Application of hyperbranched polyurethane acrylate resin in UV photocureable coating

Abstract

The invention discloses an application of hyperbranched polyurethane acrylate resin in a UV photocureable coating, and belongs to the technical field of photocureable coatings, the coating comprises the following components: hyperbranched polyurethane acrylate resin, DPHA, TA, HDDA, TMPTA, a photoinitiator TPO, and a photoinitiator PETA. According to the invention, novel hyperbranched polyurethane acrylate resin is synthesized firstly, and through introduction of a hyperbranched core and hybridization of polyurethane and acrylate resin, the curing speed and coating hardness of a curing film prepared from the resin are improved, and the toughness of a rigid curing film is also improved, so that high wear and scratch resistance of a high-hardness material is realized. And on the basis that the core resin component is modified, the UV photocureable coating containing the hyperbranched polyurethane acrylate resin, of which the performance parameters in all aspects are comprehensively improved, is obtained.

Description

Technical Field

[0001] The invention belongs to the technical field of photocurable coatings, and in particular relates to application of a hyperbranched polyurethane acrylate resin in UV photocurable coatings. Background Art

[0002] As an efficient and environmentally friendly coating technology, photocurable resin coatings have been widely used in the coatings industry in recent years. Among them, polyurethane acrylate (PUA) photocurable resin coatings have become a research hotspot due to their excellent performance and wide application fields.

[0003] With the continuous development and improvement of light-curing technology, PUA light-curing resin coatings have gradually shown their unique advantages. By introducing acrylate groups, PUA light-curing resin coatings not only inherit the excellent wear resistance, weather resistance and chemical resistance of polyurethane materials, but also have the advantages of fast curing, environmental protection and energy saving of light-curing resin coatings.

[0004] PUA light-curing resin coating has many excellent performance characteristics. First, it has a high curing speed and efficiency, can complete the curing process in a short time, and improve production efficiency. Secondly, PUA light-curing resin coating has good adhesion and flexibility, can be closely combined with the substrate to form a continuous and uniform coating. In addition, it also has excellent wear resistance, weather resistance and chemical resistance, which can maintain the beauty and performance of the coating for a long time.

[0005] PUA light-curing resin coatings are widely used in many fields. In the field of wooden furniture, it can be used to make coatings with high gloss, wear resistance and easy cleaning; in the automotive industry, PUA light-curing resin coatings can be used for coating of automotive interior and exterior trims to improve the appearance quality and durability of the car; in the field of electronic appliances, it can be used to make coatings with excellent insulation, weather resistance and wear resistance. In addition, PUA light-curing resin coatings can also be used in the fields of construction, aerospace and so on.

[0006] With the increasing awareness of environmental protection and the continuous development of coating technology, the development prospects of PUA photocurable resin coatings are very broad. However, there are still many problems with the PUA photocurable resin coatings on the market. In the future, PUA photocurable resin coatings will make further progress in many aspects: improve the curing speed and efficiency to achieve a faster and more efficient coating process; optimize the coating performance, improve the coating's wear resistance, weather resistance and chemical resistance; expand the application field, and apply PUA photocurable resin coatings to more fields to meet the needs of different industries; strengthen the research and development of environmental protection performance, reduce the impact of coatings on the environment during use, and achieve green coating. Due to the problems of component selection in the coating formula and the most basic limitations of the performance of photocurable resins, the various performance parameters of the current PUA photocurable resin coatings cannot be balanced, and the general formula of the same resin cannot meet the application of multiple scenarios. Summary of the invention

[0007] In order to solve the above problems, the present invention proposes an application of a hyperbranched polyurethane acrylate resin in a UV light-curing coating, wherein a core component in the coating formula is provided: a new hyperbranched polyurethane acrylate UV light-curing resin and a preparation method thereof, and a coating formula based on the resin is proposed, and the specific scheme is as follows:

[0008] The invention discloses an application of a hyperbranched polyurethane acrylate resin in a UV light-curing coating. The coating comprises the following components: a hyperbranched polyurethane acrylate resin, DPHA, TA, HDDA, TMPTA, a photoinitiator TPO and a photoinitiator PETA.

[0009] Preferably, the components in the coating include, by mass, 100-150 parts of hyperbranched polyurethane acrylate resin, 50-80 parts of DPHA, 30-60 parts of TA, 20-40 parts of HDDA, 10-30 parts of TMPTA, 5-8 parts of photoinitiator TPO, and 10-15 parts of photoinitiator PETA.

[0010] Preferably, the hyperbranched polyurethane acrylate resin has a structure as shown in structural formula I:

[0011]

[0012] Wherein, R' represents polydipentaerythritol, and the structure of R is one or more of the following structural formulas II, III, and IV:

[0013]

[0014] Preferably, the method for preparing the hyperbranched polyurethane acrylate resin comprises the following steps:

[0015] S1, preparing a capping agent;

[0016] S2, the end-capping agent reacts with the hyperbranched polyester polyol to generate a hyperbranched polyurethane acrylate UV light-curing resin;

[0017] The end-capping agent includes IH shown in structural formula V or IF shown in structural formula VI or ethyl isocyanate acrylate:

[0018]

[0019]

[0020] Preferably, the preparation of the capping agent in S1 specifically comprises: mixing IPDI and the catalyst under an argon atmosphere, adding the capping agent HEA or the capping agent FM1D, and reacting to obtain the capping agent IH or the capping agent IF.

[0021] Preferably, the reaction is carried out under stirring conditions.

[0022] Preferably, the molar ratio of IPDI in S1 to the end-capping agent HEA or the end-capping agent FM1D is 1:(1-1.2).

[0023] Preferably, the catalyst in S1 is T-12 catalyst, and the dosage is 200-500 ppm based on IPDI.

[0024] Preferably, in the reaction of S1, the reaction temperature is 30-75°C and the reaction time is 3-4h.

[0025] Preferably, the catalyst in S1 is a composite catalyst, which includes T-12 catalyst and TEA, and the molar ratio of the two is 1:(1-4), and the amount of the catalyst is 200-500ppm based on the amount of IPDI.

[0026] Preferably, in the reaction of S1, the reaction temperature is 60-75°C and the reaction time is 1-2h.

[0027] Preferably, the reaction in S2 specifically comprises: dissolving the IH or IF obtained in step S1 into a solvent under an argon atmosphere, adding a hyperbranched polyester polyol, and reacting by heating to obtain a hyperbranched polyurethane acrylate UV light-curing resin.

[0028] Preferably, the amount of the hyperbranched polyester polyol in S2 is equivalent to the added IH or IF.

[0029] Preferably, in the reaction of S2, the reaction temperature is 30-100°C and the reaction time is 24-48h.

[0030] Preferably, the reaction in S2 is stopped after the disappearance of the isocyanate group NCO is detected.

[0031] Preferably, the solvent in S2 includes one or more of MEK, EOEOEA and NVP.

[0032] Preferably, in the reaction of S2, 1,4-butanediol (BDO) is further added in an amount of 8-15% of the molar amount of the hyperbranched polyol.

[0033] Preferably, in the reaction of S2, the reaction temperature is 80-100° C., the reaction time is 24-48 h, and the reaction is stopped after the disappearance of the isocyanate group NCO is detected.

[0034] Beneficial Effects

[0035] The present invention first synthesizes a new hyperbranched polyurethane acrylate resin, and by introducing a hyperbranched core and hybridizing polyurethane with an acrylate resin, the curing speed and coating hardness of the cured film prepared by the resin are improved, and the toughness of the rigid cured film is improved, thereby achieving high wear and scratch resistance of high-hardness materials. It has been found through research that during the application of the resin, the use of a simple and general coating formula cannot achieve a comprehensive improvement in the performance of the cured film. Therefore, the present invention optimizes the coating formula on the basis of modifying the core resin component, and obtains a general parameter comprehensive upgrade solution. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 This is the MS-ESI spectrum of the end-capping agent IH obtained in the preparation example;

[0037] Figure 2 FT-IR spectrum of the hyperbranched polyurethane acrylate UV light-curing resin obtained in the preparation example;

[0038] Figure 3 The GPC curves of the hyperbranched polyurethane acrylate UV light-curing resin and the hyperbranched polyol obtained in the preparation example are shown. DETAILED DESCRIPTION

[0039] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0040] Unless otherwise defined, all professional and scientific terms used herein have the same meanings as those familiar to those skilled in the art. In addition, any methods and materials similar or equivalent to those described herein may be applied to the present invention. The preferred implementation methods and materials described herein are for demonstration purposes only and are not intended to limit the content of this application.

[0041] The experimental methods in the following examples are conventional methods unless otherwise specified, and the experimental materials used in the following examples are purchased from commercial channels unless otherwise specified.

[0042] Preparation example and method:

[0043] A hyperbranched polyurethane acrylate UV light-curing resin is prepared according to the following method for use: a hyperbranched polyurethane acrylate UV light-curing resin with a specific parameter is obtained by using different numbered preparation examples. The coating formula provided by the present invention includes but is not limited to the hyperbranched polyurethane acrylate UV light-curing resin prepared in the following preparation examples:

[0044] Preparation of hyperbranched polyurethane acrylate UV light curing resin:

[0045] S1, preparing a capping agent;

[0046] S2, the end-capping agent reacts with the hyperbranched polyol to generate a hyperbranched polyurethane acrylate UV light-curing resin;

[0047] The capping agent includes IH shown in structural formula V or IF shown in structural formula VI.

[0048] The preparation of the end-capping agent described in S1 specifically includes: mixing IPDI and the catalyst under an argon atmosphere, adding the end-capping agent HEA or the end-capping agent FM1D, and reacting to obtain the end-capping agent IH or the end-capping agent IF.

[0049] The reaction is carried out under stirring conditions.

[0050] The molar ratio of IPDI to the end-capping agent HEA or the end-capping agent FM1D in S1 is 1:(1-1.2).

[0051] The catalyst in S1 is T-12 catalyst, and the dosage is 200-500ppm based on IPDI.

[0052] In the reaction described in S1, the reaction temperature is 30-75°C and the reaction time is 3-4h.

[0053] The catalyst described in S1 is a composite catalyst, which includes T-12 catalyst and TEA, and the molar ratio of the two is 1:(1-4). The amount of the catalyst is 200-500ppm based on the amount of IPDI.

[0054] In the reaction described in S1, the reaction temperature is 60-75° C. and the reaction time is 1-2 h.

[0055] The reaction in step S2 specifically includes: dissolving the IH or IF obtained in step S1 into a solvent under an argon atmosphere, adding a hyperbranched polyol, and reacting by heating to obtain a hyperbranched polyurethane acrylate UV light-curing resin.

[0056] The amount of the hyperbranched polyol described in S2 is equivalent to the added IH or IF.

[0057] In the reaction of S2, the reaction temperature is 30-100°C and the reaction time is 24-48h.

[0058] The reaction described in S2 is stopped after the disappearance of the isocyanate group NCO is detected.

[0059] S2 The solvent includes one or more of MEK, EOEOEA, and NVP.

[0060] In the reaction described in S2, 1,4-butanediol (BDO) is further added in an amount of 8-15% of the molar amount of the hyperbranched polyol.

[0061] The reaction in S2 has a reaction temperature of 80-100° C. and a reaction time of 24-48 hours. The reaction is stopped after the disappearance of the isocyanate group NCO is detected.

[0062] Preparation Example 1 Preparation of hyperbranched polyurethane acrylate UV light-curing resin:

[0063] S1, preparing a capping agent;

[0064] S2, the end-capping agent reacts with the hyperbranched polyol to generate a hyperbranched polyurethane acrylate UV light-curing resin;

[0065] The capping agent includes IH shown in structural formula V or IF shown in structural formula VI.

[0066] The preparation of the end-capping agent described in S1 specifically includes: mixing IPDI and the catalyst under an argon atmosphere, adding the end-capping agent HEA or the end-capping agent FM1D, and reacting to obtain the end-capping agent IH or the end-capping agent IF.

[0067] The reaction is carried out under stirring conditions.

[0068] The molar ratio of IPDI to the end-capping agent HEA or the end-capping agent FM1D in S1 is 1:1.

[0069] The catalyst described in S1 is T-12 catalyst, and the dosage is 200ppm based on the dosage of IPDI.

[0070] The reaction described in S1, the reaction temperature is 30°C, and the reaction time is 3h.

[0071] The reaction in step S2 specifically includes: dissolving the IH or IF obtained in step S1 into a solvent under an argon atmosphere, adding a hyperbranched polyol, and reacting by heating to obtain a hyperbranched polyurethane acrylate UV light-curing resin.

[0072] The hyperbranched polyol described in S2 is H500, the dosage is 0.01 mol, and the added end-capping agent is IH or IF, the added dosage is 0.19 mol.

[0073] The reaction described in S2 is carried out at a temperature of 50° C. and a reaction time of 24-48 hours. The reaction is stopped after the disappearance of the isocyanate group NCO is detected.

[0074] The solvent in S2 is MEK, and the added amount is 25%wt of the entire reaction system.

[0075] Preparation Example 2 Preparation of hyperbranched polyurethane acrylate UV light-curing resin:

[0076] S1, preparing a capping agent;

[0077] S2, the end-capping agent reacts with the hyperbranched polyol to generate a hyperbranched polyurethane acrylate UV light-curing resin;

[0078] The capping agent includes IH shown in structural formula V or IF shown in structural formula VI.

[0079] The preparation of the end-capping agent described in S1 specifically includes: mixing IPDI and the catalyst under an argon atmosphere, adding the end-capping agent HEA or the end-capping agent FM1D, and reacting to obtain the end-capping agent IH or the end-capping agent IF.

[0080] The reaction is carried out under stirring conditions.

[0081] The molar ratio of IPDI to the end-capping agent HEA or the end-capping agent FM1D in S1 is 1:1.

[0082] The catalyst described in S1 is T-12 catalyst, and the dosage is 200ppm based on the dosage of IPDI.

[0083] The reaction described in S1, the reaction temperature is 30°C, and the reaction time is 3h.

[0084] The reaction in step S2 specifically includes: dissolving the IH or IF obtained in step S1 into a solvent under an argon atmosphere, adding a hyperbranched polyol, and reacting by heating to obtain a hyperbranched polyurethane acrylate UV light-curing resin.

[0085] The hyperbranched polyol described in S2 is F500, the amount used is 0.01 mol, and the added end-capping agent is IH or IF, the amount added is 0.19 mol.

[0086] The reaction described in S2 is carried out at a temperature of 50° C. and a reaction time of 24-48 hours. The reaction is stopped after the disappearance of the isocyanate group NCO is detected.

[0087] The solvent in S2 is MEK, and the added amount is 25%wt of the entire reaction system.

[0088] Preparation Example 3 Preparation of hyperbranched polyurethane acrylate UV light-curing resin:

[0089] S1, preparing a capping agent;

[0090] S2, the end-capping agent reacts with the hyperbranched polyol to generate a hyperbranched polyurethane acrylate UV light-curing resin;

[0091] The capping agent includes IH shown in structural formula V or IF shown in structural formula VI.

[0092] The preparation of the end-capping agent described in S1 specifically includes: mixing IPDI and the catalyst under an argon atmosphere, adding the end-capping agent HEA or the end-capping agent FM1D, and reacting to obtain the end-capping agent IH or the end-capping agent IF.

[0093] The reaction is carried out under stirring conditions.

[0094] The molar ratio of IPDI to the end-capping agent HEA or the end-capping agent FM1D in S1 is 1:1.

[0095] The catalyst described in S1 is T-12 catalyst, and the dosage is 200ppm based on the dosage of IPDI.

[0096] The reaction described in S1, the reaction temperature is 30°C, and the reaction time is 3h.

[0097] The reaction in step S2 specifically includes: dissolving the IH or IF obtained in step S1 into a solvent under an argon atmosphere, adding a hyperbranched polyol, and reacting by heating to obtain a hyperbranched polyurethane acrylate UV light-curing resin.

[0098] The hyperbranched polyol described in S2 is HE500, the dosage is 0.01 mol, and the added end-capping agent is IH or IF, the added dosage is 0.19 mol.

[0099] The reaction described in S2 is carried out at a temperature of 50° C. and a reaction time of 24-48 hours. The reaction is stopped after the disappearance of the isocyanate group NCO is detected.

[0100] The solvent in S2 is EOEOEA, and the added amount is 25%wt of the entire reaction system.

[0101] Preparation Example 4 Preparation of hyperbranched polyurethane acrylate UV light-curing resin:

[0102] S1, preparing a capping agent;

[0103] S2, the end-capping agent reacts with the hyperbranched polyol to generate a hyperbranched polyurethane acrylate UV light-curing resin;

[0104] The capping agent includes IH shown in structural formula V or IF shown in structural formula VI.

[0105] The preparation of the end-capping agent described in S1 specifically includes: mixing IPDI and the catalyst under an argon atmosphere, adding the end-capping agent HEA or the end-capping agent FM1D, and reacting to obtain the end-capping agent IH or the end-capping agent IF.

[0106] The reaction is carried out under stirring conditions.

[0107] The molar ratio of IPDI to the end-capping agent HEA or the end-capping agent FM1D in S1 is 1:1.

[0108] The catalyst described in S1 is T-12 catalyst, and the dosage is 200ppm based on the dosage of IPDI.

[0109] The reaction described in S1, the reaction temperature is 30°C, and the reaction time is 3h.

[0110] The reaction in step S2 specifically includes: dissolving the IH or IF obtained in step S1 into a solvent under an argon atmosphere, adding a hyperbranched polyol, and reacting by heating to obtain a hyperbranched polyurethane acrylate UV light-curing resin.

[0111] The hyperbranched polyol described in S2 is HN500, the dosage is 0.01 mol, and the added end-capping agent is IH or IF, the added dosage is 0.19 mol.

[0112] The reaction described in S2 is carried out at a temperature of 30° C. and a reaction time of 24-48 hours. The reaction is stopped after the disappearance of the isocyanate group NCO is detected.

[0113] The solvent in S2 is NVP, and the amount added is 25%wt of the entire reaction system.

[0114] Preparation Example 5 Preparation of hyperbranched polyurethane acrylate UV light-curing resin:

[0115] S1, preparing a capping agent;

[0116] S2, the end-capping agent reacts with the hyperbranched polyol to generate a hyperbranched polyurethane acrylate UV light-curing resin;

[0117] The capping agent includes IH shown in structural formula V or IF shown in structural formula VI.

[0118] The preparation of the end-capping agent described in S1 specifically includes: mixing IPDI and the catalyst under an argon atmosphere, adding the end-capping agent HEA or the end-capping agent FM1D, and reacting to obtain the end-capping agent IH or the end-capping agent IF.

[0119] The reaction is carried out under stirring conditions.

[0120] The molar ratio of IPDI to the end-capping agent HEA or the end-capping agent FM1D in S1 is 1:1.

[0121] The catalyst described in S1 is T-12 catalyst, and the dosage is 200ppm based on the dosage of IPDI.

[0122] The reaction described in S1, the reaction temperature is 30°C, and the reaction time is 3h.

[0123] The reaction in step S2 specifically includes: dissolving the IH or IF obtained in step S1 into a solvent under an argon atmosphere, adding a hyperbranched polyol, and reacting by heating to obtain a hyperbranched polyurethane acrylate UV light-curing resin.

[0124] The hyperbranched polyol described in S2 is FE500, the dosage is 0.01 mol, and the added end-capping agent is IH or IF, the added dosage is 0.19 mol.

[0125] The reaction described in S2 is carried out at a temperature of 50° C. and a reaction time of 24-48 hours. The reaction is stopped after the disappearance of the isocyanate group NCO is detected.

[0126] The solvent in S2 is EOEOEA, and the added amount is 25%wt of the entire reaction system.

[0127] Preparation Example 6 Preparation of hyperbranched polyurethane acrylate UV light-curing resin:

[0128] S1, preparing a capping agent;

[0129] S2, the end-capping agent reacts with the hyperbranched polyol to generate a hyperbranched polyurethane acrylate UV light-curing resin;

[0130] The capping agent includes IH shown in structural formula V or IF shown in structural formula VI.

[0131] The preparation of the end-capping agent described in S1 specifically includes: mixing IPDI and the catalyst under an argon atmosphere, adding the end-capping agent HEA or the end-capping agent FM1D, and reacting to obtain the end-capping agent IH or the end-capping agent IF.

[0132] The reaction is carried out under stirring conditions.

[0133] The molar ratio of IPDI to the end-capping agent HEA or the end-capping agent FM1D in S1 is 1:1.

[0134] The catalyst described in S1 is T-12 catalyst, and the dosage is 200ppm based on the dosage of IPDI.

[0135] The reaction described in S1, the reaction temperature is 30°C, and the reaction time is 3h.

[0136] The reaction in step S2 specifically includes: dissolving the IH or IF obtained in step S1 into a solvent under an argon atmosphere, adding a hyperbranched polyol, and reacting by heating to obtain a hyperbranched polyurethane acrylate UV light-curing resin.

[0137] The hyperbranched polyol described in S2 is FN500, the dosage is 0.01 mol, and the added end-capping agent is IH or IF, the added dosage is 0.19 mol.

[0138] The reaction described in S2 is carried out at a temperature of 30° C. and a reaction time of 24-48 hours. The reaction is stopped after the disappearance of the isocyanate group NCO is detected.

[0139] The solvent in S2 is NVP, and the amount added is 25%wt of the entire reaction system.

[0140] Preparation Example 7 Preparation of hyperbranched polyurethane acrylate UV light-curing resin:

[0141] S1, preparing a capping agent;

[0142] S2, the end-capping agent reacts with the hyperbranched polyol to generate a hyperbranched polyurethane acrylate UV light-curing resin;

[0143] The capping agent includes IH shown in structural formula V or IF shown in structural formula VI.

[0144] The preparation of the end-capping agent described in S1 specifically includes: mixing IPDI and the catalyst under an argon atmosphere, adding the end-capping agent HEA or the end-capping agent FM1D, and reacting to obtain the end-capping agent IH or the end-capping agent IF.

[0145] The reaction is carried out under stirring conditions.

[0146] The molar ratio of IPDI to the end-capping agent HEA or the end-capping agent FM1D in S1 is 1:1.

[0147] The catalyst described in S1 is T-12 catalyst, and the dosage is 200ppm based on the dosage of IPDI.

[0148] The reaction described in S1, the reaction temperature is 30°C, and the reaction time is 3h.

[0149] The reaction in step S2 specifically includes: dissolving the IH or IF obtained in step S1 into a solvent under an argon atmosphere, adding a hyperbranched polyol, and reacting by heating to obtain a hyperbranched polyurethane acrylate UV light-curing resin.

[0150] The hyperbranched polyol described in S2 is AE500, the dosage is 0.01 mol, and the added end-capping agent is IH or IF, the added dosage is 0.19 mol.

[0151] The reaction described in S2 is carried out at a temperature of 50° C. and a reaction time of 24-48 hours. The reaction is stopped after the disappearance of the isocyanate group NCO is detected.

[0152] The solvent in S2 is EOEOEA, and the added amount is 25%wt of the entire reaction system.

[0153] Preparation Example 8 (Based on Preparation Example 7) Preparation of hyperbranched polyurethane acrylate UV light-cured resin:

[0154] S1, preparing a capping agent;

[0155] S2, the end-capping agent reacts with the hyperbranched polyol to generate a hyperbranched polyurethane acrylate UV light-curing resin;

[0156] The capping agent includes IH shown in structural formula V or IF shown in structural formula VI.

[0157] The preparation of the end-capping agent described in S1 specifically includes: mixing IPDI and the catalyst under an argon atmosphere, adding the end-capping agent HEA or the end-capping agent FM1D, and reacting to obtain the end-capping agent IH or the end-capping agent IF.

[0158] The reaction is carried out under stirring conditions.

[0159] The molar ratio of IPDI to the end-capping agent HEA or the end-capping agent FM1D in S1 is 1:1.

[0160] The catalyst described in S1 is a composite catalyst, which includes T-12 catalyst and TEA, the molar ratio of the two is 1:1, and the amount of catalyst used is 200ppm based on the amount of IPDI.

[0161] The reaction described in S1, the reaction temperature is 60°C, and the reaction time is 1h.

[0162] The reaction in step S2 specifically includes: dissolving the IH or IF obtained in step S1 into a solvent under an argon atmosphere, adding a hyperbranched polyol, and reacting by heating to obtain a hyperbranched polyurethane acrylate UV light-curing resin.

[0163] The hyperbranched polyol described in S2 is AE500, the dosage is 0.01 mol, and the added end-capping agent is IH or IF, the added dosage is 0.19 mol.

[0164] The reaction described in S2 is carried out at a temperature of 50° C. and a reaction time of 24-48 hours. The reaction is stopped after the disappearance of the isocyanate group NCO is detected.

[0165] The solvent in S2 is EOEOEA, and the added amount is 25%wt of the entire reaction system.

[0166] Preparation Example 9 (Based on Preparation Example 7) Preparation of hyperbranched polyurethane acrylate UV light-cured resin:

[0167] S1, preparing a capping agent;

[0168] S2, the end-capping agent reacts with the hyperbranched polyol to generate a hyperbranched polyurethane acrylate UV light-curing resin;

[0169] The capping agent includes IH shown in structural formula V or IF shown in structural formula VI.

[0170] The preparation of the end-capping agent described in S1 specifically includes: mixing IPDI and the catalyst under an argon atmosphere, adding the end-capping agent HEA or the end-capping agent FM1D, and reacting to obtain the end-capping agent IH or the end-capping agent IF.

[0171] The reaction is carried out under stirring conditions.

[0172] The molar ratio of IPDI to the end-capping agent HEA or the end-capping agent FM1D in S1 is 1:1.

[0173] The catalyst described in S1 is a composite catalyst, which includes T-12 catalyst and TEA, the molar ratio of the two is 1:4, and the amount of catalyst used is 200ppm based on the amount of IPDI.

[0174] The reaction described in S1, the reaction temperature is 75°C, and the reaction time is 1h.

[0175] The reaction in step S2 specifically includes: dissolving the IH or IF obtained in step S1 into a solvent under an argon atmosphere, adding a hyperbranched polyol, and reacting by heating to obtain a hyperbranched polyurethane acrylate UV light-curing resin.

[0176] The hyperbranched polyol described in S2 is AE500, the dosage is 0.01 mol, and the added end-capping agent is IH or IF, the added dosage is 0.19 mol.

[0177] The reaction described in S2 is carried out at a temperature of 50° C. and a reaction time of 24-48 hours. The reaction is stopped after the disappearance of the isocyanate group NCO is detected.

[0178] The solvent in S2 is EOEOEA, and the added amount is 25%wt of the entire reaction system.

[0179] Preparation Example 10 (Based on Preparation Example 7) Preparation of hyperbranched polyurethane acrylate UV light-curing resin:

[0180] S1, preparing a capping agent;

[0181] S2, the end-capping agent reacts with the hyperbranched polyol to generate a hyperbranched polyurethane acrylate UV light-curing resin;

[0182] The capping agent includes IH shown in structural formula V or IF shown in structural formula VI.

[0183] The preparation of the end-capping agent described in S1 specifically includes: mixing IPDI and the catalyst under an argon atmosphere, adding the end-capping agent HEA or the end-capping agent FM1D, and reacting to obtain the end-capping agent IH or the end-capping agent IF.

[0184] The reaction is carried out under stirring conditions.

[0185] The molar ratio of IPDI to the end-capping agent HEA or the end-capping agent FM1D in S1 is 1:1.

[0186] The catalyst described in S1 is T-12 catalyst, and the dosage is 200ppm based on the dosage of IPDI.

[0187] The reaction described in S1, the reaction temperature is 30°C, and the reaction time is 3h.

[0188] The reaction in step S2 specifically includes: dissolving the IH or IF obtained in step S1 into a solvent under an argon atmosphere, adding a hyperbranched polyol, and reacting by heating to obtain a hyperbranched polyurethane acrylate UV light-curing resin.

[0189] The hyperbranched polyol described in S2 is AE500, the dosage is 0.01 mol, and the added end-capping agent is IH or IF, the added dosage is 0.19 mol.

[0190] The solvent in S2 is EOEOEA, and the added amount is 25%wt of the entire reaction system.

[0191] The reaction described in S2 is further carried out by adding 1,4-butanediol (BDO) in an amount of 8% of the molar amount of the hyperbranched polyol.

[0192] The reaction in S2 has a reaction temperature of 80° C. and a reaction time of 24-48 hours. The reaction is stopped after the disappearance of the isocyanate group NCO is detected.

[0193] Preparation Example 11 (Based on Preparation Example 7) Preparation of hyperbranched polyurethane acrylate UV light-curing resin:

[0194] S1, preparing a capping agent;

[0195] S2, the end-capping agent reacts with the hyperbranched polyol to generate a hyperbranched polyurethane acrylate UV light-curing resin;

[0196] The capping agent includes IH shown in structural formula V or IF shown in structural formula VI.

[0197] The preparation of the end-capping agent described in S1 specifically includes: mixing IPDI and the catalyst under an argon atmosphere, adding the end-capping agent HEA or the end-capping agent FM1D, and reacting to obtain the end-capping agent IH or the end-capping agent IF.

[0198] The reaction is carried out under stirring conditions.

[0199] The molar ratio of IPDI to the end-capping agent HEA or the end-capping agent FM1D in S1 is 1:1.

[0200] The catalyst described in S1 is T-12 catalyst, and the dosage is 200ppm based on the dosage of IPDI.

[0201] The reaction described in S1, the reaction temperature is 30°C, and the reaction time is 3h.

[0202] The reaction in step S2 specifically includes: dissolving the IH or IF obtained in step S1 into a solvent under an argon atmosphere, adding a hyperbranched polyol, and reacting by heating to obtain a hyperbranched polyurethane acrylate UV light-curing resin.

[0203] The hyperbranched polyol described in S2 is AE500, the dosage is 0.01 mol, and the added end-capping agent is IH or IF, the added dosage is 0.19 mol.

[0204] The solvent in S2 is EOEOEA, and the added amount is 25%wt of the entire reaction system.

[0205] The reaction described in S2 is further carried out by adding 1,4-butanediol (BDO) in an amount of 15% of the molar amount of the hyperbranched polyol.

[0206] The reaction in S2 has a reaction temperature of 80° C. and a reaction time of 24-48 hours. The reaction is stopped after the disappearance of the isocyanate group NCO is detected.

[0207] The synthetic linear PUA oligomer ITH1000 was used as a control and experimental material to test the resin performance.

[0208] The hyperbranched polyurethane acrylate UV light-curing resin obtained in Preparation Examples 1-7 was characterized:

[0209] The FT-IR spectrum of the hyperbranched polyurethane acrylate UV light-cured resin obtained in Preparation Example 1-7 is shown in Figure 2 The characteristic peaks of FT-IR spectrum are shown in Table 1, and the GPC curve is shown in Figure 3 The molecular weight and its distribution are shown in Table 2.

[0210] Table 1 Characteristic peaks of FT-IR spectra of a series of hyperbranched PUAs

[0211]

[0212]

[0213] Table 2 Molecular weight and distribution of hyperbranched PUA and

[0214]

[0215] The above characterization results show that the method of the present invention successfully forms a hyperbranched PUA with the expected structure and molecular weight distribution.

[0216] The performance of the hyperbranched polyurethane acrylate UV light-curing resin obtained in Preparation Example 1-7 was tested:

[0217] The synthesized hyperbranched PUA was mixed evenly with 2 wt % of photoinitiator TPO as shown in Table 3, added into a clean brown glass bottle, placed in a 60° C. vacuum oven for degassing for 30 min, and sealed to obtain a hyperbranched PUA UV-curable resin.

[0218] The prepared flat glass was fixed on a horizontal plane, and the hard plastic plate was fixed on the flat glass. The UV-curable PUA resin was coated on the hard plastic plate with a coating rod with a gap of 0.25 mm. The cured film was placed in a 60°C vacuum oven for leveling for 5 minutes, and then the coating was placed in a UV curing box for UV curing for 2 minutes to obtain a UV-cured film of hyperbranched polyurethane acrylate. The power of the high-pressure mercury lamp used for curing was 2 kW and the wavelength was 365 nm. The obtained cured film was tested for mechanical properties. The test results are shown in Table 4.

[0219] Table 3 UV curing PUA resin formula

[0220]

[0221] The above mechanical properties tests include:

[0222] Pencil hardness test:

[0223] The pencil hardness test was carried out according to standard ASTM D3363, with a pencil load of 750 g and repeated twice.

[0224] Adhesion test:

[0225] The adhesion test was carried out according to the standard ASTM D3359, using method B, i.e. the cross-cut method, with a cutting distance of 1 cm.

[0226] Wear resistance test:

[0227] The wear resistance of UV-cured resin was tested according to the standard ISO7784-1-2016 using a Taber abrasion tester; the loss mass of the cured film after 100 rotations of abrasion at a load of 6N was measured, and the grades were B1-B5 from best to worst.

[0228] Scratch resistance test:

[0229] According to the standard ISO12137:1997, the scratch resistance of the cured film is tested by the pointed stylus method, and the scratch resistance is determined by gradually increasing the load on the stylus. The paint film is broken as the standard, the load range is 1-4kg, and 0.5kg is a variable value.

[0230] Table 4 Surface properties of PUA cured films

[0231]

[0232] Note: The pencil hardness level is H-9H from low to high; the scratch resistance load range is 1-4kg, with 0.5kg as a variable value; the wear resistance test level is B1-B5 from good to bad; the adhesion test level is 5B-0B from good to bad.

[0233] When using the same active diluent, the surface hardness varies with the end-capping agent, according to AE500>

[0234] The order of HE500>FE500. Because AE500 hyperbranched PUA has the smallest molecular weight, in the presence of the same mass fraction of active diluent, AE500 has the largest molar fraction and the highest crosslinking density, providing physical force support for the cured film, so the hardness of the AE500 film is the highest, reaching 8H; after the IF end-capping agent is modified with caprolactone, the molecular chain has higher flexibility and reduces the hardness of the cured film, and the hardness of the FE500 film is only 3H.

[0235] The flexible EOEOEA acts as a plasticizer, which reduces the hardness of the cured film. The surface hardness of FE500 drops from 4H of F500 film to 3H. NVP with a rigid structure and DPHA and TA with high double bond content can significantly improve the surface hardness of PUA cured film. The surface hardness of HN500 reaches 8H, and the hardness of HED500 increases from 4H to 6H.

[0236] High hardness brings excellent scratch resistance to the cured film. The scratch resistance level of the cured film is above 3.5kg. The HN500 and AE500 cured films have exceeded the highest standard of 4kg, which can effectively protect the substrate from scratches.

[0237] The wear resistance of PUA cured film is relatively poor, because excellent wear resistance requires not only high hardness but also excellent toughness of the cured film. The wear resistance of high-hardness AE500 film, HN500 film and high-flexibility FN500 film is improved compared with other cured films, but still cannot meet the requirements for high wear-resistant samples. In terms of active diluents, the use of EOEOEA reduces the hardness of the cured film, while the use of NVP reduces the flexibility of the cured film. If you want to further improve the wear resistance of the film, you can use EOEOEA and NVP in combination.

[0238] Hyperbranched PUAs all have a high content of strongly polar group urethane bonds, so hyperbranched PUA cured films can be tightly bonded to the substrate, and the adhesion level reaches the highest 5B level.

[0239] Based on the above preparation examples, the present invention provides an optimized UV light-curing coating formula, which is as follows:

[0240] Example Application of hyperbranched polyurethane acrylate resin in UV light curing coating

[0241] The hyperbranched polyurethane acrylate resin prepared in the above preparation example was used to prepare a UV light-curing coating according to the formulation in Table 5, and the photoinitiator shown in Table 5 was used.

[0242] Table 5 Example hyperbranched polyurethane acrylate resin UV light curing coating formula

[0243]

[0244]

[0245] Performance test: According to the formula shown in Table 5, the coating components including the photoinitiator were mixed evenly and added into a clean brown glass bottle, placed in a 60°C vacuum oven for degassing for 30 minutes, and sealed for storage to obtain a hyperbranched PUA UV-curable resin.

[0246] The prepared flat glass was fixed on a horizontal plane, and the hard plastic plate was fixed on the flat glass. The UV-curable PUA resin was coated on the hard plastic plate with a coating rod with a gap of 0.25 mm. The cured film was placed in a 60°C vacuum oven for leveling for 5 minutes, and then the coating was placed in a UV curing box for UV curing for 2 minutes to obtain a UV-cured film of hyperbranched polyurethane acrylate. The power of the high-pressure mercury lamp used for curing was 2 kW and the wavelength was 365 nm. The obtained cured film was tested for mechanical properties. The test results are shown in Table 6.

[0247] Table 6 Surface properties of cured films prepared from the coating obtained in Example

[0248]

[0249]

[0250] The optimized coating formula can be applied to the various core resins provided by the present invention. The performance parameters of the obtained cured film are comprehensively improved, and the key performance parameters are stable for different formula ratios. The pencil hardness can be stabilized at 7H-8H, the scratch resistance level is above 3.9kg, and most of them are stable at above 4kg, the highest standard. The wear resistance is the parameter that has been most optimized, which is stable at B7-B8, and the adhesion level reaches 5B.

[0251] It can be seen that by adopting the optimized coating formula provided by the present invention in combination with the hyperbranched polyurethane acrylate resin of Xinhecheng, a UV light-curing coating containing a hyperbranched polyurethane acrylate resin with improved mechanical properties in all aspects is obtained.

[0252] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

[0253] The present invention and its implementation methods are described above, which is not restrictive. The drawings are only one of the implementation methods of the present invention, and the actual application is not limited thereto. In short, if ordinary technicians in the field are inspired by it and design methods and embodiments similar to the technical solution without creativity without departing from the purpose of the invention, they should all fall within the protection scope of the present invention.

Claims

1. Application of a hyperbranched polyurethane acrylate resin in UV light-curing coatings, characterized in that: The coating comprises the following components: hyperbranched polyurethane acrylate resin, DPHA, TA, HDDA, TMPTA, photoinitiator TPO and photoinitiator PETA.

2. The use of the hyperbranched polyurethane acrylate resin in UV light-curing coating according to claim 1, characterized in that: The components in the coating include, by weight, 100-150 parts of hyperbranched polyurethane acrylate resin, 50-80 parts of DPHA, 30-60 parts of TA, 20-40 parts of HDDA, 10-30 parts of TMPTA, 5-8 parts of photoinitiator TPO, and 10-15 parts of photoinitiator PETA.

3. The use of the hyperbranched polyurethane acrylate resin in UV light-curing coating according to claim 1, characterized in that: The structure of the hyperbranched polyurethane acrylate resin is shown in structural formula I: Structural formula Ⅰ Wherein, R' represents polydipentaerythritol, and the structure of R is one or more of the following structural formulas II, III, and IV: Structural formula Ⅱ Structural formula Ⅲ Structural formula IV.

4. The use of the hyperbranched polyurethane acrylate resin in UV light-curing coating according to claim 1, characterized in that: The preparation method of the hyperbranched polyurethane acrylate resin comprises the following steps: S1, preparing a capping agent; S2, the end-capping agent reacts with the hyperbranched polyester polyol to generate a hyperbranched polyurethane acrylate UV light-curing resin; The end-capping agent includes IH shown in structural formula V or IF shown in structural formula VI or ethyl isocyanate acrylate: Structure V Structural formula VI.

5. The use of the hyperbranched polyurethane acrylate resin in UV light curing coating according to claim 4, characterized in that: The preparation of the end-capping agent described in S1 specifically includes: mixing IPDI and the catalyst under an argon atmosphere, adding the end-capping agent HEA or the end-capping agent FM1D, and reacting to obtain the end-capping agent IH or the end-capping agent IF.

6. The use of the hyperbranched polyurethane acrylate resin in UV light curing coating according to claim 5, characterized in that: The molar ratio of IPDI to the end-capping agent HEA or the end-capping agent FM1D in S1 is 1:(1-1.2).

7. The use of the hyperbranched polyurethane acrylate resin in UV light curing coating according to claim 5, characterized in that: The catalyst in S1 is T-12 catalyst, and the dosage is 200-500ppm based on IPDI; the reaction in S1 has a reaction temperature of 30-75°C and a reaction time of 3-4h.

8. The use of the hyperbranched polyurethane acrylate resin in UV light curing coating according to claim 4, characterized in that: The reaction described in S2 specifically includes: dissolving the IH or IF obtained in step S1 into a solvent under an argon atmosphere, adding a hyperbranched polyester polyol, and heating the reaction to obtain a hyperbranched polyurethane acrylate UV light-curing resin, and the amount of the hyperbranched polyester polyol described in S2 is equivalent to the added IH or IF.

9. The use of the hyperbranched polyurethane acrylate resin in UV light curing coating according to claim 4, characterized in that: The reaction in S2 has a reaction temperature of 30-100° C. and a reaction time of 24-48 hours. The reaction in S2 is stopped after the disappearance of the isocyanate group NCO is detected.

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