阅读说明：本技术 一种聚氨酯组合物、其制备方法和应用 (Polyurethane composition, preparation method and application thereof ) 是由 朱英丹 金晨 E·阿夫托莫诺夫 于 2019-08-21 设计创作，主要内容包括：本发明涉及一种组合物、其制备和应用,以及用该组合物涂覆得到的产品。该组合物包含：(a)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)多异氰酸酯,(a2)具有异氰酸酯反应性基团的化合物,所述具有异氰酸酯反应性基团的化合物包含聚合物多元醇,所述聚合物多元醇选自下列的一种或多种：聚醚多元醇和聚烯烃多元醇,(a3)任选的乳化剂,(a4)任选的溶剂,和(a5)任选的反应性稀释剂；(b)有机抗氧化剂,所述抗氧化剂的量为0.01重量%-2.4重量%,基于所述组合物的固体组分的总重量计；(c)螯合剂；和(d)水。根据本发明的组合物具有良好的耐高温黄变性。(The present invention relates to a composition, its preparation and use, and to the products coated with the composition. The composition comprises: (a) a polyurethane polymer that is the reaction product of: (a1) a polyisocyanate, (a 2) a compound having isocyanate reactive groups, the compound having isocyanate reactive groups comprising a polymer polyol selected from one or more of the following: polyether polyols and polyolefin polyols, (a 3) optionally an emulsifier, (a 4) optionally a solvent, and (a 5) optionally a reactive diluent; (b) an organic antioxidant in an amount of 0.01 wt% to 2.4 wt%, based on the total weight of the solid components of the composition; (c) a chelating agent; and (d) water. The compositions according to the invention have good resistance to yellowing at high temperatures.)

1. A composition, comprising:

(a) a polyurethane polymer that is the reaction product of:

(a1) a polyisocyanate,

(a2) a compound having isocyanate reactive groups, the compound having isocyanate reactive groups comprising a polymer polyol selected from one or more of the following: polyether polyols and polyolefin polyols,

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

(a4) optionally a solvent, and

(a5) optionally a reactive diluent;

(b) an organic antioxidant in an amount of 0.01 wt% to 2.4 wt%, based on the total weight 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 of claim 1, wherein the amount of polymer polyol is 70% to 100% by weight, based on the total weight of the compound having isocyanate reactive groups (a 2).

3. The composition of claim 1, wherein the amount of the organic antioxidant (b) is from 0.06 wt% to 2.0 wt%, based on the total weight of the solid components of the composition.

4. The composition according to claim 1, wherein the amount of the chelating agent (c) is 0.04 to 1.8 wt. -%, preferably 0.04 to 1 wt. -%, further preferably 0.05 to 1 wt. -%, most preferably 0.1 to 1 wt. -%, based on the total weight of the solid components of the composition.

5. The composition of claim 1, wherein the chelating agent (c) is present in the form of one or more of: chelator salts and chelator acids.

6. The composition of claim 5, wherein the chelator salt is a chelator water soluble salt selected from one or more of the following: ethylenediaminetetraacetate, tartrate, citrate, pyrophosphate, tripolyphosphate, hexametaphosphate, and gluconate.

7. The composition of claim 5, wherein the chelating agent acid is one or more of: ethylenediaminetetraacetic acid, nitrilotriacetic acid, tartaric acid, citric acid, pyrophosphoric acid, and gluconic acid.

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

9. The composition of any one of claims 1 to 8, wherein the composition is a coating or an adhesive.

10. A process for the preparation of a composition as claimed in any one of claims 1 to 9, 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), the optional stabilizer (e), the optional crosslinking agent (f) and the optional additives (g) in any desired manner.

11. The method of claim 10, wherein the polyurethane polymer (a) and water (d) form an aqueous polyurethane dispersion, and the organic antioxidant (b), the chelating agent (c), the optional stabilizer (e), the optional crosslinking agent (f), and the optional additive (g) are introduced to form the composition.

12. The process according to any one of claims 10 to 11, wherein the chelating agent (c) is added in the form of an aqueous solution.

13. Use of a composition according to any one of claims 1 to 9 for the preparation of a coated product.

14. A coating method comprising the steps of: applying a composition as claimed in any one of claims 1 to 9 to a substrate surface and then curing.

15. A coated product comprising a substrate and a coating formed by applying the composition of any one of claims 1-9 to the substrate.

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

i. applying a composition according to any one of claims 1 to 9 to at least one surface of a substrate;

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 a further substrate to obtain the bonded product.

17. The method of claim 16, further comprising, between steps ii and iii, step iv:

irradiating the substrate surface treated in step ii with actinic radiation.

18. The method of claim 16, 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.

19. A bonded product made according to the method of any of claims 16-18.

Technical Field

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

Background

The polyurethane polymer and water can be mixed to form an aqueous polyurethane dispersion. The aqueous polyurethane dispersions can be used in the field of coatings and adhesives. In the field of adhesives, it is common to apply an aqueous polyurethane dispersion to a substrate surface, then heat to remove the water from the dispersion by evaporation, followed by heat activation (e.g., infrared heating) of the coating, and finally contact the substrate surface to which the dispersion is applied with other substrate surfaces to obtain a bonded product. In practice, if the temperature required for thermal activation is high, not only is more energy required, but also manual application and bonding difficulties increase, and it is therefore desirable in the industry to find an adhesive suitable for thermal activation at low temperatures.

US 4870129A discloses an adhesive comprising a crosslinker containing isocyanate functional groups and an aqueous polyurethane dispersion containing hydroxyl groups, wherein the thermal activation temperature required for the coating formed by the composition is from 40 ℃ to 80 ℃. However, the adhesive has the disadvantages of being easily yellowed and being unattractive.

Yellowing of adhesives is often caused by oxidation of their polymers. When the adhesive is exposed to heat or UV light, the oxidation process is accelerated, leading to 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 obtained by using the adhesive are reduced. In practice, coatings and adhesives are often applied in high temperature environments. For example: the adhesive is applied to the glass fibers during the sizing process, the adhesive is first applied to the glass fibers and then dried at an elevated temperature to form the plastic panel.

EP0356655B1 discloses a composition for application to a reinforcement material comprising at least one crosslinkable polyurethane, 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 multidentate compound or has the formula (RH)_2nC_n)₂N(CH₂)_xN(C_nH_2nR)₂The compound of (1). The glass fiber reinforced polymer treated with the above composition has good mechanical properties even after long term exposure to solvents, high temperatures 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 comprises a thermoplastic polyester, a polyoxyalkylene, ethylene glycol, polyvinyl alcohol, a polyolefin latex, polyvinyl acetate, an epoxy resin, starch, a combination of an epoxy polymer and polyvinyl alcohol, a combination of an epoxy polymer and polyurethane; component B is a metal chelator selected from multidentate compounds or having the formula (RH)_2nC_n)₂N(CH₂)_xN(C_nH_2nR)₂A compound of (1); both components C and D are antioxidants. The treatment of the fibres with the above composition results in products having good mechanical properties after prolonged 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 multidentate compound. The adhesive has high strength even at high temperatures.

Although the technical proposal solves the problems of aging and mechanical property reduction of the coating and the adhesive at high temperature, the technical proposal does not solve the problem of yellowing of the coating and the adhesive when being heated.

CN104387548 discloses a polyurethane resin which is not easy to yellow, 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, wherein the amount of pyrophosphate is 10 wt% to 75 wt% based on the weight of polyurethane solids.

CN106928422 discloses a method for preparing yellowing-resistant polyurethane, comprising the steps of: (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 is resistant to yellowing.

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

Disclosure of Invention

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

The composition according to the invention comprises:

(a) a polyurethane polymer that is the reaction product of:

(a1) a polyisocyanate,

(a2) a compound having isocyanate reactive groups, the compound having isocyanate reactive groups comprising a polymer polyol selected from one or more of the following: polyether polyols and polyolefin polyols,

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

(a4) optionally a solvent, and

(a5) optionally a reactive diluent;

(b) an organic antioxidant in an amount of 0.01 wt% to 2.4 wt%, based on the total weight 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.

In one aspect of the present invention, there is provided a process for the preparation of a composition provided according to the present invention, 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), the optional stabilizer (e), the optional crosslinking agent (f) and the optional additives (g) in any desired manner.

In a further aspect of the invention, the use of a composition provided according to the invention for the preparation of a coated product.

In yet 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 the surface of a substrate and subsequently cured.

In 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 onto the substrate.

In yet another aspect of the present invention, there is provided a method of manufacturing a bonded product, comprising the steps of:

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

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 a further substrate to obtain the bonded product.

In yet another aspect of the invention, a bonded product made by the method provided according to the invention is provided.

The compositions according to the invention have good resistance to yellowing.

Detailed Description

The present invention provides a composition comprising:

(a) a polyurethane polymer that is the reaction product of:

(a1) a polyisocyanate,

(a2) a compound having isocyanate reactive groups, the compound having isocyanate reactive groups comprising a polymer polyol selected from one or more of the following: polyether polyols and polyolefin polyols,

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

(a4) optionally a solvent, and

(a5) optionally a reactive diluent;

(b) an organic antioxidant in an amount of 0.01 wt% to 2.4 wt%, based on the total weight 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 in the field of coatings and adhesives, and products 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 and form a coating upon application. The composition according to the invention may be a coating or an adhesive.

The term "coating" as used herein refers to a composition that can be applied to the surface of an object by various coating processes to form a strong and continuous solid coating having a certain strength.

The term "adhesive" as used herein refers to a composition that can be applied to the surface of an object by different coating processes, form a coating on the surface of the object itself or on the surface of one object to another, and bond the surface of the object itself or the surface of one object to another. Also used as synonyms for adhesives and/or sealants and/or adhesives.

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 preferably does not contain hydrolysable groups.

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

Polyisocyanate (a 1)

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, more preferably 5% to 35% by weight, most preferably 10% to 30% by weight, based on the total weight of the components 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 ester diisocyanate, lysine triisocyanate, bis (isocyanatomethyl) sulfide, bis (isocyanatoethyl) sulfide, bis (isocyanatopropyl) sulfide, bis (isocyanatohexyl) sulfide, hexamethylene diisocyanate, and the like, 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-heptanetetraisocyanate, 2, 6-diisocyanatomethyl-3, 5-dithia-1, 7-heptanetetraisocyanate, 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 alicyclic polyisocyanate is preferably as followsOne 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-Pentanediisocyanate (PDI), m-tetramethylxylylene diisocyanate (m-TMXDI), methylenebis (4-cyclohexyl isocyanate), and cyclohexane diisothiocyanate, most preferably one or more of the following: isophorone diisocyanate and methylene bis (4-cyclohexyl isocyanate).

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 (phenylisocyanate), 4' -methylenebis (2-methylphenylisocyanate), bibenzyl-4, 4 '-diisocyanate, bis (isocyanatophenyl) ethylene, bis (isocyanatomethyl) benzene, bis (isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene, α, α, α', alpha' -tetramethylxylylene diisocyanate, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanatomethylphenyl) ether, bis (isocyanatoethyl) o-phenylenePhthalate, 2, 6-bis (isocyanatomethyl) furan, 2-isocyanatophenyl-4-isocyanatophenyl sulfide, bis (4-isocyanatophenyl) sulfide, bis (4-isocyanatomethylphenyl) 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 (phenyl isothiocyanate), 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 group]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: toluene diisocyanate, 1, 2-diisocyanatobenzene, 1, 3-diisocyanatobenzene, 1, 4-diisocyanatobenzene, diphenylmethane diisocyanate and 2, 4-diisocyanatotoluene.

The polyisocyanates 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-isocyanatophenyl-4-isothiocyanatophenyl sulfide and 2-isocyanatoethyl-2-isothiocyanatoethyl disulfide.

The polyisocyanate may also be a halogen substituent of the above-mentioned polyisocyanates, such as 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 having isocyanate reactive group (a 2)

The term "isocyanate-reactive group" as used herein refers to a group containing Zerewitinov-active hydrogen. Zerevitinov-active hydrogens are defined in Romp's Chemical Dictionary (Rommp 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 amount of the compound having isocyanate reactive groups is preferably 5% to 95% by weight, preferably 10% to 90% by weight, based on the total weight of the components for preparing the polyurethane polymer.

The amount of the polymer polyol is preferably 70 wt% to 100 wt%, further preferably 75 wt% to 100 wt%, still further preferably 80 wt% to 100 wt%, most preferably 90 wt% to 100 wt%, based on the total weight of the compound having an isocyanate reactive group.

The compound having an isocyanate-reactive group preferably does not contain a group that can form a hydrolyzable group.

The term "group which can form a hydrolyzable group" herein refers to an ester group, a carbonate group, an amide group and an acid anhydride group.

The polymer polyol is preferably a polyether polyol.

The polyether polyol preferably has a hydroxyl functionality of from 1.5 to 6.0, most preferably from 1.8 to 3.0.

The hydroxyl value of the polyether polyol is preferably from 50 mg KOH/g to 700mg KOH/g, most preferably from 50 KOH/g to 600 mg KOH/g.

The polyether polyols preferably have a number average molecular weight of from 400 g/mol to 4000g/mol, most preferably from 500 g/mol to 3000 g/mol.

The polyether polyol is preferably one or more of the following: polyaddition products of alkylene oxides, condensation products of polyols or polyol mixtures, and alkoxylation products of polyfunctional alcohols, amines and amino alcohols, further preferably alkoxylation products of polyfunctional alcohols, amines and amino alcohols, most preferably one or more of the following: a poly (propylene oxide) polyol having a number average molecular weight of 400 g/mol to 4000g/mol and a polyoxytetramethylene polyol having a number average molecular weight of 400 g/mol to 4000 g/mol.

The polyaddition product of alkylene oxides is preferably one or more of the following: addition polymerization products of ethylene oxide, 1, 2-propylene oxide, 1, 2-butylene oxide, 2, 3-butylene oxide, tetrahydrofuran, styrene or epichlorohydrin, and also their co-addition polymerization products and graft products.

The alkoxylation products of the polyfunctional alcohols, amines and amino alcohols are preferably alkoxylation products of hydroxy-functional starter molecules such as ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, hexanediol, diethylene glycol, trimethylolpropane, glycerol, pentaerythritol, sorbitol or mixtures thereof with propylene oxide or butylene oxide.

The polyether polyols herein having a correspondingly high hydroxyl content but particularly low molecular weights may be water-soluble.

However, the polyether polyol is particularly preferably one or more of the following: a water insoluble poly (propylene oxide) polyol having a number average molecular weight of from 500 g/mol to 3000g/mol and a water insoluble poly (tetramethylene oxide) polyol having a number average molecular weight of from 500 g/mol to 3000 g/mol.

By "water-insoluble polyol" is meant herein that the polyol has a solubility in water at 23 ℃ of less than 10 g/liter, preferably less than 5 g/liter. In other words, the polyol precipitated out when it was dispersed in water in the experiment.

Emulsifier (a 3)

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

The amount of the emulsifier is from 0.1 wt% to 20 wt% based on the total weight of the components that make up 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 and 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 during or after the preparation of the polyurethane polymer by partial or complete addition of neutralizing agents to form salts.

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.

Solvent (a 4)

The amount of the solvent is from 0.001 wt% to 20 wt%, based on the total weight of the components to prepare 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.

Reactive diluent (a 5)

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

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

The acrylate is preferably methacrylate.

External emulsifier (a 6)

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

The amount of the external emulsifier component ranges from 0.001 wt% to 10 wt% based on the total weight of the components from which the polyurethane polymer is prepared.

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.

The amount of the polyurethane polymer is preferably from 10 wt% to 99.5 wt%, based on the total weight of the solid components of the composition.

The amount of the polyurethane polymer is most preferably from 90 wt% to 99.5 wt%, based on the total weight of the solid components of the composition.

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

Organic antioxidant (b)

The amount of the organic antioxidant (b) is preferably from 0.06 wt% to 2.0 wt%, based on the total weight of the solid components 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 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, polycyclic hindered phenols, and alkylthio hindered phenols.

The amine antioxidant is preferably one or more of the following: phenylenediamine antioxidants, diphenylamine antioxidants, phenyl-alpha-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 a metal ion, in particular a heavy metal ion or a transition metal ion.

The amount of the chelating agent is preferably 0.04 wt% to 1.8 wt%, further preferably 0.04 wt% to 1 wt%, still further preferably 0.05 wt% to 1 wt%, most preferably 0.1 wt% to 1 wt%, based on the total weight of the solid components of the composition.

The chelating agent is preferably present in one or more of the following forms: the chelating agent salt, chelating agent acid and chelating agent ester are further preferably present in the form of a chelating agent salt and/or a chelating agent acid, most preferably in the form of 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 water, most preferably not less than 1g/100g water, measured at room temperature at 20 ℃.

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

The water soluble salt of the chelating agent is preferably one or more of: ethylenediaminetetraacetate, tartrate, citrate, pyrophosphate, tripolyphosphate, hexametaphosphate, aminotrimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid and gluconate, further preferably one or more of the following: ethylenediaminetetraacetate, tartrate, citrate, pyrophosphate, tripolyphosphate, hexametaphosphate and gluconate, most preferably one or more of the following: ethylenediaminetetraacetate and pyrophosphate.

The edetate is preferably tetrasodium edetate.

The pyrophosphate is preferably sodium pyrophosphate.

The chelator acid may be insoluble in water or may be soluble.

The chelating agent acid preferably has a pH of 1 to 6.

The chelating agent acid is preferably one or more of the following: aminocarboxylic acids, hydroxycarboxylic acids, inorganic polyphosphoric acids, hydroxyaminocarboxylic acids, organic polyphosphonic acids and polycarboxylic acids, further preferably one or more of the following: ethylenediaminetetraacetic acid, nitrilotriacetic acid, tartaric acid, citric acid, pyrophosphoric acid, tripolyphosphoric acid, hexametaphosphoric acid and gluconic acid, with one or more of the following being further preferred: ethylenediaminetetraacetic acid, nitrilotriacetic acid, tartaric acid, citric acid, pyrophosphoric acid and gluconic acid, most preferably one or more of the following: ethylenediaminetetraacetic acid and nitrilotriacetic acid.

The aminocarboxylic acid is preferably nitrilotriacetic acid.

Stabilizer (e)

The composition may further comprise a stabilizer. The stabilizer advantageously reduces hydrolysis of the composition, thereby extending 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 suitable 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 stabilizer is preferably present in an amount of from 0.5 wt% to 10 wt%, most preferably from 0.5 wt% to 2 wt%, based on the total weight of the solid components 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 crosslinker is preferably present in an amount of 0.1 wt% to 10 wt%, based on the total weight of the solid components 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 preferably does not contain hydrolysable groups.

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

the composition is preferably a coating or adhesive, more preferably an adhesive, 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), optional stabilizer (e), optional crosslinking agent (f) and optional additive (g) are introduced to obtain the composition.

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

The water in the composition can be introduced before the polyurethane polymer is formed, can be introduced during the polyurethane polymer formation, or 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 in the preparation of the polyurethane polymer.

The polyurethane polymer is preferably prepared by 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 can be carried out in a conventional manner.

The polyisocyanate and the compound having an isocyanate-reactive group may be added in one portion or in multiple portions, and may be the same component or different components from those previously added.

The organic solvent present in the polyurethane polymer can be removed by distillation. The organic solvent may be removed during the formation of the polyurethane polymer or may be removed 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 the total 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 may be added directly or may be formed in the composition in an acid-base neutralized form. The acid-base neutralization may be complete or partial neutralization, preferably complete neutralization.

The chelating agent may be added during chain extension or neutralization for preparing the polyurethane polymer, or may be added after chain extension, or may be added during or after dispersion of the polyurethane polymer in water, or may be added during or after distillation of the polyurethane polymer.

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 one or more of the following: 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 one or more of the following: 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 "applying" may be 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

The method preferably further comprises between step ii and step iii a step iv:

irradiating the substrate surface treated in step ii with actinic radiation.

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;

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 a further 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 "applying" may be 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 the substrate surface applied with the adhesive" may mean heating and drying only the substrate surface, or may mean heating and drying a part of the substrate including the substrate surface applied with the adhesive or the entire substrate.

The "heating and drying" can remove volatile components. The volatile component may be water.

The "heating and drying" is preferably one or more of the following: infrared thermal radiation, near infrared thermal radiation, microwaves and the use of convection ovens or spray dryers at elevated temperatures.

The temperature of the heating is as high as possible, 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 not less than 35 ℃ on the surface of the substrate treated in step ii, most preferably immediately after the treatment in step ii.

The "irradiation of the actinic radiation to the substrate surface treated in step ii" may mean irradiation of only the substrate surface, or may mean irradiation of 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 an inert gas or oxygen-depleted gas in the absence of oxygen or radiation with a radiation-transparent medium covering the site 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 mercury vapor can be modified in the UV radiation or solar radiation with a medium-or high-pressure mercury vapor lamp, optionally doped with other elements, such as gallium or iron, or it can be modified with a laser, a pulsed lamp, a halogen lamp or an excimer radiator.

The actinic radiation is most preferably UV radiation. Most preferably, fixedly mounted mercury radiation is used among the UV radiation.

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 80 mJ/cm²Further preferably 80 mJ/cm²-5000 mJ/cm²More preferably 200 mJ/cm²-2000 mJ/cm²Most preferably 1250mJ/cm²-1950mJ/cm²。

Within the above range, the radiation dose of actinic radiation is as high as possible, 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 substrate surface treated in step iv is preferably contacted with the substrate itself or a further substrate within one hour, more preferably within 30 minutes, even more preferably within 10 minutes, most preferably within 5 minutes to obtain the bonded product.

The additional substrate may be any substrate that requires adhesion.

The additional substrate may or may not be the same as the substrate.

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 treated in step iv with the substrate itself or the further substrate, a further heat treatment may be carried out.

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

It is preferred that no heat need be introduced to the substrate surface prior to contacting the substrate surface treated in step ii or treated in step iv with the substrate itself or another substrate.

Adhesive product

The adhesive product is preferably a shoe.

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 values and 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.

The use of "including," "comprising," and "containing" herein is meant to encompass the presence of only the recited elements as well as the presence of other elements not recited in addition to the recited elements.

All percentages in the present invention are by weight unless otherwise indicated.

The analysis and measurement according to the invention were carried out at a temperature of 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 analyzer from Mettler Toledo in accordance with 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.

Isocyanate functionality was determined according to GPC.

The pH was measured at 23 ℃ using a PB-10pH meter from Sartorius, Germany.

The number average molecular weight was determined by gel permeation chromatography using tetrahydrofuran as the mobile phase against polystyrene standards at 23 ℃.

Hydroxyl number was determined according to ASTM D4274.

Raw materials and reagents

Desmophen^®3600: low functionality polyether polyols having a functionality of 2, a number average molecular weight of 2000g/mol and a hydroxyl number of 56 mg KOH/g are available from Kostew, Germany.

Desmodur^®T-80: toluene diisocyanate mixtures, commercially available from Kossi Innovation GmbH, Germany.

Ethylenediaminetetraacetic acid tetrasodium salt (EDTA 4 Na): the content of the tetrasodium salt of the ethylenediaminetetraacetic acid is 4.3 x 10^-7The pH of the aqueous solution was 10.35 in mol/g, and the aqueous solution was available from national pharmaceutical products chemical Co., Ltd, and had a solubility of 100g/100g as measured at room temperature of 20 ℃.

Sodium pyrophosphate: the content of sodium pyrophosphate is 4.3 x 10^-7The pH of the aqueous solution was 9.89 mol/g, and the aqueous solution was available from national pharmaceutical products chemical Co., Ltd, and had a solubility of 6.2g/100g as measured at room temperature of 20 ℃.

Nitrilotriacetic acid: the content of nitrilotriacetic acid is 4.3 x 10^-7The pH value of the aqueous solution is 2.92, and the aqueous solution is available from national pharmaceutical group chemical reagent Co., Ltd, and the solubility is measured at room temperature of 20 DEG C<0.01g/100g。

2, 6-di-tert-butyl-4-methylphenol: organic antioxidants, available from merck chemistry.

Preparation of the compositions in the inventive and comparative examples

Preparation of aqueous polyurethane dispersions

380.2g Desmophen^®3600 was dehydrated at 110 ℃ and 15 mbar for 1 hour, 7.6g of 2, 2-dimethylolpropionic acid were added and cooled while stirring. 62.8g Desmodur were added at 60 ℃^®T-80, stirred at 80-90 ℃ until an isocyanate content of 2.1% is reached. The mixture was then dissolved in 676g of acetone and cooled to 50 ℃ to obtain a reaction solution. 7.3g of an aqueous solution of 31% strength sodium hydroxide are added to the reaction solution and stirred for 5 minutes, followed by the addition of a solution of 6.8g of 2- (2-aminoethoxy) ethanol in 41g of water. After stirring vigorously for 30 minutes, this mixture was dispersed by adding 648g of water, followed by distillation to separate out the acetone, to give an aqueous polyurethane dispersion having a solids content of 40.1% by weight.

Preparation of the composition

Table 1 shows the compositions and performance test results of the compositions in the inventive examples and comparative examples.

The organic antioxidant, the chelating agent and the prepared aqueous polyurethane dispersion were mixed in the amounts shown in table 1, and the mixture was stirred or shaken to obtain a uniform composition.

Performance testing

Yellowing resistance test method

20g of each of the compositions of the inventive and comparative examples were weighed into flat-bottomed teflon pans and stored at room temperature to give a dry coating. The thickness of the coating is 0.74 mm + -0.08 mm. The coating was cut into several portions uniformly, and one portion was baked in an oven at 80 ℃ for 7 hours. The remaining coating was kept at ambient temperature as a reference for the color change contrast.

The color contrast is based on the CIELAB method. The samples were placed on the same white background and tested for L, a, b values using a BYK colorimeter. The Δ b value is equal to the difference between the b value of the sample subjected to high temperature treatment and the b value of the same sample stored at room temperature without high temperature treatment. The larger the Δ b value, the more yellowing the sample.

The results of the performance tests are shown in table 1.

Table 1: composition and performance test results of the compositions in the inventive examples and comparative examples

n.b.: the composition flocculated and failed to form a coating.

When comparing inventive examples 1-5 and comparative examples 1-7, it can be seen that the Δ b value of the coatings formed using the composition according to the invention is much smaller than in the case of the comparative composition, indicating that the yellowing resistance of the coatings formed using the composition according to the invention is much better than in the case of the comparative composition.

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. Therefore, any changes, which come within the meaning and range of equivalency of the claims, are to be embraced within their scope.