PVC material composite water-based adhesive and preparation method thereof

[0023] In a preferred embodiment, the method of preparing the urethane-modified acrylic prepolymer comprises the steps of:

[0024] Step a: parts by weight, 2 to 4 parts of the polyether polyol is added to the kettle at 90 ~ 105 ℃ vacuum dewatered 1.5 ~ 2.5h, cooled to 50 ~ 60 ℃, nitrogen gas, under a nitrogen atmosphere 11 was added to 18 parts of diisocyanate, warmed to 70 ~ 75 ℃, stirred for 1 ~ 2h, to give a mixture A;

[0025] Step b: 1 to 4 parts of 2,2-dimethylol propionic acid was added 5 to 10 parts by N- methylpyrrolidone uniformly mixed, added to A and the mixture stirred for 1 to 3H;

[0026] Step c: temperature was raised to 75 ~ 80 ℃, was added 2 to 5 parts of hydroxyethyl acrylate and 1 to 3 parts of isopropanol was stirred for 1 ~ 2h, cooled to 50 ~ 65 ℃, adding 8 to 12 parts of methyl methacrylate, after continued cooling to below 40 ℃, adding 1 to 2 parts of triethanolamine and stirred for 0.3 ~ 0.7h, added to 50 parts of water to obtain 40-modified urethane acrylate oligomer.

[0027] In a more preferred embodiment, the method of preparing the urethane-modified acrylic prepolymer comprises the steps of:

[0028] Step a: in parts by weight, and 3 parts of polyether polyol is added to the kettle, after at 100 deg.] C vacuum dehydration 2h, cooled to 55 ℃, purged with nitrogen, was added 15 parts of the diisocyanate in a nitrogen atmosphere, heated to 70 ℃, stirred for 1.5h, to obtain a mixture A;

[0029] Step b: 2.5 parts of 2,2-dimethylol propionic acid (CAS No. 4767-03-7) was added 7 parts of N- methylpyrrolidone (CAS No. 872-50-4) and mixed uniformly, added A mixture was stirred 2H;

[0030] Step c: temperature was raised to 80 ℃, was added 3.5 parts of hydroxyethyl acrylate (CAS No. 818-61-1), and 2 parts of isopropyl alcohol (CAS No. 67-63-0) was stirred for 1.5h, cooled to 55 ℃, was added 10 parts of methyl methacrylate (CAS No. 80-62-6), continue to cool to below 40 ℃, 1.5 parts of triethanolamine (CAS No. 102-71-6), stirred for 0.5h, added to 45 parts of water after the obtained urethane modified acrylic prepolymer.

[0031] Polyether polyol

[0032] In a preferred embodiment, the polyether polyol is selected from polypropylene oxide, polyethylene glycol, polypropylene glycol, polymer polyol, one or more combinations thereof.

[0033] In a more preferred embodiment, the polyether polyol preferably polyethylene glycol.

[0034] In a preferred embodiment, the polyether polyol has a relative molecular weight of 1500 to 3000.

[0035] In a more preferred embodiment, the relative molecular weight of the polyether polyol is 2000.

[0036] The present invention is polyethylene glycol commercially available, may be purchased from, for example, PEG-2000, Shek spent relative molecular weight of 2,000.

[0037] Diisocyanate

[0038] In a preferred embodiment, the diisocyanate include 1,4-dimethyl-cyclohexane diisocyanate and hexamethylene diisocyanate.

[0039] In a preferred embodiment, the 1,4-dimethyl-cyclohexane diisocyanate and hexamethylene weight diisocyanate ratio of 1: (0.3 to 0.6).

[0040] In a more preferred embodiment, the weight-dimethyl-1,4-cyclohexane diisocyanate, hexamethylene diisocyanate ratio of 1: 0.45.

[0041] The inventors have found that in the development process, when the specific feedstock and preparation method of the obtained polyurethane-modified acrylic prepolymer, the resulting adhesive bond strength significantly improve mentioned. The inventors believe that reducing the space-dimethyl-1,4-cyclohexane diisocyanate peculiar saturated aliphatic cyclic structure occupied by a proportion of hexamethylene diisocyanate linear molecular chain structure, but also to some extent steric structure, accelerating the crosslinking reactive -NCO groups to -OH groups in the system occurs; and dimethyl 1,4-cyclohexane diisocyanate sterically hindered saturated alicyclic structure protective effect to a certain extent inhibits the free rotation of molecular chains in the system, promoting formation of a three-dimensional structure of a mechanical entanglement with the interface, resulting adhesive enhance denseness cross-linked interpenetrating network structure, the water can not penetrate into the adhesive film, the resulting adhesives have improved adhesive strength and water resistance, firm adhesion PVC material. However, the inventors found during its practical application, resulting adhesive poor leveling, sizing process prone to agglomeration; after use and prone to yellowing after prolonged use, aesthetic impact PVC material degrees, limiting the use of promotional materials.

[0042] (Petroleum resins)

[0043] Petroleum resin is a byproduct of ethylene apparatus C5, C9 fraction as raw material, obtained by cationic polymerization of a low molecular weight polymer. Which is insoluble in water, soluble in organic solvents, having low acid resistance and chemical characteristics.

[0044] In a preferred embodiment, the softening point of the petroleum resin is 91 ~ 98 ℃.

[0045] In a more preferred embodiment, the softening point of the petroleum resin is 93 ℃.

[0046] The softening point refers to the next for a given heat load, the temperature at which the resin modification; of the present invention, the softening point test method is not particularly limited, and may employ various softening well known to the skilled person point test method, such as global law.

[0047] In a preferred embodiment, the resin is selected from petroleum resins, hydrogenated resins EPA, nine carbon resin A nine carbon EPA and copolymer resins in various combinations or EPA.

[0048] In a more preferred embodiment, the resin is a petroleum resin EPA.

[0049] The petroleum resins are commercially available, for example, EPA resin purchased from Exxon, Model E1310, a softening point of 93 ℃.

[0050] (Rosin)

[0051] In a preferred embodiment, the rosin resin is hydrogenated rosin resin.

[0052] The hydrogenated rosin resin is commercially available, for example, purchased from Shanghai Chemical Co. Allison, a hydrogenated rosin resin, a softening point (ring and ball method) of ≥71.0 ℃.

[0053] In a preferred embodiment, the modified acrylic urethane prepolymer, a petroleum resin, rosin resin weight ratio of 1: (0.38 to 0.44) :( 0.15 to 0.35).

[0054] In a more preferred embodiment, the modified acrylic urethane prepolymer, a petroleum resin, rosin resin weight ratio of 1: 0.41: 0.25.

[0055] The inventors have surprisingly found that in a further development, after the use of a certain proportion of the softening point range and EPA resins and hydrogenated rosin resin, the resulting adhesive bond strength and leveling has been significantly improved. This is because the addition of a certain proportion of the softening point range and EPA resins and hydrogenated rosin resin, diluting the interpenetrating network structure of the crosslinked macromolecular chains excessive entanglement, while the molecular structure of the resin EPA branched chain aliphatic hydrocarbon double bonds may be present on the structure to further enhance the stability of the amount of conventional systems network structure, promote the formation of a uniform system of small size latex particles, latex particles and enhance proper spacing to prevent excessive agglomeration blocking phenomenon, so that application gel process a colloidal dispersion can be uniformly embedded into the irregularities and gaps at the surface of the substrate or to further enhance the adhesive strength of the resulting adhesive and leveling. However, since EPA and hydrogenated rosin resin in the resin composition is more complex, a small amount of hydroxyl group contained in its molecule, a carboxyl group, will produce a chromophore oxidation decomposition occurs, yellowing after prolonged use of the resultant adhesive was not obtained improve.

[0056] (Organosiloxane monomer)

[0057] In a preferred embodiment, the organosiloxane and a vinyl monomer containing a bulky structure organosiloxane monomer.

[0058] In a preferred embodiment, the organosiloxane monomer is selected from styrene ethyltrimethoxysilane (CAS No. 134000-44-5), styryl ethyltrimethoxysilane (CAS No. is 119181-19-0), [2- (trimethoxysilyl) vinyl (1E)] - one kind of benzene (CAS No. 70531-02-1) or any combination thereof.

[0059] In a more preferred embodiment, the organosiloxane monomer is styrene ethyltrimethoxysilane.

[0060] The inventors have surprisingly found that in a further development of exploration, when introduced into the organosiloxane monomer containing a vinyl group and a bulky structure in the system, not only can effectively solve the problem of the adhesives used yellow hair, and the bond strength obtained further enhanced. This is because, styrene ethyltrimethoxysilane alkoxy group and an unsaturated double bond may be produced with suitable polymeric acrylic prepolymer residual unsaturated double bonds, thereby forming the tightly crosslinked latex particle surface structure, have raised bonding strength; styrene-conjugated structure while ethyltrimethoxysilane the radical may be preferentially attacked, EPA prevent the hydrogenated rosin resin and a resin other internal groups attack oxidative yellowing.

[0061] And the plasticizer of the present invention is not particularly limited, and various plasticizers well known to those skilled in the art, such as glycerin triglycidyl ether.

[0062] The initiator of the present invention is not particularly limited, and well known to those skilled in the various initiators, such as potassium persulfate.

[0063] The present invention is the promoter is not particularly limited, and various promoters known to the skilled person, for example N, N- dimethylaniline and saccharin.

[0064] A second aspect of the present invention provides a method for preparing said PVC material compounded with a water-based adhesive, comprising the steps of: urethane modified acrylic prepolymer, a petroleum resin, rosin resin, a plasticizer, organosiloxane after uniformly mixing a monomer, initiator and accelerator were added, that is, too.

[0067] Example 1

[0068] Embodiments of the present invention to provide an aqueous adhesive PVC composite material, comprising the following raw materials: modified acrylic urethane prepolymer 42.5 parts, 17.5 parts of a petroleum resin, 10.5 parts of a rosin resin, a plasticizer, 5 parts of 7 organosiloxane monomer parts of the initiator 3 parts, 6 parts of accelerator.

[0069] The petroleum resin is a resin Exxon EPA, Model E1310, a softening point of 93 ℃. The rosin resin is hydrogenated rosin resin, may be purchased from Shanghai Chemical Co. Allison, a hydrogenated rosin resin. The organosiloxane monomer is styrene ethyltrimethoxysilane. The plasticizer is glycerol triglycidyl ether; the initiator is potassium persulfate; the accelerator is N, N- dimethylaniline and saccharin in a weight ratio of 1: 0.6.

[0070] The method of preparing the urethane-modified acrylic prepolymer comprises the steps of:

[0071] Step a: in parts by weight, and 3 parts of polyether polyol is added to the kettle, after at 100 deg.] C vacuum dehydration 2h, cooled to 55 ℃, purged with nitrogen, was added 15 parts of the diisocyanate in a nitrogen atmosphere, heated to 70 ℃, stirred for 1.5h, to obtain a mixture A;

[0072] Step b: 2.5 parts of 2,2-dimethylol propionic acid were added 7 parts of N- methylpyrrolidone uniformly mixed, added to A and the mixture stirred 2H;

[0073] Step c: temperature was raised to 80 ℃, was added 3.5 parts of hydroxyethyl acrylate and 2 parts of isopropanol was stirred for 1.5h, cooled to 55 ℃, 10 parts of methyl methacrylate was added, continue to cool to below 40 ℃, 1.5 parts of three ethanolamine and stirred for 0.5h, after adding 45 parts of water to give a urethane-modified acrylic prepolymer.

[0074] The polyether polyol is preferably a polyethylene glycol, purchased from Shek spent PEG-2000, a relative molecular weight of 2,000. The diisocyanates include 1,4-dimethyl-cyclohexane diisocyanate and hexamethylene diisocyanate, in a weight ratio of 1: 0.45.

[0075] PVC composite material described above prepared water-based adhesive, comprising the steps of: urethane modified acrylic prepolymer, a petroleum resin, rosin resin, a plasticizer, a uniformly mixed organosiloxane monomer, initiator and accelerator were added , that is, too.

[0076] Example 2

[0077] 2 embodiment of the present invention to provide an aqueous adhesive PVC composite material, comprising the following raw materials: polyethylene-modified urethane acrylate oligomer 35 parts, 15 parts of petroleum resin, 9 parts of a rosin resin, a plasticizer, 4 parts of organosiloxane monomer 6.5 parts, 1 part of initiator, 5 parts of accelerator.

[0078] The petroleum resin is a resin Exxon EPA, Model E1310, a softening point of 93 ℃. The rosin resin is hydrogenated rosin resin, may be purchased from Shanghai Chemical Co. Allison, a hydrogenated rosin resin. The organosiloxane monomer is styrene ethyltrimethoxysilane. The plasticizer is glycerol triglycidyl ether; the initiator is potassium persulfate; the accelerator is N, N- dimethylaniline and saccharin in a weight ratio of 1: 0.6.

[0079] The method of preparing the urethane-modified acrylic prepolymer comprises the steps of:

[0080] Step a: in parts by weight, 2 parts polyether polyol is added to the kettle, after at 90 deg.] C vacuum dehydration 1.5h, cooled to 50 ℃, purged with nitrogen, was added 11 parts of the diisocyanate in a nitrogen atmosphere, warmed to 70 ℃, stirred for 1h, to give a mixture A;

[0081] Step b: 1 parts of 2,2-dimethylol propionic acid were added 5 parts of N- methylpyrrolidone uniformly mixed, added to A and the mixture stirred IH;

[0082] Step c: temperature was raised to 75 ℃, was added 2 parts of hydroxyethyl acrylate and 1 part of isopropyl alcohol were stirred IH, cooled to 50 ℃, 8 parts of methyl methacrylate was added, continue to cool to below 40 ℃, 1 part of triethanolamine after stirring 0.3H, was added 40 parts of water to give a urethane-modified acrylic prepolymer.

[0083] The polyether polyol is preferably a polyethylene glycol, purchased from Shek spent PEG-2000, a relative molecular weight of 2,000. The diisocyanates include 1,4-dimethyl-cyclohexane diisocyanate and hexamethylene diisocyanate, in a weight ratio of 1: 0.3.

[0084] The above-described PVC composite prepared an aqueous adhesive, the same as in Example 1.