiol group, polythiols comprising thioether groups, polyesterthiols, and aromatic thio compounds.

The compound comprising at least one thiol group is preferably one or more of the following: methanedithiol, 1, 2-ethanedithiol, 1-propanedithiol, 1, 2-propanedithiol, 1, 3-propanedithiol, 2-propanedithiol, 1, 4-butanedithiol, 2, 3-butanedithiol, 1, 5-pentanethiol, 1, 6-hexanedithiol, 1, 2, 3-propanetrithiol, 1-cyclohexanedithiol, 1, 2-cyclohexanedithiol, 2-dimethylpropane-1, 3-dithiol, 3, 4-dimethoxybutane-1, 2-dithiol and 2-methylcyclohexane-2, 3-dithiol.

The polythiol comprising a thioether group is preferably one or more of: 2, 4-dimercaptomethyl-1, 5-dimercapto-3-thiapentane, 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane, 4, 8-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane, 4, 7-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane, 5, 6-bis- (mercaptoethylthio) -1, 10-dimercapto-3, 8-dithiadecane, 4, 5-bis- (mercaptoethylthio) -1, 10-dimercapto-3, 8-dithodecane, tetrakis (mercaptomethyl) methane, 1, 3, 3-tetrakis (mercaptomethylthio) propane, 1, 5, 5-tetrakis (mercaptomethylthio) -3-thiapentane, 1, 6, 6-tetrakis (mercaptomethylthio) -3, 4-dithian-ane, 2-mercaptoethylthio-1, 3-dimercaptopropane, 2, 3-bis (thio (2-mercaptoethyl)) -1-n-propanethiol, 2-bis (mercaptomethyl) -1, 3-dimercaptopropane, bis- (mercaptomethyl) sulfide, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) sulfide, bis (mercapto-ethyl) disulfide, bis (mercaptopropyl) sulfide, Bis (mercaptopropyl) disulfide, bis (mercaptomethylthio) methane, tris (mercaptomethylthio) methane, bis (mercaptoethylthio) methane, tris (mercapto-ethylthio) methane, bis (mercaptopropylthio) methane, 1, 2-bis (mercaptomethylthio) ethane, 1, 2-bis (mercaptoethylthio) ethane, 2-mercaptoethylthio) ethane, 1, 3-bis (mercaptomethylthio) propane, 1, 3-bis (mercaptopropylthio) propane, 1, 2, 3-tris (mercaptomethylthio) propane, 1, 2, 3-tris (mercapto-ethylthio) propane, 1, 2, 3-tris (mercaptopropylthio) propane, tetrakis (mercaptomethylthio) methane, tetrakis (mercaptoethylthiomethyl) methane, tetrakis (mercaptopropylthiomethyl) methane, 2, 5-dimercapto-1, 4-dithiane, 2, 5-bis (mercaptomethyl) -1, 4-dithiane and oligomers thereof obtainable according to JP-A07118263, 1, 5-bis (mercaptopropyl) -1, 4-dithiane, 1, 5-bis (2-mercaptoethylthiomethyl) -1, 4-dithiane, 2-mercaptomethyl-6-mercapto-1, 4-dithiacycloheptane, 2, 4, 6-trimercapto-1, 3, 5-trithiane, 2, 4, 6-trimercapto-methyl-1, 3, 5-trithiane and 2- (3-bis (mercaptomethyl) -2-thioisopropyl) -1, 3-dithiacyclopentane.

The polyester thiol is preferably one or more of the following: ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), (2-mercaptoacetate) diethylene glycol, diethylene glycol (3-mercaptopropionate), (3-mercaptopropionate) 2, 3-dimercapto-1-propanol ester, 3-mercapto-1, 2-propanediol bis (2-mercaptoacetate), 3-mercapto-1, 2-propanediol bis (3-mercaptopropionate), trimethylolpropane-tris (2-mercapto-acetate), trimethylolpropane-tris (3-mercaptopropionate), trimethylolethane-tris (2-mercaptoacetate), trimethylolethane-tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol, diethylene glycol bis (3-mercaptopropionate), and mixtures thereof, Pentaerythritol tetrakis (3-mercaptopropionate), glycerol tris (2-mercaptoacetate), glycerol tris (3-mercaptopropionate), 1, 4-cyclohexanediol bis (2-mercaptoacetate), 1, 4-cyclohexanediol bis (3-mercaptopropionate), hydroxymethyl sulfide-bis (2-mercaptoacetate), hydroxymethyl sulfide-bis (3-mercaptopropionate), hydroxyethyl sulfide (2-mercaptoacetate), hydroxyethyl sulfide (3-mercaptopropionate), hydroxymethyl disulfide (2-mercaptoacetate), hydroxymethyl disulfide (3-mercaptopropionate), (2-mercaptoethyl ester) thioglycolate, and bis (2-mercaptoethyl ester) thiodipropionate.

The aromatic thio compound is preferably one or more of the following: 1, 2-dimercaptobenzene, 1, 3-dimercaptobenzene, 1, 4-dimercaptobenzene, 1, 2-bis (mercaptomethyl) benzene, 1, 4-bis (mercaptomethyl) benzene, 1, 2-bis (mercaptoethyl) benzene, 1, 4-bis (mercaptoethyl) benzene, 1, 2, 3-trimercaptobenzene, 1, 2, 4-trimercaptobenzene, 1, 3, 5-trimercaptobenzene, 1, 2, 3-tris- (mercaptomethyl) benzene, 1, 2, 4-tris (mercaptomethyl) benzene, 1, 3, 5-tris (mercaptomethyl) benzene, 1, 2, 3-tris (mercaptoethyl) benzene, 1, 3, 5-tris (mercaptoethyl) benzene, 1, 2, 4-tris (mercaptoethyl) benzene, 2, 5-methanebenzenedithiol, 3, 4-methanebenzenedithiol, benzene, 1, 2, 4-methanedithiol, 1, 2-dimercaptobenzene, 1, 3-tris (mercaptoethyl) benzene, 1, 3, 5-methanedithiol, benzene, 1, 1, 4-naphthalenedithiol, 1, 5-naphthalenedithiol, 2, 6-naphthalenedithiol, 2, 7-naphthalenedithiol, 1, 2, 3, 4-tetramercaptobenzene, 1, 2, 3, 5-tetramercaptobenzene, 1, 2, 4, 5-tetramercaptobenzene, 1, 2, 3, 4-tetrakis (mercaptomethyl) benzene, 1, 2, 3, 5-tetrakis (mercaptomethyl) benzene, 1, 2, 4, 5-tetrakis (mercaptomethyl) benzene, 1, 2, 3, 4-tetrakis (mercaptoethyl) benzene, 1, 2, 3, 5-tetrakis (mercaptoethyl) benzene, 1, 2, 4, 5-tetrakis (mercaptoethyl) benzene, 2 '-dimercaptobiphenyl and 4, 4' -dimercaptobiphenyl.

The amino group-containing compound is preferably a mono-, di-, trifunctional amine and/or a mono-, di-, trifunctional hydroxylamine, further preferably one or more of the following: aliphatic and/or cycloaliphatic primary and/or secondary monoamines, diamines and triamines, most preferably one or more of the following: 1, 2-ethylenediamine, 1-amino-3, 3, 5-trimethyl-5-aminomethylcyclohexane (isophoronediamine), diethylenetriamine, diethanolamine, ethanolamine and N- (2-hydroxyethyl) -ethylenediamine.

The isocyanate-reactive group-containing compound preferably does not contain one or more of the following: polyether polyols and polyolefin polyols.

Emulsifier (a3)

The term "emulsifier" herein is a compound comprising emulsifying groups or latent emulsifying groups.

The amount of the emulsifier is 0.1 wt% to 20 wt% based on 100 wt% of the amount of the component for preparing the 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.

Cosmetic container (a4)

The amount of the solvent is 0.001 wt% to 20 wt% based on 100 wt% of the amount of the components for preparing the polyurethane polymer.

The 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 solvent may be added only at the beginning of the preparation, or may be added in part during the preparation as needed.

Reaction diluent (a5)

The amount of the reactive diluent is from 0.001 wt% to 90 wt%, based on 100 wt% of the amount of the components to prepare the polyurethane polymer.

The reaction diluent is preferably one or more of the following: acrylic acid and acrylic esters.

The acrylate is preferably methacrylate.

External emulsifier (a6)

The components for preparing the polyurethane polymer may further comprise an external emulsifier (a 6).

The amount of the external emulsifier component is 0.001 wt% to 10 wt% based on 100 wt% of the amount of the component for preparing the polyurethane polymer.

The external emulsifier is preferably a fatty alcohol polyether, most preferably one or more of the following: aliphatic ethylene glycol polyethers and aliphatic propylene glycol polyethers.

Organic antioxidant (b)

The amount of the organic antioxidant (b) is preferably 50ppm to 5000ppm based on 100% by weight of the solid component of the composition.

The amount of the organic antioxidant (b) is further preferably 0.01 wt% to 0.5 wt%, even more preferably 0.01 wt% to 0.1 wt%, most preferably 0.06 wt% to 0.1 wt%, based on 100 wt% of the amount of the solid component of the composition.

The organic antioxidant is preferably one or more of the following: metal carbamate compounds, phenolic antioxidants, amine antioxidants and heterocyclic antioxidants, with phenolic antioxidants being most preferred.

The metal in the metal carbamate is preferably one or more of the following: copper, zinc, molybdenum and antimony.

The phenolic antioxidant is preferably one or more of the following: alkyl hindered phenols, thioether structure-containing hindered phenol esters, polycyclic hindered phenols, and alkylthio hindered phenols, and most preferably 2, 6-di-t-butyl-4-methylphenol.

The amine antioxidant is preferably one or more of phenylenediamine antioxidants, diphenylamine antioxidants, phenyl- α -naphthylamine antioxidants and phenothiazine antioxidants.

The heterocyclic antioxidant is preferably one or more of the following: sulfur-containing compounds and nitrogen-containing heterocyclic compounds.

Chelating agent (c)

The term chelating agent herein refers to a compound capable of forming a stable complex with metal ions, in particular heavy metal ions or transition metal ions.

The amount of the chelating agent is preferably 0.01 wt% to 1.95 wt%, further preferably 0.01 wt% to 1 wt%, most preferably 0.05 wt% to 1 wt%, based on 100 wt% of the solid component of the composition.

The chelating agent is preferably present as a chelating agent salt, chelating agent acid or chelating agent ester, most preferably as a chelating agent salt.

The chelating agent salt is preferably a water soluble salt of a chelating agent.

The solubility of the water-soluble salt of the chelating agent in water is preferably not less than 0.15g/100g of water, more preferably not less than 1g/100g of water, most preferably 1g/100g of water to 100g/100g of water, as measured at room temperature of 20 ℃.

The water-soluble salt of the chelating agent preferably satisfies the following conditions: the content of the water-soluble salt of the chelating agent in the aqueous solution of the water-soluble salt of the chelating agent is 4.3 x 10^-7At mol/g, the pH is greater than 5, preferably greater than 6, more preferably greater than 9, most preferably from 9.5 to 11.

The water soluble salt of the chelating agent is preferably one or more of: ethylenediaminetetraacetate, tartrate, citrate, pyrophosphate, tripolyphosphate, hexametaphosphate, and gluconate.

The water soluble salt of the chelating agent is preferably one or more of: monovalent cation salts and multivalent cation salts. The content of the water-soluble monovalent cation salt of the chelating agent is preferably not less than 45% by weight based on 100% by weight of the water-soluble salt of the chelating agent.

The water soluble monovalent cation salt of the chelating agent is preferably one or more of: ethylenediaminetetraacetic acid monovalent cation salt, tartaric acid monovalent cation salt, citric acid monovalent cation salt, pyrophosphoric acid monovalent cation salt, tripolyphosphoric acid monovalent cation salt, hexametaphosphoric acid monovalent cation salt, aminotrimethylenephosphonic acid monovalent cation salt, ethylenediaminetetramethylenephosphonic acid monovalent cation salt, diethylenetriaminepentamethylenephosphonic acid monovalent cation salt, and gluconic acid monovalent cation salt, further preferably one or more of the following: ethylenediaminetetraacetic acid monovalent cation salts, tartaric acid monovalent cation salts, citric acid monovalent cation salts, pyrophosphoric acid monovalent cation salts, tripolyphosphoric acid monovalent cation salts, hexametaphosphoric acid monovalent cation salts, and gluconic acid monovalent cation salts, most preferably one or more of the following: ethylenediaminetetraacetic acid monovalent cation salts and pyrophosphoric acid monovalent cation salts.

The ethylenediaminetetraacetic acid monovalent cation salt is preferably one or more of the following: one or more of disodium ethylenediaminetetraacetate, trisodium ethylenediaminetetraacetate, tetrasodium ethylenediaminetetraacetate, diammonium ethylenediaminetetraacetate, dipotassium ethylenediaminetetraacetate and tetrapotassium ethylenediaminetetraacetate, most preferably one or more of the following: tetrasodium ethylenediaminetetraacetate and tetrapotassium ethylenediaminetetraacetate.

The monovalent cation salt of tartaric acid is preferably sodium potassium tartrate.

The monovalent cation salt of citric acid is preferably triammonium citrate.

The monovalent cation salt of pyrophosphate is preferably tetrasodium pyrophosphate.

The water soluble multivalent cation salt of the chelating agent is preferably one or more of: magnesium pyrophosphate, magnesium citrate, calcium gluconate, magnesium gluconate, and magnesium tartrate.

The content of the water-soluble multivalent cation salt of the chelating agent is preferably less than 70 wt.%, based on 100 wt.% of the water-soluble salt of the chelating agent.

The water-soluble monovalent cation salt of the chelating agent and the water-soluble multivalent cation salt of the chelating agent may be added as separate compounds, or may be added as compound salts containing the water-soluble monovalent cation salt of the chelating agent and the water-soluble multivalent cation salt of the chelating agent, such as disodium magnesium ethylenediaminetetraacetate and disodium calcium ethylenediaminetetraacetate. The content of the water-soluble monovalent cation salt of the chelating agent when added in the form of a compound salt is calculated as follows: Σ monovalent cation molar mass × monovalent cation number/(Σpolyvalent cation molar mass × polyvalent cation number + Σmonovalent cation molar mass × monovalent cation number), the content of water-soluble monovalent salt in, for example, disodium magnesium ethylenediaminetetraacetate salts is calculated by: 23 × 2/(23 × 2+24) ═ 65.7%.

The water soluble salt of the chelating agent is most preferably one or more of the following: tetrasodium ethylenediaminetetraacetate, tetrapotassium ethylenediaminetetraacetate, and tetrasodium pyrophosphate.

Stabilizer (e)

The composition may further comprise a stabilizer. The stabilizer is beneficial to reducing the hydrolysis of the composition and prolonging the pot life of the composition.

As used herein, the term "pot life" refers to the period of time between the initial mixing of two or more mutually reactive components of a composition to the point where the resulting composition has a viscosity at 25 ℃ of 2500cps when measured using a Brookfield R/S rheometer with a C50-1 spindle according to ASTM standard D7395-07.

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 0.5 to 10% by weight, most preferably 0.5 to 2% by weight, based on 100% by weight of the solid component of the composition.

Crosslinking agent (f)

The composition may further comprise a cross-linking agent.

The cross-linking agent is preferably one or more of the following: isocyanate group-containing compounds and polycarbodiimide group-containing compounds.

The content of the crosslinking agent is preferably 0.1 wt% to 10 wt% based on 100 wt% of the solid component of the composition.

Additive (g)

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.

A polymer (h) different from the polyurethane polymer

The composition may further comprise a polymer different from the polyurethane polymer.

The polymer different from the polyurethane polymer is preferably one or more of the following: polyester polymers, polyurethane-polyacrylate polymers, polyester-polyacrylate polymers, alkyd resins, polyamide/imide polymers, and polyepoxide polymers.

The polymer different from the polyurethane polymer preferably comprises one or more of the following groups: hydroxyl, amino and thiol groups.

The polymer different from the polyurethane polymer preferably comprises hydrolysable groups.

The term "hydrolyzable group" as used herein refers to polyester groups, polycarbonate groups and polyanhydride groups.

The weight ratio of the polymer different from the polyurethane polymer to the polyurethane polymer is preferably 1: 10-10: 1.

The composition is preferably a coating or an adhesive, more preferably an adhesive, and most preferably an anti-yellowing adhesive.

Process for preparing a composition

Preferably, the polyurethane polymer (a) and water (d) form an aqueous polyurethane dispersion, and then the organic antioxidant (b), chelating agent (c), optionally a stabilizer (e), optionally a crosslinking agent (f), and optionally an additive (g) are introduced to obtain the composition.

Preferably, the polyurethane polymer (a) and water (d) form an aqueous polyurethane dispersion, and the composition is obtained by introducing the organic antioxidant (b), the chelating agent (c), optionally a stabilizer (e), optionally a crosslinking agent (f), optionally an additive (g) and optionally a polymer (h) different from the polyurethane polymer.

The water in the composition can be introduced before the polyurethane polymer is formed, can be introduced during the formation of the polyurethane polymer, and can be introduced after the polyurethane polymer is formed. The water is preferably introduced after the polyurethane polymer is formed.

The water and polyurethane polymer are mixed to form an aqueous polyurethane dispersion.

The term aqueous polyurethane dispersion is also used as a synonym for aqueous polyurethaneurea dispersions and/or aqueous polyurethane polyurea dispersions and/or aqueous polyurea dispersions.

A catalyst, such as dibutyltin dilaurate, may be added for the polyurethane polymer preparation.

The 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 the components of the polyurethane polymer may be in a conventional manner.

The polyisocyanate and the isocyanate-reactive group-containing compound may be added in one portion or in multiple portions, either the same or different from the previously added portions.

The organic solvent present in the polyurethane polymer can be removed by distillation. The organic solvent may be removed during or after the polyurethane polymer is formed.

The amount of residual organic solvent in the polyurethane polymer is preferably less than 1.0% by weight, based on 100% by weight of the polyurethane polymer.

The chelating agent may be added as a solid or as an aqueous solution. Preferably in the form of an aqueous solution of the chelating agent, which will facilitate the dispersion of the chelating agent.

The water-soluble salts of the chelating agents can be added directly or can be formed in the composition in an acid-base neutralized form. The acid-base neutralization may be complete or incomplete neutralization, preferably complete neutralization.

The acid may be a free acid capable of undergoing a neutralization reaction with a base to form a water-soluble salt of the chelating agent. The free acid is preferably one or more of the following: aminocarboxylic acids, hydroxycarboxylic acids, inorganic polyphosphoric acids, hydroxyaminocarboxylic acids, organic polyphosphonic acids, and polycarboxylic acids.

The aminocarboxylic acid is preferably ethylenediaminetetraacetic acid and/or nitrilotriacetic acid.

The hydroxycarboxylic acid is preferably one or more of the following: tartaric acid, citric acid and gluconic acid.

The inorganic polyphosphoric acid is preferably one or more of the following: tripolyphosphoric acid, hexametaphosphoric acid and pyrophosphoric acid.

The hydroxyamino-carboxylic acid is preferably hydroxyethylethylenediaminetriacetic acid and/or dihydroxyethylglycine.

The solids content of the aqueous polyurethane dispersion is preferably from 30% to 70% by weight, based on 100% by weight of the aqueous polyurethane dispersion.

Coating method

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 by applying the adhesive 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.

Method for manufacturing bonded product

Preferably, the method further comprises a step iv between steps ii and iii.

The method for manufacturing a bonded product preferably comprises the steps of:

i. applying an adhesive provided according to the present invention to at least one surface of a substrate;

ii heating and drying the substrate surface to which the adhesive is applied;

irradiating the substrate surface treated in step ii with actinic radiation; and

contacting the surface of the substrate treated in step iv with the surface of the substrate itself or of an additional substrate to obtain the bonded product.

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 by applying the adhesive 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.

The heating and drying of the surface of the substrate to which the adhesive is applied may mean heating and drying only the surface of the substrate, or 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 actinic radiation irradiation is preferably carried out at a temperature of the surface of the step ii treated substrate of not less than 35 c, most preferably immediately after the step ii treatment.

The actinic radiation irradiating the substrate surface treated in step ii may refer to irradiating only the substrate surface, or may refer to irradiating a part of the substrate including the substrate surface or the entire substrate.

The actinic radiation crystallizes and cures the adhesive.

The actinic radiation is preferably UV radiation, solar radiation, radiation with inert gases or oxygen-depleted gases excluding oxygen, or radiation with a radiation-transparent medium covering the area to be irradiated, most preferably UV radiation or solar radiation.

The inert gas is preferably nitrogen or carbon dioxide. The radiation-transparent medium is preferably a synthetic film, glass or a liquid such as water.

The UV radiation or solar radiation can be modified with medium-or high-pressure mercury vapor lamps, optionally doped with other elements, such as gallium or iron, or with lasers, pulsed lamps, halogen lamps or excimer radiators.

The actinic radiation is most preferably UV radiation. The UV radiation is most preferably mercury radiation using a fixed installation.

When the substrate has a three-dimensional surface of a complicated shape, it is preferable to perform irradiation using a plurality of irradiation devices, which are arranged appropriately so that the surface receives the irradiation uniformly.

The wavelength of the actinic radiation is preferably from 200nm to 750 nm.

The dose of actinic radiation is preferably not less than 80mJ/cm²Further preferably 80mJ/cm²-5000mJ/cm²More preferably 200mJ/cm²-2000mJ/cm²Most preferably 1250mJ/cm²-1950mJ/cm²。

Within the above range, the higher the dose of actinic radiation, the better, but should not be above the radiation dose limit at which the substrate deforms in an uncontrolled manner or suffers other damage.

The contact is preferably carried out before the temperature of the substrate surface is lowered to a temperature lower than the temperature at which the adhesive can adhere, and more preferably before the temperature of the substrate surface is not lower than 60 ℃.

The surface of the substrate treated in step iv is preferably contacted with the substrate itself or an additional substrate within one hour, more preferably within 30 minutes, still more preferably within 10 minutes, and most preferably within 5 minutes to obtain the bonded product.

The additional substrate may be any substrate that requires adhesion.

The additional substrate and the base material may be the same or different.

The additional substrate is preferably coated, heated and treated with actinic radiation as the substrate.

The additional substrate is preferably not treated with a primer, high energy radiation or ozone prior to contacting the substrate surface.

The high-energy radiation may be ionizing radiation, in particular plasma.

After contacting the substrate surface treated in step ii or step iv with the substrate itself or the additional substrate, a further heat treatment may be carried out.

After contacting the surface of the substrate treated in step ii or iv with the substrate itself or the additional substrate, a further cooling treatment may be performed to reduce the temperature of the bonded product to room temperature.

The method of introducing heat is preferably one or more of the following: convection ovens or spray dryers, infrared thermal radiation, near infrared thermal radiation, microwaves and objects in contact with substrates coated with the adhesives of the invention are used to transfer heat at elevated temperatures.

Preferably, no heat is introduced to the substrate surface after said step ii treatment or after said step iv treatment before said substrate surface is contacted with said substrate itself or another substrate.

Adhesive product

The adhesive product is preferably a shoe.