A polyurethane / acrylate primer and a method for preparing the same

Abstract

The application discloses a polyurethane / acrylate primer and a preparation method thereof. The primer comprises A component and B component. The A component comprises, in parts by weight, 5-15 parts of an acrylate polymer, 5-15 parts of a hydroxyl-terminated polyurethane, 10-25 parts of a polyhydric alcohol, 0.01-0.1 parts of a catalyst and 60-90 parts of an organic solvent. The B component is a short-chain isocyanate. The acrylate polymer has a number average molecular weight of 4000-9000 and comprises, in parts by weight, 0.02-0.1 parts of an initiator, 40-60 parts of a reaction solvent, 10-25 parts of a hydroxy acrylate, 50-80 parts of a (methyl) acrylate and 10-25 parts of a (methyl) acrylate siloxane ester. The primer has hydroxyl and siloxane functional groups. The acrylate resin and the polyurethane resin are cross-linked to form a net-structure polymer. The compatibility of the polymer with a base material and chemical linkage formed by the polymer make the primer of the application have excellent bonding properties with organic glass, inorganic glass and polyurethane films.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of polyurethane / acrylate primer preparation, and is particularly applied to improving the bonding strength of organic glass or inorganic glass and polyurethane film. BACKGROUND

[0002] The common glass interlayer film materials at present mainly include polyvinyl butyral, ethylene-vinyl acetate copolymer, ionic polymer, thermoplastic polyurethane (TPU), etc. Among them, the special structure of polyurethane endows it with excellent mechanical properties and high and low temperature adaptability, and it has good adhesion to inorganic glass, polycarbonate (organic PC) and polymethyl methacrylate (organic glass, PMMA) materials, and is an ideal interlayer film material. In the thermal compounding process of inorganic glass and organic glass, the TPU film spreads, infiltrates and solidifies on the surfaces of the two substrates, and finally bonds into laminated glass. However, in the thermal compounding process, the high molecular weight of TPU and the low process temperature of organic glass are not conducive to the infiltration of the film on the substrate surface, resulting in weakened bonding strength of the laminated glass and the safety hazard of delamination.

[0003] In order to improve the bonding strength of TPU film and glass substrate, a primer can be coated on the surface of the glass before thermal compounding. At present, the primer in the field of inorganic glass / TPU film / organic glass is relatively advanced, and there are few related literature patents. Chinese invention CN 101113308A describes a single-component interface treatment agent, which mainly improves the interfacial bonding strength of TPU film and organic glass. However, the TPU film solution of the interlayer is one of the raw materials of the invention, and the high molecular weight of TPU makes the solution not fully infiltrate the glass substrate, thereby affecting the bonding performance of the treatment agent and the glass substrate. Therefore, the primer suitable for the field of inorganic / organic laminated glass, especially the primer capable of simultaneously improving the interfacial bonding strength of TPU film and organic and inorganic glass, has great significance for research and development. SUMMARY

[0004] In view of the deficiencies of the prior art, the purpose of the present application is to provide a polyurethane / acrylate primer capable of simultaneously improving the bonding strength of organic and inorganic glass and TPU film and a preparation method thereof.

[0005] The present application provides a polyurethane / acrylate primer in the first aspect, which comprises A component and B component,

[0006] The A component comprises, by weight parts, 5-15 parts of acrylate polymer, 5-15 parts of hydroxyl-terminated polyurethane, 10-25 parts of polyol, 0.01-0.1 parts of catalyst and 60-90 parts of organic solvent;

[0007] B component is short chain isocyanate;

[0008] The number average molecular weight of the acrylate polymer is 4000 ~ 9000, including by weight: initiator 0.02 ~ 0.1 parts, reaction solvent 40 ~ 60 parts, hydroxy acrylate 10 ~ 25 parts, (methyl) acrylate 50 ~ 80 parts, (methyl) acrylate siloxane base 10 ~ 25 parts. Preferably, the preparation method of the acrylate polymer comprises the following steps:

[0009] (1) the initiator, reaction solvent is mixed under the condition of 60 ~ 90 ℃ oil bath temperature;

[0010] (2) the mixed solution of hydroxy acrylate, (methyl) acrylate and (methyl) acrylate siloxane base is slowly added to the reaction system, after the completion of dropwise addition, continue to react for 2 ~ 6 hours to obtain the reaction liquid; preferably the dropwise adding time is 40 ~ 80 minutes;

[0011] (3) the reaction liquid of step (2) is treated to obtain the acrylate polymer; the treatment is preferably transferring the reaction liquid to 500 ~ 1000 parts of precipitant for precipitation, vacuum drying at room temperature to obtain the acrylate polymer.

[0012] Further, the hydroxy acrylate is preferably one or more of hydroxy ethyl acrylate, hydroxy propyl acrylate, 4-hydroxy butyl acrylate, 6-hydroxy hexyl acrylate; the (methyl) acrylate is preferably one or more of methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-hexyl methacrylate, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-hexyl acrylate; the (methyl) acrylate siloxane base is preferably one or more of methacryloyl methyl trimethoxysilane, methacryloyl propyl triethoxysilane, methacryloyl methyl triethoxysilane, acryloyl methyl trimethoxysilane, acryloyl methyl triethoxysilane.

[0013] Further, the initiator is preferably one of azobisisobutyronitrile, azobisisopentyl nitrile, azobisisoheptyl nitrile, benzoyl peroxide, lauroyl peroxide; the reaction solvent is preferably one of acetone, butanone, ethyl acetate; the precipitant is preferably one of methanol, ethanol.

[0014] Further, the hydroxyl-terminated polyurethane is synthesized from polyester polyol, small molecule alcohol chain extender and diisocyanate, and the number average molecular weight is 4000 ~ 9000.

[0015] Further, the polyester polyol is polycaprolactone with a molecular weight of 500-2000, diol of polycarbonate series, preferably one or more of Japan Daicel PCL205, PCL208, PCL212, PCL210, PCL220, ROPOL PC11, ROPOL PC12 products.

[0016] Further, the small molecule alcohol chain extender is preferably one or more of ethylene glycol, diethylene glycol, 1, 2-propylene glycol, dipropylene glycol, 1, 4-butanediol, 1, 6-hexanediol.

[0017] Further, the diisocyanate is preferably one or more of hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexyl methane-4, 4-diisocyanate (H 12 MDI), 1, 4-cyclohexane diisocyanate (CHDI).

[0018] Further, the polyol is diol or triol with a molecular weight of 200-1000, preferably one or more of BASF PolyTHF 250, PolyTHF 650, PolyTHF 1000, Japan Daicel PCL205, PCL305, PCL308, PCL210, ROPOL PC11 products.

[0019] Further, the catalyst is preferably one or more of bismuth octoate, stannous octoate, dibutyl tin dilaurate, dimethyl tin dioctyl adipate, triethylamine, triethylene diamine or bis (2, 2-morpholinoethyl) ether.

[0020] Further, the organic solvent is preferably one or more of ethyl acetate, butyl acetate, acetone, butanone, isobutyl ketone, cyclohexanone.

[0021] Further, the short-chain isocyanate is preferably one or more of the addition product of HDI-TMP, HDI trimer, IPDI, IPDI trimer diluent, H 12 MDI.

[0022] The second aspect of the present application provides a preparation method of a polyurethane / acrylate primer, comprising the following steps:

[0023] (1) Preparation of A component: weigh and mix the measured acrylate polymer, hydroxyl-terminated polyurethane, polyol, catalyst and organic solvent to obtain a uniform mixture;

[0024] (2) Preparation of the primer: mix A component and B component according to the mass ratio to obtain a uniform mixture.

[0025] Preferably, the mass ratio of the A component and the B component is 2-14:1.

[0026] The present application prepares an acrylate polymer with hydroxyl and siloxane groups, a hydroxyl-terminated polyurethane, and a two-component primer prepared from a short-chain isocyanate, a polyol, etc. The primer of the present application is suitable for use in the field of inorganic / TPU film / organic composite laminated glass. In use, the acrylate resin with hydroxyl and siloxane functional groups and the polyurethane resin will cross-link to form a network structure polymer. The compatibility of the polymer with the substrate and the chemical linkage formed make the primer of the present application exhibit excellent bonding performance with organic glass, inorganic glass, and polyurethane TPU film. First, the acrylate structure segment in the primer is a homologous series resin with organic glass, which can improve the adhesion of the primer to the organic glass substrate. Second, the introduction of the siloxane group helps to improve the adhesion of the primer to the inorganic glass substrate. Finally, the polyurethane structure segment in the primer also has good adhesion with the TPU film, and the chemical linkage formed between the residual NCO on the surface of the primer-coated substrate and the TPU film makes the adhesion performance more excellent. Therefore, the primer of the present application can act as a bridge between the (inorganic or organic) glass substrate and the TPU film, significantly improving the bonding strength of the laminated glass. DETAILED DESCRIPTION

[0027] To make the objectives, technical solutions, and advantages of the present application clearer, the technical solutions of the embodiments of the present application are described below clearly and completely, and the amounts of the components are all in parts by weight. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the described embodiments of the present application, all other embodiments obtained by a person of ordinary skill in the art belong to the scope of protection of the present application.

[0028] Embodiment 1

[0029] Preparation of the A component of the primer:

[0030] (1) 0.1 parts of azobisisobutyronitrile, 40 parts of acetone were mixed at 65 ℃ oil bath temperature for 15 minutes, and a mixture of 15 parts of hydroxyethyl acrylate, 65 parts of methyl methacrylate, and 20 parts of methacryloyloxypropyl triethoxysilane was slowly added to the reaction system, the dropping time was 60 minutes, and after the dropping was completed, the reaction was continued for 2.5 hours. The reaction solution was transferred to 600 parts of methanol for precipitation, and vacuum dried at room temperature to obtain an acrylate polymer with a number average molecular weight of 4080;

[0031] (2) A hydroxyl-terminated polyurethane with a number average molecular weight of 6200 was prepared from 20 parts of ROPOL PC11, 5.3 parts of PCL205, 2.5 parts of 1, 6-hexanediol, and 14 parts of IPDI;

[0032] (3) 8 parts of the above acrylic ester polymer, 15 parts of the above hydroxyl-terminated polyurethane, 7 parts of PolyTHF 250, 8 parts of PCL305, 0.05 parts of dibutyltin dilaurate, 30 parts of ethyl acetate, 50 parts of acetone are mixed and stirred uniformly to obtain a primer A component;

[0033] Preparation of the primer: the above A component and B component (HDI-TMP adduct) are mixed uniformly at a mass ratio of 7:1.

[0034] Example 2

[0035] Preparation of the primer A component:

[0036] (1) 0.1 parts of azobisisobutyronitrile, 50 parts of acetone are mixed at 65 ℃ oil bath temperature for 15 minutes, and a mixed solution of 15 parts of hydroxyethyl acrylate, 15 parts of methyl methacrylate, 55 parts of methyl acrylate and 15 parts of methacryloyloxypropyl triethoxysilane is slowly added into the reaction system, the dropping time is 60 minutes, after the completion of dropping, the reaction is continued for 2.5 hours, the reaction solution is transferred into 800 parts of methanol for precipitation, vacuum drying at room temperature to obtain an acrylic ester polymer, the number average molecular weight is 4340;

[0037] (2) 21 parts of PCL208, 3 parts of 1, 6-hexanediol, 11.5 parts of HDI polymeric MDI with a number average molecular weight of 4750 are mixed and stirred uniformly to obtain a primer B component; 12 (2) 21 parts of PCL208, 3 parts of 1, 6-hexanediol, 11.5 parts of HDI polymeric MDI with a number average molecular weight of 4750 are mixed and stirred uniformly to obtain a primer B component;

[0038] (3) 10 parts of the above acrylic ester polymer, 10 parts of the above hydroxyl-terminated polyurethane, 5 parts of PCL305, 10 parts of ROPOLPC11, 0.05 parts of dibutyltin dilaurate, 40 parts of butyl acetate, 40 parts of acetone are mixed and stirred uniformly to obtain a primer A component;

[0039] Preparation of the primer: the above A component and B component (HDI-TMP adduct with HDI polymeric MDI at a mass ratio of 4:1) are mixed uniformly at a mass ratio of 8:1. 12 Preparation of the primer: the above A component and B component (HDI-TMP adduct with HDI polymeric MDI at a mass ratio of 4:1) are mixed uniformly at a mass ratio of 8:1.

[0040] Example 3

[0041] (1) 0.06 parts of azobisisovaleronitrile, 50 parts of acetone are mixed at 65 ℃ oil bath temperature for 20 minutes, and a mixed solution of 10 parts of hydroxyethyl acrylate, 10 parts of hydroxypropyl acrylate, 70 parts of methyl methacrylate and 10 parts of methacryloyloxymethyl triethoxysilane is slowly added into the reaction system, the dropping time is 45 minutes, after the completion of dropping, the reaction is continued for 3 hours, the reaction solution is transferred into 800 parts of methanol for precipitation, vacuum drying at room temperature to obtain an acrylic ester polymer, the number average molecular weight is 5130;

[0042] (2) a hydroxyl-terminated polyurethane with a number average molecular weight of 8400 prepared by polymerization of 30 parts of PCL220, 3.1 parts of diethylene glycol, and 8.8 parts of IPDI;

[0043] (3) 12 parts of the above acrylic ester polymer, 5 parts of the above hydroxyl-terminated polyurethane, 7 parts of PolyTHF 650, 15 parts of PCL308, 0.04 parts of bismuth octoate, 40 parts of butyl acetate, and 40 parts of cyclohexanone were mixed and stirred uniformly to obtain a base coating agent A component;

[0044] Preparation of the base coating agent: the above A component and a B component (a mixture of HDI-TMP adduct and IPDI with a mass ratio of 5:1) were mixed uniformly at a mass ratio of 5.5:1.

[0045] Example 4

[0046] (1) 0.06 parts of azobis diisopropyl nitrile, 50 parts of butanone were mixed at 85°C for 15 minutes, and a mixture of 15 parts of hydroxypropyl acrylate, 25 parts of methyl methacrylate, 50 parts of ethyl acrylate, and 10 parts of acryloyloxymethyl triethoxysilane was slowly added dropwise into the reaction system, the dropping time was 45 minutes, and after the dropping was completed, the reaction was continued for 3.5 hours. The reaction solution was transferred into 800 parts of methanol for precipitation, and vacuum dried at room temperature to obtain an acrylic ester polymer with a number average molecular weight of 4960;

[0047] (2) a hydroxyl-terminated polyurethane with a number average molecular weight of 5300 prepared by polymerization of 10 parts of ROPOL PC11, 17 parts of PCL208, 2.5 parts of 1, 4-butanediol, 5.5 parts of IPDI, and 7 parts of MDI; 12

[0048] (3) 10 parts of the above acrylic ester polymer, 10 parts of the above hydroxyl-terminated polyurethane, 20 parts of PCL305, 0.04 parts of bismuth octoate, 40 parts of cyclohexanone, and 40 parts of butanone were mixed and stirred uniformly to obtain a base coating agent A component;

[0049] Preparation of the base coating agent: the above A component and a B component (a mixture of HDI-TMP adduct and IPDI with a mass ratio of 5:1) were mixed uniformly at a mass ratio of 5.5:1.

[0050] Example 5

[0051] Preparation of the base coating agent A component:

[0052] ​(1) 0.03 parts of azobisisobutyronitrile, 60 parts of methyl ethyl ketone were mixed at 85 °C oil bath temperature for 30 minutes, and a mixture of 20 parts of hydroxypropyl acrylate, 60 parts of ethyl methacrylate, 10 parts of acryloyloxy-methyl trimethoxysilane and 10 parts of methacryloyloxypropyl triethoxysilane was slowly added into the reaction system, the dropping time was 60 minutes, after the dropping was completed, the reaction was continued for 4 hours, the reaction solution was transferred into 600 parts of ethanol for precipitation, vacuum drying at room temperature to obtain an acrylate polymer, the number average molecular weight was 6380;

[0053] (2) a hydroxyl-terminated polyurethane with a number average molecular weight of 6100 prepared by polymerization of 25 parts of ROPOL PC12, 3.3 parts of dipropylene glycol, 5.2 parts of IPDI and 1.3 parts of CHDI;

[0054] (3) 13 parts of the above acrylate polymer, 9 parts of the above hydroxyl-terminated polyurethane, 20 parts of PCL210, 0.05 parts of dibutyltin dilaurate, 40 parts of ethyl acetate and 40 parts of methyl ethyl ketone were mixed and stirred uniformly to obtain a primer A component;

[0055] Preparation of the primer: the above A component was mixed with a B component (HDI trimer and HDI prepolymer prepared by mixing HDI and MDI at a mass ratio of 3:1) at a mass ratio of 7.5:1. 12 The primer was prepared by mixing the above A component with a B component (HDI trimer and HDI prepolymer prepared by mixing HDI and MDI at a mass ratio of 3:1) at a mass ratio of 7.5:1.

[0056] Example 6

[0057] Preparation of the primer A component:

[0058] (1) 0.03 parts of azobisisobutyronitrile, 50 parts of methyl ethyl ketone were mixed at 85 °C oil bath temperature for 20 minutes, and a mixture of 10 parts of 4-hydroxybutyl acrylate, 40 parts of n-propyl methacrylate, 40 parts of methyl methacrylate and 10 parts of methacryloyloxypropyl triethoxysilane was slowly added into the reaction system, the dropping time was 60 minutes, after the dropping was completed, the reaction was continued for 4 hours, the reaction solution was transferred into 600 parts of ethanol for precipitation, vacuum drying at room temperature to obtain an acrylate polymer, the number average molecular weight was 6620;

[0059] (2) a hydroxyl-terminated polyurethane with a number average molecular weight of 5000 prepared by polymerization of 26.5 parts of PCL205, 4.5 parts of 1, 4-butanediol, 23 parts of HDI and MDI; 12 The primer was prepared by mixing the above A component with a B component (HDI trimer and HDI prepolymer prepared by mixing HDI and MDI at a mass ratio of 3:1) at a mass ratio of 7.5:1.

[0060] (3) 10 parts of the above acrylate polymer, 10 parts of the above hydroxyl-terminated polyurethane, 5 parts of PolyTHF 1000, 15 parts of PCL308, 0.05 parts of dibutyltin dilaurate, 40 parts of butyl acetate and 40 parts of acetone were mixed and stirred uniformly to obtain a primer A component;

[0061] Preparation of the primer: the A component and the B component (HDI trimer) are mixed uniformly at a mass ratio of 5.6:1.

[0062] Example 7

[0063] Preparation of the primer A component:

[0064] (1) 0.02 parts of benzoyl peroxide, 60 parts of acetone are mixed at 70 °C oil bath temperature for 30 minutes, a mixture of 10 parts of hydroxyethyl acrylate, 75 parts of n-hexyl methacrylate and 15 parts of methacryloyloxypropyl triethoxysilane is slowly added to the reaction system, the dropping time is 75 minutes, after the completion of dropping, continue to react for 5 hours, the reaction solution is transferred to 700 parts of ethanol for precipitation, vacuum drying at room temperature to obtain an acrylate polymer, the number average molecular weight is 7860;

[0065] (2) the end hydroxyl polyurethane with a number average molecular weight of 8700 is prepared by polymerization of 40 parts of PCL220, 0.8 parts of dipropylene glycol, 4.4 parts of IPDI and 1 part of HDI; 12 MDI polymerization to prepare the end hydroxyl polyurethane with a number average molecular weight of 4900;

[0066] (3) 7 parts of the above acrylate polymer, 13 parts of the above end hydroxyl polyurethane, 20 parts of ROPOL PC11, 0.03 parts of bismuth isooctoate, 40 parts of butyl acetate and 40 parts of ethyl acetate are mixed and stirred uniformly to obtain the primer A component;

[0067] Preparation of the primer: the A component and the B component (HDI-TMP adduct and IPDI mixed at a mass ratio of 2:1) are mixed uniformly at a mass ratio of 8.5:1.

[0068] Example 8

[0069] Preparation of the primer A component:

[0070] (1) 0.02 parts of benzoyl peroxide, 50 parts of acetone are mixed at 65 °C oil bath temperature for 20 minutes, a mixture of 15 parts of hydroxyethyl acrylate, 30 parts of isopropyl acrylate, 40 parts of methyl methacrylate, 15 parts of acryloyloxymethyl trimethoxysilane and 10 parts of methacryloyloxypropyl triethoxysilane is slowly added to the reaction system, the dropping time is 75 minutes, after the completion of dropping, continue to react for 5 hours, the reaction solution is transferred to 700 parts of methanol for precipitation, vacuum drying at room temperature to obtain an acrylate polymer, the number average molecular weight is 8060;

[0071] (2) the end hydroxyl polyurethane with a number average molecular weight of 8700 is prepared by polymerization of 40 parts of PCL220, 0.8 parts of dipropylene glycol, 4.4 parts of IPDI and 1 part of HDI;

[0072] (3) 6 parts of the above acrylic ester polymer, 6 parts of the above hydroxyl-terminated polyurethane, 10 parts of PolyTHF 650, 5 parts of PCL210, 10 parts of PCL308, 0.05 parts of bismuth octoate, 40 parts of ethyl acetate, 40 parts of isobutyl ketone are mixed and stirred uniformly to obtain the primer A component.

[0073] Preparation of the primer: the above A component and B component (HDI trimer and HDI-TMP adduct obtained by mixing HDI and TMP at a mass ratio of 2:1) are mixed uniformly at a mass ratio of 8.5:1. 12 MDI is mixed at a mass ratio of 3:1, and the obtained product is mixed uniformly at a mass ratio of 7.2:1.

[0074] Comparative Example 1

[0075] Preparation of the primer A component:

[0076] (1) 0.02 parts of benzoyl peroxide, 60 parts of acetone are mixed at 70°C for 30 minutes, 100 parts of n-hexyl methacrylate are slowly added to the reaction system, the dropping time is 75 minutes, after the dropping is completed, the reaction is continued for 5 hours, the reaction solution is transferred to 500 parts of ethanol for precipitation, and vacuum drying at room temperature is carried out to obtain an acrylic ester polymer, and the number average molecular weight is 8200;

[0077] (2) 16 parts of PCL208, 20 parts of ROPOL PC11, 1.5 parts of 1, 3-propanediol, 13 parts of HDI trimer are mixed and stirred uniformly to obtain the primer A component. 12 MDI polymerization to prepare a hydroxyl-terminated polyurethane with a number average molecular weight of 4900;

[0078] (3) 7 parts of the above acrylic ester polymer, 13 parts of the above hydroxyl-terminated polyurethane, 20 parts of ROPOL PC11, 0.03 parts of bismuth octoate, 40 parts of butyl acetate, 40 parts of ethyl acetate are mixed and stirred uniformly to obtain the primer A component.

[0079] Preparation of the primer: the above A component and B component (HDI-TMP adduct and IPDI obtained by mixing HDI and TMP at a mass ratio of 2:1) are mixed uniformly at a mass ratio of 8.5:1.

[0080] Comparative Example 2

[0081] Preparation of the primer A component:

[0082] (1) 30 parts of PCL220, 3.1 parts of diethylene glycol, 8.8 parts of IPDI are polymerized to prepare a hydroxyl-terminated polyurethane with a number average molecular weight of 8400;

[0083] (2) 13 parts of the above hydroxyl-terminated polyurethane, 2 parts of γ-mercaptopropyl trimethoxysilane, 7 parts of PolyTHF 650, 15 parts of PCL308, 0.04 parts of bismuth octoate, 40 parts of butyl acetate, 40 parts of cyclohexanone are mixed and stirred uniformly to obtain the primer A component.

[0084] Preparation of the primer: the above A component and B component (HDI-TMP adduct and IPDI mixed in a mass ratio of 5:1) were mixed uniformly in a mass ratio of 8:1.

[0085] Comparative Example 3

[0086] (1) An acrylate polymer with a number average molecular weight of 6620 was prepared by the same method as in step (1) of Example 6.

[0087] (2) 10 parts of the above acrylate polymer, 5 parts of PolyTHF 1000, 15 parts of PCL308, 4.9 parts of PCL205, 0.83 parts of 1, 4-butanediol, 0.05 parts of dibutyltin dilaurate, 40 parts of butyl acetate, and 40 parts of acetone were mixed and stirred uniformly to obtain the primer A component.

[0088] Preparation of the primer: the above A component and B component (HDI trimer and HDI-TMP adduct mixed in a mass ratio of 2:1) were mixed uniformly in a mass ratio of 4.5:1. 12

[0089] Comparative Example 4

[0090] (1) An acrylate polymer with a number average molecular weight of 6380 was prepared by the same method as in step (1) of Example 5.

[0091] (2) A hydroxyl-terminated polyurethane with a number average molecular weight of 42000 was prepared by polymerization of 40 parts of ROPOL PC12, 0.67 parts of dipropylene glycol, and 5.3 parts of IPDI.

[0092] (3) 13 parts of the above acrylate polymer, 9 parts of the above hydroxyl-terminated polyurethane, 20 parts of PCL210, 0.05 parts of dibutyltin dilaurate, 40 parts of ethyl acetate, and 40 parts of butanone were mixed and stirred uniformly to obtain the primer A component.

[0093] Preparation of the primer: the above A component and B component (HDI trimer and HDI-TMP adduct mixed in a mass ratio of 2:1) were mixed uniformly in a mass ratio of 4.5:1. 12

[0094] ​​The primer of Examples 1-8 and Comparative Examples 1-4 is subjected to adhesion performance test. Test method: the primer of Examples 1-8 and Comparative Examples 1-4 is coated on the surface of inorganic glass and organic glass substrates respectively, and polyurethane adhesive film is prepared by hot pressing to bond inorganic glass sample and organic glass sample; on the above glass sample, a 25mm wide sample strip is prepared, and the peeling strength is tested by 90° peeling method, and compared with the blank sample without primer coating. The peeling strength a and b are the test results of the inorganic glass sample and the organic glass sample after being placed at room temperature for 48 hours. When the peeling strength is greater than the strength of the polyurethane adhesive film or the glass substrate itself, the sample strip is broken or the surface of the glass substrate is damaged, and the true peeling strength cannot be measured, which is considered as the best bonding effect. As can be seen from the data in Table 1, the two-component polyurethane / acrylate primer of the present application can significantly improve the bonding strength of the polyurethane adhesive film to the organic glass and inorganic glass.

[0095] Table 1 Performance table of primer of Examples 1-8 and Comparative Examples 1-4 and blank sample

[0096] Peel strength a (N / mm) Peel strength b (N / mm) Example 1 Sample broke, could not be peeled completely Sample broke, could not be peeled completely Example 2 Sample broke, could not be peeled completely Sample broke, could not be peeled completely Example 3 Sample broke, could not be peeled completely Sample broke, could not be peeled completely Example 4 Sample broke, could not be peeled completely Sample broke, could not be peeled completely Example 5 Sample broke, could not be peeled completely Sample broke, could not be peeled completely Example 6 Sample broke, could not be peeled completely Sample broke, could not be peeled completely Example 7 Sample broke, could not be peeled completely Sample broke, could not be peeled completely Example 8 Sample broke, could not be peeled completely Sample broke, could not be peeled completely Comparative Example 1 5.1 5.9 Comparative Example 2 5.7 4.5 Comparative Example 3 6.6 6.1 Comparative Example 4 5.3 4.8 Blank 4.2 3.4

Claims

1. A polyurethane / acrylate primer, comprising component A and component B, Component A comprises, by weight: 5-15 parts of acrylate polymers, 5-15 parts of hydroxyl-terminated polyurethanes, 10-25 parts of polyols, 0.01-0.1 parts of catalysts, and 60-90 parts of organic solvents; Component B is a short-chain isocyanate; The acrylate polymer has a number average molecular weight of 4000-9000 and comprises, by weight: 0.02-0.1 parts initiator, 40-60 parts reaction solvent, 10-25 parts hydroxy acrylate, 50-80 parts (meth)acrylate, and 10-25 parts (meth)acrylate siloxane ester. The hydroxyl-terminated polyurethane is synthesized from polyester polyol, small molecule alcohol chain extender and diisocyanate, with a number average molecular weight of 4000 to 9000. The polyester polyol is a diol of polycaprolactone or polycarbonate series with a molecular weight of 500 to 2000. The small molecule alcohol chain extender is selected from one or more of ethylene glycol, diethylene glycol, 1,2-propanediol, dipropylene glycol, 1,4-butanediol, and 1,6-hexanediol.

2. The primer according to claim 1, characterized in that, The hydroxy acrylate is selected from one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate, and 6-hydroxyhexyl acrylate.

3. The primer according to claim 1, characterized in that, The (meth)acrylate is selected from one or more of methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-hexyl methacrylate, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, and n-hexyl acrylate.

4. The primer according to claim 1, characterized in that, The (meth)acrylate siloxane is selected from one or more of methacryloyloxymethyltrimethoxysilane, methacryloyloxypropyltriethoxysilane, methacryloyloxymethyltriethoxysilane, acryloyloxymethyltrimethoxysilane, and acryloyloxymethyltriethoxysilane.

5. The primer according to claim 1, characterized in that, The polyester polyol is one or more of the following products: Daicel PCL205, PCL208, PCL212, PCL210, PCL220, ROPOL PC11, and ROPOL PC12.

6. The primer according to claim 1, characterized in that, The diisocyanate is selected from hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and dicyclohexylmethane-4,4-diisocyanate (HDI). 12 One or more of MDI, 1,4-cyclohexane diisocyanate (CHDI).

7. The primer according to claim 1, characterized in that, The polyol is a diol or triol with a molecular weight of 200 to 1000.

8. The primer according to claim 7, characterized in that, The polyol is selected from one or more of BASF PolyTHF 250, PolyTHF 650, PolyTHF 1000, Daicel PCL205, PCL305, PCL308, PCL210, and ROPOL PC11 products.

9. The primer according to claim 1, characterized in that, The short-chain isocyanate is selected from HDI-TMP adducts, HDI trimers, IPDI, IPDI trimer dilutions, and H... 12 One or more of the following: MDI.

10. A method for preparing a primer according to any one of claims 1-9, comprising the following steps: (1) Preparation of component A: Weigh the measured amounts of acrylate polymer, hydroxyl-terminated polyurethane, polyol, catalyst, and organic solvent and stir to mix evenly; (2) Preparation of primer: Mix component A and component B evenly according to the mass ratio; the mass ratio of component A to component B is 2 ~ 14:1.