A polyurethane acrylate emulsion, a preparation method and application thereof

Abstract

This invention relates to a polyurethane acrylate emulsion, its preparation method, and its application. The raw materials for preparing the polyurethane acrylate emulsion include, by weight, the following components: 1-10 parts by weight of an intermediate, 2-10 parts by weight of hydroxyl acrylate, 2-15 parts by weight of styrene, 3-10 parts by weight of alkyl acrylate, and 0.1-1 parts by weight of an initiator. The raw materials for preparing the intermediate include 5'-methoxy-2'-methylbiphenyl-3-carboxylic acid, glycidyl ether tert-carbonate, and diisocyanate. The polyurethane acrylate emulsion provided by this invention, through the design of its raw materials, can be used in tack coats and can significantly improve the drying speed and anti-tack properties of tack coats.

Description

Technical Field

[0001] This invention belongs to the field of pencil paint technology, specifically relating to a polyurethane acrylate emulsion, its preparation method, and its application. Background Technology

[0002] In pencil production, to improve the pencil's appearance, a tip-dip treatment is typically applied to one end, thus satisfying consumers' aesthetic preferences. Nitrocellulose lacquer, with its unique properties such as quick drying, ease of application, and pleasant feel, is widely used in pencil coating. Currently, solvent-based tip-dip lacquer is used in the tip-dip process. While it dries quickly, it involves the use of large amounts of flammable and explosive solvents during production. These solvents can harm the health of workers and pollute the surrounding environment. Furthermore, residual solvents on the pencils during use can also adversely affect consumers' health.

[0003] CN113249001A discloses a water-based quick-drying pencil paint for drawing tips and tops, wherein the water-based quick-drying pencil paint for drawing tips and tops is composed of the following components in the following mass ratio: 20-80% water-based emulsion, 5-40% pigments and fillers, 2-10% wetting and dispersing agent, 0.4-6% additives, 0.1-8% film-forming aids, and 1-40% diluent; CN113185907A discloses an environmentally friendly water-based pencil paint for drawing tips, comprising the following components: 5-30 parts deionized water, 12-30 parts alkyd resin, 25-50 parts modified water-based polyurethane, 12-20 parts water-based epoxy ester modified acrylic resin, 0.1-15 parts water-based cured product, 8-20 parts additives, 10-45 parts fillers, and 8-30 parts water-based color paste. However, current water-based tack coats have the disadvantages of slow drying speed and poor anti-tack properties, which cannot meet production requirements. Therefore, there is an urgent need to design a polyurethane acrylate emulsion that can be used in tack coats to improve its fast drying speed and anti-tack properties. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a polyurethane acrylate emulsion, its preparation method, and its application. The polyurethane acrylate emulsion provided by the present invention, through the design of its raw materials, can be used in tack coats and can significantly improve the drying speed and anti-tack properties of tack coats.

[0005] To achieve this objective, the present invention adopts the following technical solution:

[0006] In a first aspect, the present invention provides a polyurethane acrylate emulsion, wherein the raw materials for preparing the polyurethane acrylate emulsion comprise the following components in parts by weight:

[0007] 1-10 parts by weight of intermediate

[0008] 2-10 parts by weight of hydroxy acrylate

[0009] 2-15 parts by weight of styrene

[0010] 3-10 parts by weight of alkyl acrylate

[0011] Initiator 0.1-1 parts by weight;

[0012] The raw materials for preparing the intermediate include 5'-methoxy-2'-methylbiphenyl-3-carboxylic acid, glycidyl ether tert-carbonate, and diisocyanate.

[0013] The polyurethane acrylate emulsion provided by this invention is a polyurethane acrylate emulsion with a core-shell structure. The intermediates used in its preparation include 5'-methoxy-2'-methylbiphenyl-3-carboxylic acid, glycidyl ether tert-carbonate, and diisocyanate. The combined use of 5'-methoxy-2'-methylbiphenyl-3-carboxylic acid and glycidyl ether tert-carbonate enables the varnish to achieve ideal drying speed and anti-tack properties. Through the design and screening of specific intermediates and other raw materials for preparing the polyurethane acrylate emulsion, the drying speed and anti-tack properties of the varnish can be significantly improved.

[0014] The intermediate is 1-10 parts by weight, for example, it can be 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, 7 parts by weight, 7.5 parts by weight, 8 parts by weight, 8.5 parts by weight, 9 parts by weight, 9.5 parts by weight, etc.

[0015] The hydroxy acrylate is in the form of 2-10 parts by weight, for example, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, 7 parts by weight, 7.5 parts by weight, 8 parts by weight, 8.5 parts by weight, 9 parts by weight, 9.5 parts by weight, etc.

[0016] The styrene is 2-15 parts by weight, for example, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, etc.

[0017] The alkyl acrylate is 3-10 parts by weight, for example, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, 7 parts by weight, 7.5 parts by weight, 8 parts by weight, 8.5 parts by weight, 9 parts by weight, 9.5 parts by weight, etc.

[0018] The initiator is 0.1-1 parts by weight, for example, it can be 0.15 parts by weight, 0.2 parts by weight, 0.25 parts by weight, 0.3 parts by weight, 0.35 parts by weight, 0.4 parts by weight, 0.45 parts by weight, 0.5 parts by weight, 0.55 parts by weight, 0.6 parts by weight, 0.65 parts by weight, 0.7 parts by weight, 0.75 parts by weight, 0.8 parts by weight, 0.85 parts by weight, 0.9 parts by weight, 0.95 parts by weight, etc.

[0019] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. The purpose and beneficial effects of the present invention can be better achieved and realized through the following preferred technical solutions.

[0020] As a preferred technical solution, the diisocyanate includes any one or a combination of at least two of isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, or diphenylmethane diisocyanate.

[0021] Preferably, the molar ratio of 5'-methoxy-2'-methylbiphenyl-3-carboxylic acid, glycidyl ether tert-carbonate (CAS No.: 26761-45-5) to diisocyanate is 1:(2.5-3):(1-1.5), for example, it can be 1:2.5:1.05, 1:2.55:1.1, 1:2.6:1.15, 1:2.65:1.2, 1:2.7:1.25, 1:2.75:1.3, 1:2.8:1.35, 1:2.85:1.4, 1:2.9:1.45, 1:2.95:1.5, etc.

[0022] Preferably, the method for preparing the intermediate includes the following steps:

[0023] (1) 5'-methoxy-2'-methylbiphenyl-3-carboxylic acid reacts with glycidyl ether tert-carbonate to give a monomer containing hydroxyl groups;

[0024] (2) The hydroxyl-containing monomer reacts with diisocyanate to obtain the intermediate.

[0025] Preferably, the reaction temperature in step (1) is 85-90℃, for example, it can be 85.5℃, 86℃, 86.5℃, 87℃, 87.5℃, 88℃, 88.5℃, 89℃, 89.5℃, etc.

[0026] Preferably, the reaction time in step (1) is 1.5-2 hours, for example, 1.55 hours, 1.6 hours, 1.65 hours, 1.7 hours, 1.75 hours, 1.8 hours, 1.85 hours, 1.9 hours, 1.95 hours, etc.

[0027] Preferably, the reaction in step (1) is carried out in the presence of a first catalyst.

[0028] Preferably, the first catalyst comprises any one or a combination of at least two of triethylamine, pyridine, quinoline, or proline.

[0029] Preferably, the mass ratio of 5'-methoxy-2'-methylbiphenyl-3-carboxylic acid to the first catalyst is 100:(0.9-3), for example, it can be 100:1, 100:1.2, 100:1.4, 100:1.6, 100:1.8, 100:2, 100:2.2, 100:2.4, 100:2.6, 100:2.8, etc.

[0030] Preferably, the reaction temperature in step (2) is 75-80℃, for example, it can be 75.5℃, 76℃, 76.5℃, 77℃, 77.5℃, 78℃, 78.5℃, 79℃, 79.5℃, etc.

[0031] Preferably, the reaction time in step (2) is 1.5-2 hours, for example, 1.55 hours, 1.6 hours, 1.65 hours, 1.7 hours, 1.75 hours, 1.8 hours, 1.85 hours, 1.9 hours, 1.95 hours, etc.

[0032] Preferably, the reaction in step (2) is carried out in the presence of a second catalyst.

[0033] Preferably, the second catalyst comprises any one or a combination of at least two of triethylamine, pyridine, quinoline, or proline.

[0034] Preferably, the mass ratio of the diisocyanate to the second catalyst is 100:(0.9-3), for example, it can be 100:1, 100:1.2, 100:1.4, 100:1.6, 100:1.8, 100:2, 100:2.2, 100:2.4, 100:2.6, 100:2.8, etc.

[0035] Preferably, the hydroxy acrylate includes any one or a combination of at least two of hydroxyethyl methacrylate, hydroxypropyl methacrylate, or hydroxypropyl acrylate.

[0036] Preferably, the alkyl acrylate includes any one or a combination of at least two of methyl methacrylate, ethyl methacrylate, or ethyl acrylate.

[0037] Preferably, the initiator includes benzoyl peroxide and / or lauroyl peroxide.

[0038] Preferably, the raw materials for preparing the polyurethane acrylate emulsion further include 10-40 parts by weight of water, for example, water can be 12 parts by weight, 15 parts by weight, 18 parts by weight, 20 parts by weight, 22 parts by weight, 25 parts by weight, 28 parts by weight, 30 parts by weight, 32 parts by weight, 35 parts by weight, 38 parts by weight, etc.

[0039] Preferably, the raw materials for preparing the polyurethane acrylate emulsion further include 1-5 parts by weight of emulsifier, for example, the emulsifier can be 1.2 parts by weight, 1.5 parts by weight, 1.8 parts by weight, 2 parts by weight, 2.2 parts by weight, 2.5 parts by weight, 2.8 parts by weight, 3 parts by weight, 3.2 parts by weight, 3.5 parts by weight, 3.8 parts by weight, 4 parts by weight, 4.2 parts by weight, 4.5 parts by weight, 4.8 parts by weight, etc.

[0040] Preferably, the emulsifier includes polyoxyethylene ether emulsifiers and / or sodium dodecyl sulfate.

[0041] In a second aspect, the present invention provides a method for preparing a polyurethane acrylate emulsion as described in the first aspect, the method comprising the following steps:

[0042] (F1) Emulsifier, intermediate, hydroxy acrylate, styrene, alkyl acrylate, a portion of water and a portion of initiator are mixed to obtain an emulsion;

[0043] (F2) A portion of the emulsion and the remaining water are mixed and subjected to a first reaction to obtain an emulsion intermediate;

[0044] (F3) After the emulsion intermediate and the remaining emulsion undergo a second reaction, the remaining initiator is added to carry out a third reaction to obtain the polyurethane acrylate emulsion.

[0045] Preferably, the mass of the water in step (F1) is 40-50% of the total mass of water, for example, it can be 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, etc.

[0046] Preferably, the mass of the initiator in step (F1) is 70-80% of the total mass of the initiator, for example, it can be 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, etc.

[0047] Preferably, the mass of the emulsion in step (F2) is 5-10% of the total mass of the emulsion, for example, it can be 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, etc.

[0048] Preferably, the remaining emulsion in step (F3) is added to the reaction system dropwise.

[0049] Preferably, the temperature of the first reaction is 75-80℃, for example, 75.5℃, 76℃, 76.5℃, 77℃, 77.5℃, 78℃, 78.5℃, 79℃, 79.5℃, etc., and the time is 0.5-0.8h, for example, 0.52h, 0.55h, 0.58h, 0.6h, 0.62h, 0.65h, 0.68h, 0.7h, 0.72h, 0.75h, 0.78h, etc.

[0050] Preferably, the temperature of the second reaction is 75-80℃, for example, 75.5℃, 76℃, 76.5℃, 77℃, 77.5℃, 78℃, 78.5℃, 79℃, 79.5℃, etc., and the time is 1.5-2h, for example, 1.55h, 1.6h, 1.65h, 1.7h, 1.75h, 1.8h, 1.85h, 1.9h, 1.95h, etc.

[0051] Preferably, the temperature of the third reaction is 75-85℃, for example, 75.5℃, 76℃, 76.5℃, 77℃, 77.5℃, 78℃, 78.5℃, 79℃, 79.5℃, etc., and the time is 0.3-0.5h, for example, 0.32h, 0.34h, 0.36h, 0.38h, 0.4h, 0.42h, 0.44h, 0.46h, 0.48h, etc.

[0052] Thirdly, the present invention provides a hair-dyeing paint, the hair-dyeing paint comprising the polyurethane acrylate emulsion as described in the first aspect.

[0053] The T of the polyurethane acrylate emulsion in the sizing agent provided by this invention g It has high viscosity, low hardness, and high hardness. It also incorporates the reactive film-forming aid glycidyl ether tert-carbonate, avoiding the need for traditional film-forming aids to delay drying. This allows the paint to dry quickly and has excellent anti-tack properties.

[0054] Preferably, the styling paint comprises the following components by weight percentage:

[0055] Polyurethane acrylate emulsion 60-80%

[0056] Titanium dioxide 5-10%

[0057] Dispersant 0.8-1.6%

[0058] Wetting agent 0.01-0.1%

[0059] Defoamer 0.2-0.5%

[0060] Thickener 0.1-0.5%

[0061] Fungicide 0.1-0.3%

[0062] Anti-sticking agent 3-5%

[0063] The remainder is water.

[0064] The water-based quick-drying adhesive provided by this invention is non-toxic to human health and the environment, and has the characteristics of fast drying speed and excellent anti-tack properties, which can meet the drying speed requirements of the production line, and will not stick together even when stacked.

[0065] The mass percentage of polyurethane acrylate emulsion in the lint coat is 60-80%, for example, it can be 62%, 64%, 66%, 68%, 70%, 72%, 74%, 76%, 78%, etc.

[0066] The titanium dioxide content in the adhesive coating is 5-10% by mass, for example, it can be 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, etc.

[0067] The dispersant in the varnish has a mass percentage content of 0.8-1.6%, for example, it can be 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, etc.

[0068] The wetting agent in the varnish has a mass percentage content of 0.01-0.1%, for example, it can be 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, etc.

[0069] The defoamer in the varnish has a mass percentage content of 0.2-0.5%, for example, it can be 0.22%, 0.24%, 0.26%, 0.28%, 0.3%, 0.32%, 0.34%, 0.36%, 0.38%, 0.4%, 0.42%, 0.44%, 0.46%, 0.48%, etc.

[0070] The thickener in the varnish has a mass percentage content of 0.1-0.5%, for example, it can be 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, etc.

[0071] The bactericide content in the varnish is 0.1-0.3% by mass, for example, it can be 0.12%, 0.14%, 0.16%, 0.18%, 0.2%, 0.22%, 0.24%, 0.26%, 0.28%, etc.

[0072] The anti-sticking agent in the adhesive has a mass percentage content of 3-5%, for example, it can be 3.2%, 3.4%, 3.6%, 3.8%, 4%, 4.2%, 4.4%, 4.6%, 4.8%, etc.

[0073] Preferably, the titanium dioxide includes rutile titanium dioxide.

[0074] Preferably, the dispersant comprises sodium polyacrylate dispersant.

[0075] Preferably, the wetting agent comprises a nonionic surfactant.

[0076] Preferably, the defoamer includes metal soap defoamers and / or mineral oil defoamers.

[0077] Preferably, the thickener comprises hydroxyethyl cellulose and / or a polyurethane thickener.

[0078] Preferably, the bactericide includes Kathon-type preservatives and bactericides.

[0079] Preferably, the anti-sticking agent comprises polyethylene wax; the polyethylene wax is an extremely hard, high-density polyethylene wax.

[0080] Fourthly, the present invention provides a method for preparing a head-dyeing paint as described in the third aspect, the method comprising: mixing the components of the head-dyeing paint evenly to obtain the head-dyeing paint.

[0081] Preferably, the preparation method specifically includes the following steps:

[0082] (S1) Mix the wetting agent, dispersant, defoamer and part of the polyurethane acrylate emulsion;

[0083] (S2) Mix the mixture obtained in step (S1) with titanium dioxide;

[0084] (S3) Mix the mixture obtained in step (S2), the thickener, and a portion of the water;

[0085] (S4) Mix the mixture obtained in step (S3) with the remaining polyurethane acrylate emulsion;

[0086] (S5) The mixture obtained in step (S4), bactericide, anti-sticking agent and remaining water are mixed to obtain the adhesive paint.

[0087] The preparation process of the smear paint provided by this invention is extremely simple and has low production cost, making it suitable for large-scale production.

[0088] Preferably, the mixing time in step (S1) is 3-5 min, for example, it can be 3.2 min, 3.4 min, 3.6 min, 3.8 min, 4 min, 4.2 min, 4.4 min, 4.6 min, 4.8 min, etc.

[0089] Preferably, the mixing in step (S1) is carried out under stirring, and the stirring speed is 400-600 r / min, for example, 420 r / min, 440 r / min, 460 r / min, 480 r / min, 500 r / min, 520 r / min, 540 r / min, 560 r / min, 580 r / min, etc.

[0090] Preferably, the mass of the polyurethane acrylate emulsion in step (S1) is 40-50% of the total mass of the polyurethane acrylate emulsion, for example, it can be 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, etc.

[0091] Preferably, the mixing in step (S2) is carried out under stirring at a speed of 1000-1200 r / min, such as 1020 r / min, 1040 r / min, 1060 r / min, 1080 r / min, 1100 r / min, 1120 r / min, 1140 r / min, 1160 r / min, 1180 r / min, etc.

[0092] Preferably, the mass of the water in step (S3) is 40-50% of the total mass of water, for example, it can be 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, etc.

[0093] Preferably, the mixing time in step (S3) is 25-30 min, for example, it can be 25.5 min, 26 min, 26.5 min, 27 min, 27.5 min, 28 min, 28.5 min, 29 min, 29.5 min, etc.

[0094] Preferably, the mixing in step (S3) is carried out under stirring, and the stirring speed is 400-1000 r / min, for example, 450 r / min, 500 r / min, 550 r / min, 600 r / min, 650 r / min, 700 r / min, 750 r / min, 800 r / min, 850 r / min, 900 r / min, 950 r / min, etc.

[0095] Preferably, step (S3) further includes a step of detecting the fineness of the resulting mixture after the mixing is completed.

[0096] In this invention, the fineness of the mixture is obtained by testing according to GB / T1724-2019 "Determination of grinding fineness of paints, varnishes and printing inks".

[0097] Preferably, the fineness of the mixture obtained in step (S3) is ≤20μm, for example, it can be 2μm, 4μm, 6μm, 8μm, 10μm, 12μm, 14μm, 16μm, 18μm, etc.

[0098] Preferably, the mixing in step (S4) is carried out under stirring at a speed of 400-600 r / min, such as 420 r / min, 440 r / min, 460 r / min, 480 r / min, 500 r / min, 520 r / min, 540 r / min, 560 r / min, 580 r / min, etc.

[0099] Preferably, the mixing in step (S5) is carried out under stirring, and the stirring speed is 400-600 r / min, for example, 420 r / min, 440 r / min, 460 r / min, 480 r / min, 500 r / min, 520 r / min, 540 r / min, 560 r / min, 580 r / min, etc.

[0100] Fifthly, the present invention provides an application of the smearing paint as described in the third aspect in pencil coating.

[0101] The numerical range described in this invention includes not only the point values ​​listed above, but also any point values ​​within the numerical ranges not listed above. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific point values ​​included in the range.

[0102] Compared with the prior art, the present invention has the following beneficial effects:

[0103] The polyurethane acrylate emulsion provided by this invention, through the design of the raw materials, can be used in pencil dipsticks and can significantly improve the drying speed and anti-tack properties of the pencil dipsticks. The drying time of the pencil dipstick is 50-75 minutes. After the pencil dipstick is applied to a pencil, the paint film between the pencils does not stick after being placed at 45°C for 2 weeks. After being placed at 45°C and 80% humidity for 2 weeks, the paint film between the pencils does not stick or only slightly sticks. Detailed Implementation

[0104] To facilitate understanding of the present invention, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as limiting the scope of the invention.

[0105] The sources of some components in the following examples, comparative examples, application examples, and comparative application examples are as follows:

[0106] (1) Titanium dioxide: Shandong Dongjia SR-237;

[0107] (2) Dispersant: BASF 4141;

[0108] (3) Wetting agent: Wellman 7100;

[0109] (4) Defoamer: Nopco NXZ;

[0110] (5) Thickener: BASF PE1331;

[0111] (6) Bactericide: Rohm and Haas LXE;

[0112] (7) Anti-sticking agent: Longkou Yijiu PE-3040A;

[0113] (8) Emulsifier:

[0114] Emulsifier-1, polyoxyethylene ether emulsifier, BASF AEO-3;

[0115] Emulsifier-2, sodium dodecyl sulfate, Anyang Shuanghuan Additives.

[0116] Preparation Example 1: Preparation of Intermediate A

[0117] (1) 1 mol of 5'-methoxy-2'-methylbiphenyl-3-carboxylic acid and 2.5 mol of glycidyl ether tert-carbonate were added to the reaction vessel, and 2.42 g of triethylamine catalyst was added. The reaction was carried out at 90 °C for 2 h to obtain a monomer containing hydroxyl groups.

[0118] (2) The temperature of the above reaction vessel was lowered to 80°C, and 1 mol of IPDI and 2.22 g of triethylamine catalyst were added to it. After reacting with the hydroxyl-containing monomer for 2 h, the intermediate A was obtained.

[0119] Preparation Example 2: Preparation of Intermediate B

[0120] (1) 1 mol of 5'-methoxy-2'-methylbiphenyl-3-carboxylic acid and 2.5 mol of glycidyl ether tert-carbonate were added to the reaction vessel, and 2.42 g of triethylamine was added. The reaction was carried out at 90 °C for 2 h to obtain a monomer containing hydroxyl groups.

[0121] (2) The temperature of the above reaction vessel was lowered to 80°C, and 1 mol of toluene diisocyanate and 1.74 g of triethylamine were added to it. After reacting with the hydroxyl-containing monomer for 2 h, the intermediate B was obtained.

[0122] Preparation Example 3: Preparation of Intermediate C

[0123] (1) 1 mol of 5'-methoxy-2'-methylbiphenyl-3-carboxylic acid and 2.5 mol of glycidyl ether tert-carbonate were added to the reaction vessel, and 2.42 g of triethylamine was added. The reaction was carried out at 90 °C for 2 h to obtain a monomer containing hydroxyl groups.

[0124] (2) The temperature of the above reaction vessel was lowered to 80°C, and 1 mol of hexamethylene diisocyanate and 1.68 g of triethylamine were added to it. After reacting with the hydroxyl-containing monomer for 2 h, the intermediate C was obtained.

[0125] Preparation of Comparative Example 1: Preparation of Intermediate D

[0126] (1) 1 mol of 5'-methoxy-2'-methylbiphenyl-3-carboxylic acid and 2.5 mol of glycidyl ether were added to the reaction vessel, and 2.42 g of triethylamine was added. The reaction was carried out at 90 °C for 2 h to obtain a monomer containing hydroxyl groups.

[0127] (2) The temperature of the above reaction vessel was lowered to 80°C, and 1 mol of IPDI and 2.22 g of triethylamine were added to it. After reacting with the hydroxyl-containing monomer for 2 h, the intermediate D was obtained.

[0128] Example 1

[0129] A polyurethane acrylate emulsion, wherein the raw materials for preparing the polyurethane acrylate emulsion comprise the following components in parts by weight:

[0130] intermediate A1 by weight

[0131] 2 parts by weight of hydroxyethyl methacrylate

[0132] 2 parts by weight of styrene

[0133] 3 parts by weight of methyl methacrylate

[0134] Initiator BPO 0.5 parts by weight

[0135] 10 parts by weight of water

[0136] Emulsifier - 11 parts by weight;

[0137] The preparation method of the polyurethane acrylate emulsion includes the following steps:

[0138] (F1) Emulsifier-1, intermediate A, hydroxyethyl methacrylate, styrene, methyl methacrylate, a portion of water (50% of the total mass of water) and a portion of initiator (80% of the total mass of initiator) are mixed and stirred for 0.5 h to obtain an emulsion;

[0139] (F2) A portion of the emulsion (5% of the total mass of the emulsion) and the remaining water were mixed in a reactor and reacted at 80°C for 0.5 h. The solution in the reactor turned blue, and an emulsion intermediate was obtained.

[0140] (F3) The remaining emulsion is added dropwise to the above reaction vessel and reacted at 80°C for 2 hours; then the temperature is raised to 85°C and the remaining initiator is added and reacted for 0.5 hours to obtain the polyurethane acrylate emulsion.

[0141] Examples 2-5, Comparative Examples 1-4

[0142] A polyurethane acrylate emulsion differs from Example 1 only in the type and / or amount (parts by weight) of the raw materials used in its preparation, as shown in Table 1. The preparation method of the polyurethane acrylate emulsion is the same as that of Example 1.

[0143] Table 1

[0144]

[0145] Application Example 1

[0146] A hair-dyeing paint, said hair-dyeing paint comprising, by weight percentage, the following components:

[0147] Example 1 provides a 60% polyurethane acrylate emulsion.

[0148] Titanium dioxide SR-23710%

[0149] Dispersant 41411.6%

[0150] Wetting agent 71000.1%

[0151] Defoamer NXZ 0.5%

[0152] Thickener PE1331 0.1%

[0153] Bactericide LXE 0.1%

[0154] Anti-sticking agent PE-3040A3%

[0155] The remainder is water;

[0156] The preparation method of the head-sticking paint includes the following steps:

[0157] (S1) Mix wetting agent 7100, dispersant 4141, defoamer NXZ and half of the polyurethane acrylate emulsion, and stir at 600 r / min for 5 minutes;

[0158] (S2) Mix the mixture obtained in step (S1) with titanium dioxide SR-237 under stirring at 1000 r / min;

[0159] (S3) Mix thickener PE1331 and a portion of water (40% of the total mass of water), add it to the mixture obtained in step (S2), disperse at 1000 r / min for 25 minutes, and test the fineness;

[0160] (S4) After the fineness of the mixture obtained in step (S3) is 20 μm, adjust it to 600 r / min and add the remaining polyurethane acrylate emulsion to the mixture obtained in step (S3).

[0161] (S5) Add bactericide LXE, anti-sticking agent PE-3040A and the remaining water to the mixture obtained in step (S4) under stirring at 400 r / min, and stir evenly to obtain the adhesive paint.

[0162] Application Example 2

[0163] A hair-dyeing paint, said hair-dyeing paint comprising, by weight percentage, the following components:

[0164] Example 2 provides a 70% polyurethane acrylate emulsion.

[0165] Titanium dioxide SR-2378%

[0166] Dispersant 41411%

[0167] Wetting agent 71000.05%

[0168] Defoamer NXZ 0.3%

[0169] Thickener PE1331 0.3%

[0170] Bactericide LXE 0.2%

[0171] Anti-sticking agent PE-3040A4%

[0172] The remainder is water;

[0173] The preparation method of the head-sticking paint includes the following steps:

[0174] (S1) Mix wetting agent 7100, dispersant 4141, defoamer NXZ and half of the polyurethane acrylate emulsion, and stir at 600 r / min for 5 minutes;

[0175] (S2) Mix the mixture obtained in step (S1) with titanium dioxide SR-237 under stirring at 1000 r / min;

[0176] (S3) Mix thickener PE1331 and a portion of water (45% of the total mass of water), add it to the mixture obtained in step (S2), disperse at 1000 r / min for 25 minutes, and test the fineness;

[0177] (S4) After the fineness of the mixture obtained in step (S3) is 20 μm, adjust it to 400 r / min and add the remaining polyurethane acrylate emulsion to the mixture obtained in step (S3).

[0178] (S5) Add bactericide LXE, anti-sticking agent PE-3040 and the remaining water to the mixture obtained in step (S4) under stirring at 400r / min, and stir evenly to obtain the adhesive paint.

[0179] Application Example 3

[0180] A hair-dyeing paint, said hair-dyeing paint comprising, by weight percentage, the following components:

[0181] Example 3 provides an 80% polyurethane acrylate emulsion.

[0182] Titanium dioxide SR-2375%

[0183] Dispersant 41410.8%

[0184] Wetting agent 71000.01%

[0185] Defoamer NXZ 0.2%

[0186] Thickener PE1331 0.5%

[0187] Bactericide LXE 0.3%

[0188] Anti-sticking agent PE-3040A5%

[0189] The remainder is water;

[0190] The preparation method of the head-sticking paint includes the following steps:

[0191] (S1) Mix wetting agent 7100, dispersant 4141, defoamer NXZ and half of the polyurethane acrylate emulsion, and stir for 5 minutes at a speed of 600 r / min;

[0192] (S2) Mix the mixture obtained in step (S1) with titanium dioxide SR-237 under stirring at 1000 r / min;

[0193] (S3) Mix thickener PE1331 and a portion of water (50% of the total mass of water), add it to the mixture obtained in step (S2), disperse at 1000 r / min for 25 minutes, and test the fineness;

[0194] (S4) After the fineness of the mixture obtained in step (S3) is 20 μm, adjust it to 400 r / min and add the remaining polyurethane acrylate emulsion to the mixture obtained in step (S3).

[0195] (S5) Add bactericide LXE, anti-sticking agent PE-3040 and the remaining water to the mixture obtained in step (S4) under stirring at 400r / min, and stir evenly to obtain the adhesive paint.

[0196] Application Example 4-5, Comparison with Application Example 1-2

[0197] A head-dyeing paint and its preparation method are disclosed. The only difference between this paint and Application Example 1 is that the polyurethane acrylate emulsion provided in Example 1 is replaced by the polyurethane acrylate emulsion provided in Examples 4-5 and Comparative Examples 1-2 in equal mass. All other raw materials, process parameters and steps are the same as in Application Example 1.

[0198] Compare and contrast with example 3-4

[0199] A head-sticking paint and its preparation method are disclosed. The only difference between this paint and Application Example 2 is that the polyurethane acrylate emulsion provided in Example 2 is replaced by the polyurethane acrylate emulsion provided in Comparative Examples 3-4 in equal mass. All other raw materials, process parameters and steps are the same as in Application Example 2.

[0200] Performance testing

[0201] (1) Anti-sticking: The paint provided in the application example and the comparative application example was applied to one end of the pencil by dip coating. The pencil length was about 175cm, the coating length was about 4cm, and the paint film thickness was about 30μm. After 48 hours of painting, 12 pencils were packed into a box with two layers, 6 pencils in each layer. The layers were tightly attached without any gaps. One box was placed in an oven at 45℃ and the other box was placed in a constant temperature and humidity chamber at 45℃ and 80% humidity. The boxes were observed for two consecutive weeks to check whether the pencils were stuck together. If the paint film was stuck between the pencils, it was considered as slight adhesion if the paint film was not damaged after separation. If the paint film was damaged after separation, it was considered as adhesion.

[0202] (2) Drying time: According to the actual dry A method in GB / T1728-2020 "Determination of Drying Time of Paint Film and Putty Film";

[0203] The sizing paints provided in the application examples and comparative application examples were tested according to the above method. The test results are shown in Table 2.

[0204] Table 2

[0205]

[0206] As can be seen from the test data in Table 2, the tack coat using the polyurethane acrylate emulsion provided by this invention has a fast drying speed and excellent anti-tack properties.

[0207] As can be seen from the comparison between Application Example 1 and Application Examples 4-5, using isophorone diisocyanate as an intermediate raw material can further improve the anti-tack and drying speed of the tack coating.

[0208] As can be seen from the comparison between Application Example 1 and Comparative Application Example 1, using glycidyl ether instead of glycidyl tert-carbonate to prepare the intermediate will slow down the drying speed of the tack paint and worsen its anti-tack properties.

[0209] The comparison between Application Example 1 and Comparative Application Example 2 shows that the absence of alkyl acrylate in polyurethane acrylate emulsions slows down the drying speed of the tack coating and reduces its anti-tack properties.

[0210] As can be seen from the comparison between Application Example 2 and Comparative Application Examples 3-4, too much or too little intermediate in polyurethane acrylate emulsion will result in slower drying speed and poorer anti-tack properties of the tack coating.

[0211] The applicant declares that this invention illustrates the polyurethane acrylate emulsion, its preparation method, and its application through the above embodiments. However, this invention is not limited to the above embodiments, meaning that this invention does not necessarily rely on the above embodiments for implementation. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of raw materials, additions of auxiliary components, and selection of specific methods, etc., all fall within the protection and disclosure scope of this invention.

Claims

1. A polyurethane acrylate emulsion, characterized in that, The raw materials for preparing the polyurethane acrylate emulsion include the following components in parts by weight: 1-10 parts by weight of intermediate 2-10 parts by weight of hydroxy acrylate 2-15 parts by weight of styrene 3-10 parts by weight of alkyl acrylate Initiator 0.1-1 parts by weight; The raw materials for preparing the intermediate include 5'-methoxy-2'-methylbiphenyl-3-carboxylic acid, glycidyl ether tert-carbonate, and diisocyanate.

2. The polyurethane acrylate emulsion according to claim 1, characterized in that, The diisocyanate includes any one or a combination of at least two of isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate or diphenylmethane diisocyanate; The molar ratio of 5'-methoxy-2'-methylbiphenyl-3-carboxylic acid, glycidyl tert-carbonate, and diisocyanate is 1:(2.5-3):(1-1.5). The preparation method of the intermediate includes the following steps: (1) 5'-methoxy-2'-methylbiphenyl-3-carboxylic acid reacts with glycidyl ether tert-carbonate to give a monomer containing hydroxyl groups; (2) The hydroxyl-containing monomer reacts with diisocyanate to obtain the intermediate; The reaction in step (1) is carried out at a temperature of 85-90℃ for 1.5-2 hours. The reaction in step (1) is carried out in the presence of a first catalyst; the first catalyst comprises any one or a combination of at least two of triethylamine, pyridine, quinoline or proline; The reaction in step (2) is carried out at a temperature of 75-80℃ for 1.5-2 hours. The reaction in step (2) is carried out in the presence of a second catalyst, which comprises any one or a combination of at least two of triethylamine, pyridine, quinoline or proline.

3. The polyurethane acrylate emulsion according to claim 1, characterized in that, The hydroxy acrylate includes any one or a combination of at least two of hydroxyethyl methacrylate, hydroxypropyl methacrylate, or hydroxypropyl acrylate. The alkyl acrylate includes any one or a combination of at least two of methyl methacrylate, ethyl methacrylate, or ethyl acrylate. The initiator includes benzoyl peroxide and / or lauroyl peroxide; The raw materials for preparing the polyurethane acrylate emulsion also include 10-40 parts by weight of water and 1-5 parts by weight of emulsifier.

4. A method for preparing a polyurethane acrylate emulsion as described in any one of claims 1-3, characterized in that, The preparation method includes the following steps: (F1) Emulsifier, intermediate, hydroxy acrylate, styrene, alkyl acrylate, a portion of water and a portion of initiator are mixed to obtain an emulsion; (F2) A portion of the emulsion and the remaining water are mixed and subjected to a first reaction to obtain an emulsion intermediate; (F3) After the emulsion intermediate and the remaining emulsion undergo a second reaction, the remaining initiator is added to carry out a third reaction to obtain the polyurethane acrylate emulsion.

5. The preparation method according to claim 4, characterized in that, The mass of the water in step (F1) is 40-50% of the total water mass; The mass of the initiator mentioned in step (F1) is 70-80% of the total mass of the initiator; The mass of the emulsion in step (F2) is 5-10% of the total mass of the emulsion; The temperature of the first reaction is 75-80℃, and the time is 0.5-0.8h; The second reaction is carried out at a temperature of 75-80℃ for 1.5-2 hours. The third reaction is carried out at a temperature of 75-85℃ for a time of 0.3-0.5h.

6. A type of paint for applying hair, characterized in that, The smear paint includes the polyurethane acrylate emulsion as described in any one of claims 1-3.

7. The paint for applying hair according to claim 6, characterized in that, The varnish for applying the hair includes the following components by weight percentage: Polyurethane acrylate emulsion 60-80% Titanium dioxide 5-10% Dispersant 0.8-1.6% Wetting agent 0.01-0.1% Defoamer 0.2-0.5% Thickener 0.1-0.5% Fungicide 0.1-0.3% Anti-sticking agent 3-5% The remainder is water; The titanium dioxide includes rutile titanium dioxide; The dispersant includes sodium polyacrylate dispersant; The wetting agent includes a nonionic surfactant; The defoamer includes metal soap defoamers and / or mineral oil defoamers; The thickener includes hydroxyethyl cellulose and / or polyurethane thickener; The bactericides include Kathon-type preservatives and bactericides; The anti-sticking agent includes polyethylene wax.

8. A method for preparing a hair-sticking paint as described in claim 6 or 7, characterized in that, The preparation method includes: mixing the components of the head-sticking paint evenly to obtain the head-sticking paint.

9. The preparation method according to claim 8, characterized in that, The preparation method specifically includes the following steps: (S1) Mix the wetting agent, dispersant, defoamer and part of the polyurethane acrylate emulsion; (S2) Mix the mixture obtained in step (S1) with titanium dioxide; (S3) Mix the mixture obtained in step (S2), the thickener, and a portion of the water; (S4) Mix the mixture obtained in step (S3) with the remaining polyurethane acrylate emulsion; (S5) Mix the mixture obtained in step (S4), the bactericide, the anti-sticking agent and the remaining water to obtain the adhesive paint; The mass of the polyurethane acrylate emulsion in step (S1) is 40-50% of the total mass of the polyurethane acrylate emulsion.

10. The application of the smudge paint as described in claim 6 or 7 in pencil coating.

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