High-strength flexible UV-cured organic silicon resin composition and preparation method thereof

Abstract

The invention relates to a high-strength flexible UV-cured organic silicon resin composition which comprises the following components in parts by weight: 20-100 parts of double-end-capped active functional group modified linear polysiloxane; 10-100 parts by weight of a modified linear siloxane oligomer containing an active functional group on the end side; 0.1 to 10 parts by weight of an unsaturated group silane oligomer; 10 to 70 parts by weight of hyperbranched MTQ type polysiloxane; and 0.1 to 10 parts by weight of a photoinitiator. According to the invention, through molecular structure design, the ratio of the components is regulated and controlled, and the UV-curable organic silicon resin composition with high strength and flexibility is prepared. The organic silicon resin composition has excellent solvent resistance, heat resistance, weather resistance and water repellency, can be applied to the fields of leather, glass screen printing and the like as an external coating, endows materials with surface textures, and enhances the surface touch, strength and wear resistance of the materials.

Description

Technical Field

[0001] The present invention relates to a silicone resin composition, and in particular to a high-strength flexible UV-cured silicone resin composition and a preparation method thereof, which can be used as an external coating in the fields of leather, glass silk-screen printing, etc., to impart texture to the surface of the material, and enhance the touch, strength and wear resistance of the surface of the material. Background Art

[0002] The patterns printed on the surface of glass products currently available on the market with organic silicone coatings have elastic and skin-friendly touch, which can prevent the glass from breaking and shattering, and have a good grip. However, the strength of the patterns printed on this organic silicone coating is low, and it is easy to be damaged by scratching with nails, and the process is usually heated and cured, which is time-consuming, energy-consuming and not environmentally friendly. Most of the products that can achieve UV light curing on the market are high-hardness coatings, which cannot meet the requirements for product flexibility and strength in the field of glass products and leather coatings. The present invention relates to a high-strength flexible UV-curable organic silicone resin composition, which can achieve light curing, take into account the properties of high resilience, high strength and high adhesion to glass substrates, and can effectively solve the existing problems on the market.

[0003] The Chinese patent, entitled "UV-curable silicone composition, preparation method and application thereof", with patent number CN 113025052A, discloses a UV-curable silicone composition, its preparation method and its application. The UV-curable silicone composition comprises, by weight, 100 parts of DT silicone resin having at least one UV-active functional group and 50-200 parts of MD silicone oil having UV-active functional groups at both ends. It has small volume shrinkage and resistance to high and low temperature impact, but high hardness and cannot meet the application fields requiring material flexibility.

[0004] The Chinese patent, entitled "An Organic Silicone Composition for UV Curing" and numbered CN 104610696 A, relates to an organic silicone composition for UV curing, which is composed of the following raw materials in parts by weight: 100 parts of polysiloxane with UV-active functional groups at both ends, 10-30 parts of organic silicone resin with UV-active functional groups, 5-10 parts of organic silicone oligomer with UV activity, and 0.1-10 parts of free radical photoinitiator. The present invention provides an organic silicone composition for UV curing, which has excellent mechanical properties, safety and environmental protection, high transparency, high strength and low shrinkage, and can be used in the fields of optical devices and electronic packaging, but its high hardness and low elasticity limit the application of the product to a great extent.

[0005] The patent is called "A UV Curing Silicone Sealant" and the patent number is CN 115820206 A. This patent relates to a UV curing silicone sealant, which belongs to the field of adhesive technology. The UV curing silicone sealant includes the following components by weight: 15-30 parts of modified silicone resin, 10-20 parts of modified UV curing crosslinker, 25-45 parts of silicone chain extender, 15-35 parts of silicone crosslinker, 1-5 parts of silicone adhesion promoter, and 8-18 parts of modified photoinitiator. The obtained UV curing silicone sealant can be quickly UV cured, has high transparency, and has excellent properties such as aging resistance and UV resistance. However, the material is soft, low in strength, and the tensile strength does not exceed 1MPa, which brings inconvenience to its application. Summary of the invention

[0006] In order to expand the application of materials in the fields of leather, glass silk-screen printing, etc. and to meet the diversified market demand for glass products, the present invention provides a UV-curable, high-strength, flexible silicone resin composition and a preparation method thereof, which imparts texture to the surface of the material and enhances the touch, strength and wear resistance of the surface of the material.

[0007] To achieve the above object, the inventors provide a high-strength flexible UV-curable silicone resin composition, which comprises the following components in parts by weight:

[0008]

[0009] The structure of the double-terminated active functional group-modified linear polysiloxane is shown in Formula 1:

[0010]

[0011] In Formula 1, R1 is an alkyl group having a carbon number of C1-C4;

[0012] R2 includes one or two of the following groups: one of methyl, ethyl, methoxy, ethoxy, propoxy, butoxy; a is an integer of 100-10000;

[0013] R3 includes one of the following groups: 2,3-epoxypropyloxymethyl, 2,3-epoxypropyloxyethyl, 2,3-epoxypropyloxypropyl, vinyl, vinyl ether, propenyl, acryloxy, methacryloxy, methacryloxymethyl, methacryloxyethyl, methacryloxypropyl;

[0014] The structure of the terminal-side modified linear siloxane oligomer containing active functional groups is shown in Formula 2:

[0015]

[0016] In Formula 2, R4 includes one of the following groups: 2,3-epoxypropyloxymethyl, 2,3-epoxypropyloxyethyl, 2,3-epoxypropyloxypropyl, vinyl, vinyl ether, propenyl, acryloxy, methacryloxy, methacryloxymethyl, methacryloxyethyl, methacryloxypropyl, mercapto, mercaptomethyl, mercaptoethyl, mercaptopropyl;

[0017] R5 includes one or two of the following groups: methyl, ethyl, methoxy, ethoxy, propoxy, butoxy;

[0018] R6 includes one or two of the following groups: 2,3-epoxypropyloxymethyl, 2,3-epoxypropyloxyethyl, 2,3-epoxypropyloxypropyl, vinyl, vinyl ether, propenyl, acryloxy, methacryloyloxy, methacryloyloxymethyl, methacryloyloxyethyl, methacryloyloxypropyl, methyl, ethyl, methoxy, ethoxy, propoxy, butoxy, mercapto, mercaptomethyl, mercaptoethyl, mercaptopropyl;

[0019] R7 includes one or two of the following groups: hydroxy, methoxy, ethoxy, propoxy, butoxy;

[0020] b and c are integers from 0 to 25 respectively;

[0021] The structural formula of the unsaturated silane oligomer is shown in Formula 3:

[0022]

[0023] In Formula 3, R8 includes one of the following groups: acryloyloxymethyl, acryloyloxyethyl, acryloyloxypropyl, methacryloyloxymethyl, methacryloyloxyethyl, methacryloyloxypropyl, vinyl, and acryl;

[0024] R9 includes one or two of the following groups: hydroxyl, methoxy, ethoxy, propoxy, butoxy, dimethyl ketoxime, methyl ethyl ketoxime, acetoxy, isopropenyloxy, isobutenyloxy, N-butylamino, N,N-diethylamino, N-methylacetamide; e is a positive integer less than or equal to 10;

[0025] The structural formula of the hyperbranched MTQ polysiloxane is shown in Formula 4:

[0026]

[0027] In formula 4, R 10 Includes one or more of the following groups: alkyl, vinyl, and silyl groups having carbon numbers of C1-C4;

[0028] R 11Including one of the following groups: 2,3-epoxypropyloxymethyl, 2,3-epoxypropyloxyethyl, 2,3-epoxypropyloxypropyl, acryloyloxymethyl, acryloyloxyethyl, acryloyloxypropyl, methacryloyloxymethyl, methacryloyloxyethyl, methacryloyloxypropyl, mercapto, mercaptomethyl, mercaptoethyl, mercaptopropyl, silyl;

[0029] f and h are respectively positive integers of 0-50. Further, f and h are respectively positive integers of 5-25.

[0030] The present invention adopts a design method for compounding a double-terminated active functional group-modified linear polysiloxane, a terminal-side active functional group-modified linear siloxane oligomer, and a hyperbranched MTQ-type polysiloxane to solve the performance defects of UV-curing organic silicon materials. On the one hand, in the designed structure, the functionality of the terminal-side active functional group-modified linear siloxane oligomer is ≥3, and the hyperbranched MTQ-type polysiloxane is a branched network structure, which improves the overall cross-linking density of the material, makes it have high film strength, and is more scratch-resistant; on the other hand, the introduced double-terminated active functional group-modified linear polysiloxane component is a macromolecular linear polysiloxane, which makes the prepared material have high flexibility, improves the softness and texture of the material, thereby solving the defects of high hardness and low strength of existing light-curing organic silicon materials and broadening the application field of the material.

[0031] Preferably, the high-strength flexible UV-curable silicone resin composition comprises the following components in parts by weight:

[0032]

[0033] By using the above weight proportion combination, the dosage of the double-terminated active functional group modified linear polysiloxane component, the hyperbranched MTQ type polysiloxane component, and the end-side active functional group modified linear siloxane oligomer component is appropriately adjusted to balance the flexibility, hardness and strength properties of the prepared material.

[0034] Preferably, the photoinitiator includes one or a mixture of two or more of the following: 2-hydroxy-2-methyl-1-phenylpropanone, 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio)phenyl]-1-propanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, diaryl iodonium salts, triaryl iodonium salts, alkyl iodonium salts, and isopropylferrocenium hexafluorophosphate.

[0035] Preferably, the double-terminated reactive functional group-modified linear polysiloxane is prepared by the following preparation method, which comprises the following steps:

[0036] At 25-45° C., adding the first functional silane monomer and silicone rubber with a viscosity greater than or equal to 10000 cp into a reaction kettle, adding an alkaline catalyst, heating to 80° C. for 2 hours, then heating to 140° C. for 2 hours under vacuum, to obtain the double-terminated active functional group-modified linear polysiloxane;

[0037] The weight parts of each component are as follows:

[0038] Silicone rubber 95-100 parts by weight;

[0039] 0.1-5 parts by weight of the first functional silane monomer;

[0040] Basic catalyst 0.1-2 parts by weight;

[0041] The molecular formula of the first functional silane monomer is shown in Formula 5:

[0042]

[0043] In Formula 5, R2 includes one or two of the following groups: methyl, ethyl, methoxy, ethoxy, propoxy, butoxy;

[0044] R3 includes one of the following groups: 2,3-epoxypropyloxymethyl, 2,3-epoxypropyloxyethyl, 2,3-epoxypropyloxypropyl, vinyl, vinyl ether, propenyl, acryloxy, methacryloxy, methacryloxymethyl, methacryloxyethyl, methacryloxypropyl;

[0045] Preferably, the first functional silane monomer includes one of the following: methacryloxypropyltrimethoxysilane, methacryloxypropylmethyldimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, etc.

[0046] The alkaline catalyst includes one of the following: tetramethylammonium hydroxide, tri-n-propylamine, dipropylamine, n-butylamine, tri-n-butylamine.

[0047] Preferably, the silicone rubber is 107 silicone rubber.

[0048] The present invention uses the high molecular weight double-terminated active functional group modified linear polysiloxane polymer to greatly improve the strength and softness of the prepared material. If the double-terminated active functional group modified linear polysiloxane component is not added to the material, the surface hardness of the prepared material is relatively large after curing, and it is easy to crack when bent.

[0049] Preferably, the terminal-side modified linear siloxane oligomer containing active functional groups is prepared by the following preparation method, which comprises the following steps:

[0050] First, two or more second functional silane monomers, organic alcohol A, and acidic ion exchange resin are added to a reaction kettle. At 30-50° C., water and another portion of organic alcohol A are mixed in a mass ratio of 1:2 and then added dropwise to the reaction kettle. After the addition is completed, the mixture is kept warm and stirred for 1 hour. Then, the mixture is heated to reflux temperature, reacted at reflux temperature for 3 hours, the ion exchange resin is removed by filtration, and the solvent is removed by distillation to obtain the linear siloxane oligomer modified with active functional groups at the end side.

[0051] The molecular formula of the second functional silane monomer is shown in Formula 6 or Formula 7 below:

[0052]

[0053] In Formula 6, R4 includes one of the following groups: 2,3-epoxypropyloxymethyl, 2,3-epoxypropyloxyethyl, 2,3-epoxypropyloxypropyl, vinyl, vinyl ether, propenyl, acryloxy, methacryloxy, methacryloxymethyl, methacryloxyethyl, methacryloxypropyl, mercapto, mercaptomethyl, mercaptoethyl, mercaptopropyl;

[0054] In Formula 6 or Formula 7, R5 includes one or two of the following groups: methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, butoxy;

[0055] R6 includes one of the following groups: methyl, ethyl, propyl, butyl;

[0056] The organic alcohol A includes one of the following: methanol, ethanol, propanol, and butanol.

[0057] Preferably, the second functional silane monomer shown in Formula 6 includes one of the following: methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, glycidyloxypropyltrimethoxysilane, mercaptopropyltrimethoxysilane, methacryloxypropylmethyldimethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, mercaptopropylmethyldimethoxysilane, mercaptopropylmethyldiethoxysilane.

[0058] Preferably, the second functional silane monomer represented by Formula 7 includes one of the following: dimethyldimethoxysilane, dimethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, propyltrimethoxysilane, methylpropyldimethoxysilane.

[0059] Wherein, the weight parts of each component are as follows:

[0060]

[0061] During the reaction, one or more second functional silane monomers represented by Formula 6 and one or more second functional silane monomers represented by Formula 7 are added.

[0062] The invention introduces a terminal-side modified linear siloxane oligomer containing active functional groups, which helps to increase the crosslinking density of the prepared material and improve the strength of the material; at the same time, it can also reduce the system viscosity of the material and facilitate the material construction operation.

[0063] Preferably, the unsaturated silane oligomer is prepared by the following preparation method, which comprises the following steps:

[0064] Preparation of unsaturated silane oligomer: add water and unsaturated silane into a reaction kettle at 30-50°C, keep warm and stir for 1 hour, then heat to 70°C, keep warm and react for 3 hours, and cool down after the reaction to obtain the unsaturated silane oligomer;

[0065] The unsaturated silane is shown in Formula 8:

[0066]

[0067] In Formula 8, R8 includes one of the following groups: acryloyloxymethyl, acryloyloxyethyl, acryloyloxypropyl, methacryloyloxymethyl, methacryloyloxyethyl, methacryloyloxypropyl, vinyl, and acryl;

[0068] R 12 Include one or two of the following groups: methoxy, ethoxy, propoxy, butoxy, dimethyl ketoxime, methyl ethyl ketoxime, acetoxy, isopropenyloxy, isobutenyloxy, N-butylamino, N,N-diethylamino, N-methylacetamide;

[0069] Wherein, the weight parts of each component are as follows:

[0070] Unsaturated silane 70-99 parts;

[0071] 3.5-5 parts water.

[0072] Preferably, the unsaturated silane includes one of the following: methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, methacryloxypropyltriethoxysilane, vinyltriethoxysilane.

[0073] The present invention introduces unsaturated silane oligomers so that the material can be quickly attached and bonded to the surface of the substrate during construction.

[0074] Preferably, the hyperbranched MTQ polysiloxane is prepared by the following preparation method, which comprises the following steps:

[0075] At 30-50° C., two or more third functional silane monomers are added dropwise to a reaction kettle containing a 5% hydrochloric acid aqueous solution and toluene. After the addition is completed, the mixture is kept warm and stirred for 1 hour, then heated to reflux temperature, kept at reflux temperature for 3 hours, cooled and allowed to stand for stratification, the upper layer is removed, and the solvent is removed from the lower layer by distillation to obtain the hyperbranched MTQ polysiloxane;

[0076] The molecular formula of the functional silane monomer is shown in Formula 9, Formula 10 or Formula 11:

[0077]

[0078] Wherein, R5 includes one or two of the following groups: methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, butoxy;

[0079] R 10 Includes one or more of the following groups: alkyl, vinyl, and silyl groups having carbon numbers of C1-C4;

[0080] R 11 Including one of the following groups: 2,3-epoxypropyloxymethyl, 2,3-epoxypropyloxyethyl, 2,3-epoxypropyloxypropyl, vinyl, propenyl, acryloxymethyl, acryloxyethyl, acryloxypropyl, methacryloxymethyl, methacryloxyethyl, methacryloxypropyl, mercapto, mercaptomethyl, mercaptoethyl, mercaptopropyl, silyl;

[0081] Wherein, the weight parts of each component are as follows:

[0082]

[0083]

[0084] During the reaction, one or more third functional silane monomers shown in formula 10 are added, and one or more third functional silane monomers shown in formula 11 are added; the input amount of the third functional silane monomer shown in formula 9 can be 0 or not 0. When the input amount of the third functional silane monomer shown in formula 9 is not 0, one or more third functional silane monomers shown in formula 9 are added.

[0085] Preferably, the third functional silane monomer represented by Formula 9 includes one of the following: mercaptopropyl trimethoxysilane, methacryloxypropyl trimethoxysilane, vinyl trimethoxysilane, glycidyloxypropyl trimethoxysilane.

[0086] Preferably, the third functional silane monomer represented by formula 10 includes one of the following: hexamethyldisiloxane, tetramethyldivinyldisiloxane, and tetramethyldihydrogendisiloxane.

[0087] Preferably, the third functional silane monomer represented by Formula 11 includes one of the following: methyl orthosilicate and ethyl orthosilicate.

[0088] The invention introduces hyperbranched MTQ type polysiloxane to further improve the strength of the material, so that the prepared material is scratch-resistant and not easy to be damaged.

[0089] The present invention also discloses a method for preparing the high-strength flexible UV-curable silicone resin composition, which comprises the following steps:

[0090] At room temperature, double-terminated active functional group-modified linear polysiloxane, end-side active functional group-modified linear siloxane oligomer, unsaturated silane oligomer, hyperbranched MTQ polysiloxane, and photoinitiator are added to a reaction kettle in parts by weight, the reaction mixture is evacuated to -0.08 MPa, and stirred for 0.5 h to obtain the high-strength flexible UV-curable silicone resin composition.

[0091] The present invention adopts the preparation method, which has simple process, convenient operation and is convenient for industrial production.

[0092] The present invention also discloses an application method of the high-strength flexible UV-curable silicone resin composition, which is:

[0093] At room temperature, the high-strength flexible UV-curable silicone resin composition or the high-strength flexible UV-curable silicone resin composition and the UV-curable resin are mixed uniformly in a mass ratio of 1:0.1-10, wherein the UV-curable resin includes an acrylic resin or an epoxy resin, and then the high-strength flexible UV-curable silicone resin composition is uniformly coated on the surface of the substrate by a roller coater, and a mold with a special texture is pressed on the surface, and the coating thickness does not exceed 1 mm. After irradiation with a 365nm ultraviolet lamp, the UV energy is 1000-1200mJ / cm 2 , curing, demoulding, and obtaining the product.

[0094] The invention also discloses a product prepared from the high-strength flexible UV-cured silicone resin composition, which is prepared by the application method.

[0095] The beneficial effects of the present invention are:

[0096] The present invention prepares a high-strength, flexible, UV-curable silicone resin composition by molecular structure design and control of the proportion of each component. The silicone resin composition has excellent solvent resistance, heat resistance, weather resistance and water repellency, and can be used as an external coating in the fields of leather, glass silk printing, etc., to give the material surface texture, enhance the material surface touch, strength and wear resistance. DETAILED DESCRIPTION

[0097] In order to explain the technical content, structural features, achieved objectives and effects of the technical solution in detail, the following is a detailed description in conjunction with specific embodiments.

[0098] Example 1

[0099] Step 1: Preparation of double-terminated active functional group modified linear polysiloxane. At 25-45°C, accurately weigh 1000g of 50000cp107 silicone rubber, 10g of methacryloxypropyltrimethoxysilane, and 2g of tetramethylammonium hydroxide, and put them into the reaction kettle in sequence, keep the temperature at 80°C for 2h, heat it to 140°C, keep it in vacuum at -0.08mpa for 2h, and then cool it down to obtain double-terminated active functional group modified linear polysiloxane.

[0100] Step 2: Preparation of terminal-side modified linear siloxane oligomers containing active functional groups. Accurately weigh 200 g of methyltrimethoxysilane, 500 g of dimethyldimethoxysilane, 100 g of methacryloxypropyltrimethoxysilane, 200 g of methacryloxypropylmethyldimethoxysilane, 200 g of methanol, and 50 g of ion exchange resin, and sequentially put them into the reaction. At 30-50° C., 360 g of a mixture of water and methanol in a mass ratio of 1:2 is added dropwise. After the addition is completed, stirring is continued for 1 hour, heated to 70° C., refluxed for 3 hours, the ion exchange resin is filtered to remove the ion exchange resin, and the methanol solvent is distilled to obtain the terminal-side modified linear siloxane oligomers containing active functional groups.

[0101] Step 3: Preparation of hyperbranched MTQ polysiloxane. Accurately weigh 936g of ethyl orthosilicate, 124g of methacryloyloxypropyltrimethoxysilane, and 324g of hexamethyldisiloxane, mix them evenly, and drop them into a reactor containing 350g of 5% hydrochloric acid aqueous solution and 450g of toluene. After the dropwise addition is completed, continue stirring for 1h, heat to 80°C, reflux for 3h, cool and stand for stratification, remove the upper layer, and distill the lower layer to remove the solvent to obtain the hyperbranched MTQ polysiloxane.

[0102] Step 4: Preparation of unsaturated silane oligomers. Accurately weigh 90 g of methacryloxypropyltrimethoxysilane and 5 g of water, add them into the reaction kettle in sequence, stir at 40° C. for one hour, heat to 70° C., keep warm for 3 hours, and cool to obtain the unsaturated silane oligomers.

[0103] Step 5: Preparation of high-strength flexible UV-curable silicone resin composition. Accurately weigh 400 g of double-terminated active functional group-modified linear polysiloxane, 220 g of end-side active functional group-modified linear siloxane oligomer, 350 g of hyperbranched MTQ polysiloxane, 20 g of unsaturated silane oligomer, and 10 g of photoinitiator 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio)phenyl]-1-propanone, and add them to the reaction kettle in sequence, evacuate to -0.08 MPa, and stir at medium speed for 0.5 h to obtain the high-strength flexible UV-curable silicone resin composition.

[0104] Example 2

[0105] Example 2 is basically the same as Example 1, except that in the preparation step of the high-strength flexible UV-curable silicone resin composition, by weight, 75 parts by weight of a double-terminated active functional group-modified linear polysiloxane, 75 parts of a terminal side-containing active functional group-modified linear siloxane oligomer, 30 parts of a hyperbranched MTQ-type polysiloxane, 1 part of an unsaturated silane oligomer, and 1 part of 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio)phenyl]-1-propanone are added sequentially to a reaction bottle, evacuated to -0.08 MPa, and stirred at medium speed for 0.5 h to obtain the high-strength flexible UV-curable silicone resin composition.

[0106] Example 3

[0107] Example 3 is basically the same as Example 1, except that in the preparation step of the high-strength flexible UV-curable silicone resin composition, by weight, 40 parts by weight of a double-terminated active functional group-modified linear polysiloxane, 22 parts of a terminal side-containing active functional group-modified linear siloxane oligomer, 35 parts of a hyperbranched MTQ-type polysiloxane, and 1 part of 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio)phenyl]-1-propanone are added sequentially to a reaction bottle, evacuated to -0.08 MPa, and stirred at medium speed for 0.5 h to obtain the high-strength flexible UV-curable silicone resin composition.

[0108] Example 4

[0109] Step 1: Preparation of double-terminated active functional group modified linear polysiloxane. At 25-45°C, accurately weigh 1000g of 20000cp107 silicone rubber, 10g of vinyltrimethoxysilane, and 1g of tri-n-propylamine, and put them into the reaction kettle in sequence, keep the temperature at 80°C for 2h, heat it to 140°C, keep it in vacuum at -0.08mpa for 2h, and then cool it down to obtain double-terminated active functional group modified linear polysiloxane.

[0110] Step 2: Preparation of terminal-side modified linear siloxane oligomers containing active functional groups. Accurately weigh 100 g of methyltrimethoxysilane, 600 g of dimethyldimethoxysilane, 80 g of vinyltrimethoxysilane, 150 g of vinylmethyldimethoxysilane, 200 g of methanol, and 50 g of ion exchange resin, and sequentially put them into the reaction. At 30 to 50° C., add 360 g of a mixture of water and methanol in a mass ratio of 1:2, and continue stirring for 1 hour after the addition is completed. Heat to 70° C., reflux for 3 hours, filter to remove the ion exchange resin, and distill to remove the methanol solvent to obtain the terminal-side modified linear siloxane oligomer containing active functional groups.

[0111] Step 3: Preparation of hyperbranched MTQ polysiloxane. Accurately weigh 936g of ethyl orthosilicate, 100g of mercaptopropyltrimethoxysilane, and 324g of hexamethyldisiloxane, mix them evenly, and drop them into a reactor containing 350g of 5% hydrochloric acid aqueous solution and 450g of toluene. After the dropwise addition is completed, stir continuously for 1h, heat to 80°C, reflux for 3h, cool and stand for stratification, remove the upper layer, and distill the lower layer to remove the solvent to obtain the hyperbranched MTQ polysiloxane.

[0112] Step 4: Preparation of unsaturated silane oligomers. Accurately weigh 90 g of methacryloxypropyltriethoxysilane and 5 g of water, add them into the reaction kettle in sequence, stir at 50° C. for one hour, heat to 70° C., keep warm for 3 hours, and cool to obtain the unsaturated silane oligomers.

[0113] Step 5: Preparation of high-strength flexible UV-curable silicone resin composition. Accurately weigh 400g of double-terminated active functional group-modified linear polysiloxane, 220g of end-side active functional group-modified linear siloxane oligomer, 350g of hyperbranched MTQ-type polysiloxane, 20g of unsaturated silane oligomer, 5g of photoinitiator 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and 5g of diphenyliodonium hexafluorophosphate, and add them to the reaction kettle in sequence, evacuate to -0.08MPa, and stir at medium speed for 0.5h to obtain the high-strength flexible UV-curable silicone resin composition.

[0114] Example 5

[0115] Example 5 is basically the same as Example 4, except that in the preparation step of the high-strength flexible UV-curable silicone resin composition, by weight, 75 parts by weight of a double-terminated active functional group-modified linear polysiloxane, 75 parts of a terminal side-containing active functional group-modified linear siloxane oligomer, 30 parts of a hyperbranched MTQ-type polysiloxane, 1 part of an unsaturated silane oligomer, 1 part of 2-hydroxy-2-methyl-1-phenylpropanone, and 1 part of diphenyliodonium hexafluorophosphate are added sequentially to a reaction bottle, evacuated to -0.08 MPa, and stirred at medium speed for 0.5 h to obtain the high-strength flexible UV-curable silicone resin composition.

[0116] Example 6

[0117] Example 6 is basically the same as Example 4, except that in the preparation step of the high-strength flexible UV-curable silicone resin composition, 30 parts by weight of double-terminated active functional group-modified linear polysiloxane, 30 parts of end-side active functional group-modified linear siloxane oligomers, 60 parts of hyperbranched MTQ-type polysiloxane, 2 parts of unsaturated silane oligomers, 1 part of 2-hydroxy-2-methyl-1-phenylacetone, and 1 part of diphenyliodonium hexafluorophosphate are added to the reaction bottle in sequence, evacuated to -0.08 MPa, and stirred at medium speed for 0.5 h to obtain the high-strength flexible UV-curable silicone resin composition.

[0118] Example 7

[0119] Step 1: Preparation of double-terminated active functional group modified linear polysiloxane. At 25-45°C, accurately weigh 950g of 20000cp107 silicone rubber, 50g of vinylmethyldimethoxysilane, and 2g of n-butylamine, and put them into the reaction kettle in sequence, keep the temperature at 80°C for 2h, heat it to 140°C, keep it at -0.08mpa vacuum for 2h, and then cool it down to obtain double-terminated active functional group modified linear polysiloxane.

[0120] Step 2: Preparation of terminal-side modified linear siloxane oligomers containing active functional groups. Accurately weigh 800 g of dimethyldimethoxysilane, 80 g of mercaptopropyltrimethoxysilane, 160 g of mercaptopropylmethyldimethoxysilane, 200 g of methanol, and 50 g of ion exchange resin, and sequentially put them into the reaction. At 30-50°C, add 400 g of a mixture of water and methanol in a mass ratio of 1:2, and continue stirring for 1 hour after the addition is completed. Heat to 70°C, reflux for 3 hours, filter to remove the ion exchange resin, and distill to remove the methanol solvent to obtain the terminal-side modified linear siloxane oligomer containing active functional groups.

[0121] Step 3: Preparation of hyperbranched MTQ polysiloxane. Accurately weigh 1080 g of tetraethyl orthosilicate, 80 g of tetramethyldivinyldisiloxane, 274 g of hexamethyldisiloxane, and 70 g of glycidyloxypropyltrimethoxysilane, mix them evenly, and drop them into a reactor containing 350 g of 5% hydrochloric acid aqueous solution and 450 g of toluene. After the dropwise addition is completed, stir continuously for 1 h, heat to 80° C., reflux for 3 h, cool and stand for stratification, remove the upper layer, and distill the lower layer to remove the solvent to obtain the hyperbranched MTQ polysiloxane.

[0122] Step 4: Preparation of unsaturated silane oligomers: 70 g of vinyltrimethoxysilane and 3.5 g of water were accurately weighed and added to a reaction kettle in sequence, stirred at 30° C. for one hour, heated to 70° C., kept warm for 3 hours, and cooled to obtain the unsaturated silane oligomers.

[0123] Step 5: Preparation of high-strength flexible UV-curable silicone resin composition. Accurately weigh 400 g of double-terminated active functional group-modified linear polysiloxane, 220 g of end-side active functional group-modified linear siloxane oligomer, 350 g of hyperbranched MTQ polysiloxane, 20 g of unsaturated silane oligomer, and 10 g of photoinitiator diaryl iodonium salt, and add them to the reaction kettle in sequence, evacuate to -0.08 MPa, and stir at medium speed for 0.5 h to obtain the high-strength flexible UV-curable silicone resin composition.

[0124] Example 8

[0125] Example 8 is basically the same as Example 7, except that in the preparation step of the high-strength flexible UV-curable silicone resin composition, by weight, 100 parts by weight of a double-terminated active functional group-modified linear polysiloxane, 100 parts of a terminal side-containing active functional group-modified linear siloxane oligomer, 30 parts of a hyperbranched MTQ polysiloxane, 1 part of an unsaturated silane oligomer, and 2 parts of 2-hydroxy-2-methyl-1-phenylpropanone are added sequentially to a reaction bottle, evacuated to -0.08 MPa, and stirred at medium speed for 0.5 h to obtain the high-strength flexible UV-curable silicone resin composition.

[0126] Example 9

[0127] Example 9 is basically the same as Example 7, except that in the preparation step of the high-strength flexible UV-curable silicone resin composition, 20 parts by weight of a double-terminated active functional group-modified linear polysiloxane, 30 parts of a terminal side-containing active functional group-modified linear siloxane oligomer, 70 parts of a hyperbranched MTQ polysiloxane, 5 parts of an unsaturated silane oligomer, and 5 parts of 2-hydroxy-2-methyl-1-phenylpropanone are added sequentially to a reaction bottle, evacuated to -0.08 MPa, and stirred at medium speed for 0.5 h to obtain the high-strength flexible UV-curable silicone resin composition.

[0128] Example 10

[0129] Step 1: Preparation of double-terminated active functional group modified linear polysiloxane. At 25-45°C, accurately weigh 1000g of 80000cp107 silicone rubber, 5g of methacryloxypropylmethyldimethoxysilane, and 10g of dipropylamine, and put them into the reaction kettle in sequence, keep the temperature at 80°C for 2h, heat it to 140°C, keep it in vacuum at -0.08mpa for 2h, and then cool it down to obtain double-terminated active functional group modified linear polysiloxane.

[0130] Step 2: Preparation of terminal-side modified linear siloxane oligomers containing active functional groups. Accurately weigh 800 g of dimethyldiethoxysilane, 80 g of methyltriethoxysilane, 160 g of mercaptopropylmethyldiethoxysilane, 200 g of ethanol, and 50 g of ion exchange resin, and sequentially put them into the reaction. At 30-50°C, add 400 g of a mixture of water and ethanol in a mass ratio of 1:2, and continue stirring for 1 hour after the addition is completed. Heat to 70°C, reflux for 3 hours, filter to remove the ion exchange resin, and distill to remove the ethanol solvent to obtain the terminal-side modified linear siloxane oligomer containing active functional groups.

[0131] Step 3: Preparation of hyperbranched MTQ polysiloxane. Accurately weigh 1080 g of ethyl orthosilicate, 80 g of tetramethyldivinyldisiloxane, 274 g of hexamethyldisiloxane, and 124 g of methacryloxypropyltrimethoxysilane, mix them evenly, and drop them into a reactor containing 400 g of 5% hydrochloric acid aqueous solution and 500 g of toluene. After the dropwise addition is completed, stir continuously for 1 h, heat to 80° C., reflux for 3 h, cool and stand for stratification, remove the upper layer, and distill the lower layer to remove the solvent to obtain the hyperbranched MTQ polysiloxane.

[0132] Step 4: Preparation of unsaturated silane oligomers: 99 g of vinyl triethoxysilane and 5 g of water were accurately weighed and added to a reaction kettle in sequence, stirred at 40° C. for one hour, heated to 70° C., kept warm for 3 hours, and cooled to obtain the unsaturated silane oligomers.

[0133] Step 5: Preparation of high-strength flexible UV-curable silicone resin composition. Accurately weigh 400 g of double-terminated active functional group-modified linear polysiloxane, 220 g of end-side active functional group-modified linear siloxane oligomer, 350 g of hyperbranched MTQ polysiloxane, 20 g of unsaturated silane oligomer, and 10 g of photoinitiator cumene ferrocenium hexafluorophosphate, and add them to the reaction kettle in sequence, evacuate to -0.08 MPa, and stir at medium speed for 0.5 h to obtain the high-strength flexible UV-curable silicone resin composition.

[0134] Embodiment 11

[0135] Example 11 is basically the same as Example 10, except that in the preparation step of the high-strength flexible UV-curable silicone resin composition, 75 parts by weight of a double-terminated active functional group-modified linear polysiloxane, 75 parts of a terminal side-containing active functional group-modified linear siloxane oligomer, 30 parts of a hyperbranched MTQ-type polysiloxane, 1 part of an unsaturated silane oligomer, and 2 parts of 2-hydroxy-2-methyl-1-phenylpropanone are added sequentially to a reaction bottle, evacuated to -0.08 MPa, and stirred at medium speed for 0.5 h to obtain the high-strength flexible UV-curable silicone resin composition.

[0136] Example 12

[0137] Example 12 is basically the same as Example 10, except that in the preparation steps of the high-strength flexible UV-curable silicone resin composition, 3 parts by weight of a double-terminated active functional group-modified linear polysiloxane, 1 part of a terminal side-containing active functional group-modified linear siloxane oligomer, 6 parts of a hyperbranched MTQ-type polysiloxane, 1 part of an unsaturated silane oligomer, and 2 parts of 2-hydroxy-2-methyl-1-phenylpropanone are added to the reaction bottle in sequence, evacuated to -0.08 MPa, and stirred at medium speed for 0.5 h to obtain the high-strength flexible UV-curable silicone resin composition.

[0138] The application method of the high-strength flexible UV-curable silicone resin composition of the present invention is as follows:

[0139] At room temperature, the high-strength flexible UV-curable silicone resin composition or the high-strength flexible UV-curable silicone resin composition and the UV-curable resin are mixed uniformly in a mass ratio of 1:0.1-10, wherein the UV-curable resin includes an acrylic resin or an epoxy resin, and then the high-strength flexible UV-curable silicone resin composition is uniformly coated on the surface of the substrate by a roller coater, and a mold with a special texture is pressed on the surface, and the coating thickness does not exceed 1 mm. After irradiation with a 365nm ultraviolet lamp, the UV energy is 1000-1200mJ / cm 2 , curing, demoulding, and the finished product are obtained.

[0140] According to the application method, the high-strength flexible UV-cured silicone resin composition product is prepared.

[0141] The high-strength flexible UV-curable silicone resin composition prepared in each example is used to prepare products according to the above preparation method.

[0142] Application Examples 1-11

[0143] At room temperature, the high-strength flexible UV-curable silicone resin compositions prepared in Examples 1-11 were evenly coated on the surface of the substrate by a roller coater, and a mold with a special texture was pressed on the surface. The coating thickness was 95 μm. After irradiation with a 365 nm ultraviolet lamp, the UV energy was 1200 mJ / cm 2 After curing and demoulding, the product is obtained.

[0144] Application Example 12

[0145] At room temperature, 13 parts by weight of the high-strength flexible UV-curable silicone resin composition prepared in Example 12 was mixed evenly with 100 parts by weight of acrylic resin, and then evenly coated on the surface of the substrate by a roller coater, and a mold with a special texture was pressed on the surface. The coating thickness was 95 μm, and the coating was irradiated with a 365 nm ultraviolet lamp with a UV energy of 1200 mJ / cm2 After curing and demoulding, the product is obtained.

[0146] Comparative Example 1

[0147] UV organic silicone rubber (commercially available product, brand name Dow Corning EA-9187L) on the foreign market was selected for experimental comparison.

[0148] Comparative Example 2

[0149] A UV silicone resin on the domestic market (commercially available product, purchased from Anhui Mingyi Silicon Industry Co., Ltd., brand MY6ND81) was selected for experimental comparison.

[0150] The performance tests of the products prepared in each application example are as follows:

[0151] Viscosity: The viscosity of the composition was measured according to the method specified in GB / T265.

[0152] Tensile strength: The tensile strength of the composition was measured according to the method specified in GB / T528-1992.

[0153] Transparency: The transparency of the composition was measured according to the method specified in GB / T2410-2008.

[0154] Hardness: The hardness of the composition was measured according to the method specified in GB / T531-1999.

[0155] Complete curing time: The time from when the composition is completely cured under 365 nm ultraviolet light is the complete curing time of the composition.

[0156] Boiling resistance: The composition was coated on a glass plate with a thickness of about 100 um, and cured under 365 nm ultraviolet light. After curing, the glass plate was placed in boiling water for 3 hours and then taken out. If the coating of the glass plate composition was intact, it was recorded as "excellent"; otherwise, it was recorded as "poor".

[0157] Resistance to UV aging: The composition is coated on a glass plate with a thickness of about 100 um and cured under 365 nm UV light. After curing, the glass plate is placed 10 cm away from the UV light source and irradiated with 365 nm UV light for 6 hours. If the glass plate composition does not turn yellow and the coating is intact, it is recorded as "excellent"; otherwise, it is recorded as "poor".

[0158] Table 1 Product testing data of high-strength flexible UV-cured silicone resin compositions prepared in various embodiments

[0159]

[0160] It can be seen from the test data in Table 1 that the high-strength flexible UV-curable silicone resin composition of the present invention has a complete curing time of less than 10 seconds, a hardness of less than 70 Shore A, and a tensile strength generally greater than 3 MPa. Compared with similar UV silicone products on the market, the high-strength flexible UV-curable silicone resin composition of the present invention cures faster and can be used as an external coating in the field of flexible coatings such as leather and glass silk-screen printing, broadening the application field of existing UV silicone products, giving the material surface texture, and enhancing the material surface touch, strength and wear resistance.

[0161] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that the process, method, article or terminal device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or terminal device. In the absence of further restrictions, the elements defined by the sentence "include..." or "comprise..." do not exclude the existence of other elements in the process, method, article or terminal device including the elements. In addition, in this article, "greater than", "less than", "exceed" and the like are understood to exclude the number itself; "above", "below", "within" and the like are understood to include the number itself.

[0162] It should be noted that, although the above embodiments have been described in this article, the patent protection scope of the present invention is not limited thereby. Therefore, based on the innovative concept of the present invention, changes and modifications made to the embodiments described herein, or equivalent structures or equivalent process changes made using the contents of the present invention specification, directly or indirectly applying the above technical solutions to other related technical fields are all included in the patent protection scope of the present invention.

Claims

1. A high-strength flexible UV-curable silicone resin composition, characterized in that: It includes the following components in parts by weight: The structure of the double-terminated active functional group-modified linear polysiloxane is shown in Formula 1: In Formula 1, R1 is an alkyl group having a carbon number of C1-C4; R2 includes one or two of the following groups: one of methyl, ethyl, methoxy, ethoxy, propoxy, butoxy; a is an integer of 100-10000; R3 includes one of the following groups: 2,3-epoxypropyloxymethyl, 2,3-epoxypropyloxyethyl, 2,3-epoxypropyloxypropyl, vinyl, vinyl ether, propenyl, acryloxy, methacryloxy, methacryloxymethyl, methacryloxyethyl, methacryloxypropyl; The structure of the terminal-side modified linear siloxane oligomer containing active functional groups is shown in Formula 2: In Formula 2, R4 includes one of the following groups: 2,3-epoxypropyloxymethyl, 2,3-epoxypropyloxyethyl, 2,3-epoxypropyloxypropyl, vinyl, vinyl ether, propenyl, acryloxy, methacryloxy, methacryloxymethyl, methacryloxyethyl, methacryloxypropyl, mercapto, mercaptomethyl, mercaptoethyl, mercaptopropyl; R5 includes one or two of the following groups: methyl, ethyl, methoxy, ethoxy, propoxy, butoxy; R6 includes one or two of the following groups: 2,3-epoxypropyloxymethyl, 2,3-epoxypropyloxyethyl, 2,3-epoxypropyloxypropyl, vinyl, vinyl ether, propenyl, acryloxy, methacryloyloxy, methacryloyloxymethyl, methacryloyloxyethyl, methacryloyloxypropyl, methyl, ethyl, methoxy, ethoxy, propoxy, butoxy, mercapto, mercaptomethyl, mercaptoethyl, mercaptopropyl; R7 includes one or two of the following groups: hydroxy, methoxy, ethoxy, propoxy, butoxy; b and c are integers from 0 to 25 respectively; The structural formula of the unsaturated silane oligomer is shown in Formula 3: In Formula 3, R8 includes one of the following groups: acryloyloxymethyl, acryloyloxyethyl, acryloyloxypropyl, methacryloyloxymethyl, methacryloyloxyethyl, methacryloyloxypropyl, vinyl, and acryl; R9 includes one or two of the following groups: hydroxyl, methoxy, ethoxy, propoxy, butoxy, dimethyl ketoxime, methyl ethyl ketoxime, acetoxy, isopropenyloxy, isobutenyloxy, N-butylamino, N,N-diethylamino, N-methylacetamide; e is a positive integer less than or equal to 10; The structural formula of the hyperbranched MTQ polysiloxane is shown in Formula 4: In formula 4, R 10 Includes one or more of the following groups: alkyl, vinyl, and silyl groups having carbon numbers of C1-C4; R 11 Including one of the following groups: 2,3-epoxypropyloxymethyl, 2,3-epoxypropyloxyethyl, 2,3-epoxypropyloxypropyl, acryloyloxymethyl, acryloyloxyethyl, acryloyloxypropyl, methacryloyloxymethyl, methacryloyloxyethyl, methacryloyloxypropyl, mercapto, mercaptomethyl, mercaptoethyl, mercaptopropyl, silyl; f and h are positive integers ranging from 0 to 50 respectively.

2. A high-strength flexible UV-curable silicone resin composition according to claim 1, characterized in that: It includes the following components in parts by weight:

3. A high-strength flexible UV-curable silicone resin composition according to claim 1, characterized in that: The photoinitiator includes one of the following or a mixture of two or more thereof: 2-hydroxy-2-methyl-1-phenylpropanone, 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio)phenyl]-1-propanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, diaryl iodonium salt, triaryl iodonium salt, alkyl iodonium salt, isopropyl ferrocenium hexafluorophosphate.

4. A high-strength flexible UV-curable silicone resin composition according to any one of claims 1 to 3, characterized in that: The double-terminated active functional group-modified linear polysiloxane is prepared by the following preparation method, which comprises the following steps: At 25-45° C., adding the first functional silane monomer and silicone rubber with a viscosity greater than or equal to 10000 cp into a reaction kettle, adding an alkaline catalyst, heating to 80° C. for 2 hours, then heating to 140° C. for 2 hours under vacuum, to obtain the double-terminated active functional group-modified linear polysiloxane; The weight parts of each component are as follows: Silicone rubber 95-100 parts by weight; 0.1-5 parts by weight of the first functional silane monomer; Basic catalyst 0.1-2 parts by weight; The molecular formula of the functional silane monomer is shown in Formula 5: In Formula 5, R2 includes one or two of the following groups: methyl, ethyl, methoxy, ethoxy, propoxy, butoxy; R3 includes one of the following groups: 2,3-epoxypropyloxymethyl, 2,3-epoxypropyloxyethyl, 2,3-epoxypropyloxypropyl, vinyl, vinyl ether, propenyl, acryloxy, methacryloxy, methacryloxymethyl, methacryloxyethyl, methacryloxypropyl; The alkaline catalyst includes one of the following: tetramethylammonium hydroxide, tri-n-propylamine, dipropylamine, n-butylamine, tri-n-butylamine.

5. A high-strength flexible UV-curable silicone resin composition according to any one of claims 1 to 3, characterized in that: The terminal side-containing active functional group-modified linear siloxane oligomer is prepared by the following preparation method, which comprises the following steps: First, two or more second functional silane monomers, organic alcohol A, and acidic ion exchange resin are added to a reaction kettle. At 30-50° C., water and another portion of organic alcohol A are mixed in a mass ratio of 1:2 and then added dropwise to the reaction kettle. After the addition is completed, the mixture is kept warm and stirred for 1 hour. Then, the mixture is heated to reflux temperature, reacted at reflux temperature for 3 hours, the ion exchange resin is removed by filtration, and the solvent is removed by distillation to obtain the linear siloxane oligomer modified with active functional groups at the end side. The molecular formula of the second functional silane monomer is shown in Formula 6 or Formula 7 below: In Formula 6, R4 includes one of the following groups: 2,3-epoxypropyloxymethyl, 2,3-epoxypropyloxyethyl, 2,3-epoxypropyloxypropyl, vinyl, vinyl ether, propenyl, acryloxy, methacryloxy, methacryloxymethyl, methacryloxyethyl, methacryloxypropyl, mercapto, mercaptomethyl, mercaptoethyl, mercaptopropyl; In Formula 6 or Formula 7, R5 includes one or two of the following groups: methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, butoxy; R6 includes one of the following groups: methyl, ethyl, propyl, butyl; The organic alcohol A includes one of the following: methanol, ethanol, propanol, and butanol. Wherein, the weight parts of each component are as follows: During the reaction, one or more second functional silane monomers represented by Formula 6 and one or more second functional silane monomers represented by Formula 7 are added.

6. A high-strength flexible UV-curable silicone resin composition according to any one of claims 1 to 3, characterized in that: The unsaturated silane oligomer is prepared by the following preparation method, which comprises the following steps: Preparation of unsaturated silane oligomer: add water and unsaturated silane into a reaction kettle at 30-50°C, keep warm and stir for 1 hour, then heat to 70°C, keep warm and react for 3 hours, and cool down after the reaction to obtain the unsaturated silane oligomer; The unsaturated silane is shown in Formula 8: In Formula 8, R8 includes one of the following groups: acryloyloxymethyl, acryloyloxyethyl, acryloyloxypropyl, methacryloyloxymethyl, methacryloyloxyethyl, methacryloyloxypropyl, vinyl, and acryl; R 12 Include one or two of the following groups: methoxy, ethoxy, propoxy, butoxy, dimethyl ketoxime, methyl ethyl ketoxime, acetoxy, isopropenyloxy, isobutenyloxy, N-butylamino, N,N-diethylamino, N-methylacetamide; Wherein, the weight parts of each component are as follows: Unsaturated silane 70-99 parts; 3.5-5 parts water.

7. A high-strength flexible UV-curable silicone resin composition according to claims 1-3, characterized in that: The hyperbranched MTQ type polysiloxane is prepared by the following preparation method, which comprises the following steps: At 30-50° C., two or more third functional silane monomers are added dropwise to a reaction kettle containing a 5% hydrochloric acid aqueous solution and toluene. After the addition is completed, the mixture is kept warm and stirred for 1 hour, then heated to reflux temperature, kept at reflux temperature for 3 hours, cooled and allowed to stand for stratification, the upper layer is removed, and the solvent is removed from the lower layer by distillation to obtain the hyperbranched MTQ polysiloxane; The molecular formula of the third functional silane monomer is shown in Formula 9, Formula 10 or Formula 11 below: Wherein, R5 includes one or two of the following groups: methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, butoxy; R 10 Includes one or more of the following groups: alkyl, vinyl, and silyl groups having carbon numbers of C1-C4; R 11 Including one of the following groups: 2,3-epoxypropyloxymethyl, 2,3-epoxypropyloxyethyl, 2,3-epoxypropyloxypropyl, vinyl, propenyl, acryloxymethyl, acryloxyethyl, acryloxypropyl, methacryloxymethyl, methacryloxyethyl, methacryloxypropyl, mercapto, mercaptomethyl, mercaptoethyl, mercaptopropyl, silyl; Wherein, the weight parts of each component are as follows: During the reaction, one or more third functional silane monomers shown in formula 10 are added, and one or more third functional silane monomers shown in formula 11 are added; the input amount of the third functional silane monomer shown in formula 9 can be 0 or not 0. When the input amount of the third functional silane monomer shown in formula 9 is not 0, one or more third functional silane monomers shown in formula 9 are added.

8. The method for preparing a high-strength flexible UV-curable silicone resin composition according to any one of claims 1 to 7, characterized in that: It includes the following steps: At room temperature, double-terminated active functional group-modified linear polysiloxane, end-side active functional group-modified linear siloxane oligomer, unsaturated silane oligomer, hyperbranched MTQ polysiloxane, and photoinitiator are added to a reaction kettle in parts by weight, the reaction mixture is evacuated to -0.08 MPa, and stirred for 0.5 h to obtain the high-strength flexible UV-curable silicone resin composition.

9. The application method of the high-strength flexible UV-curable silicone resin composition according to claims 1-7, characterized in that: The application method: At room temperature, the high-strength flexible UV-curable silicone resin composition or the high-strength flexible UV-curable silicone resin composition and the UV-curable resin are mixed uniformly in a mass ratio of 1:0.1-10, wherein the UV-curable resin includes an acrylic resin or an epoxy resin, and then the high-strength flexible UV-curable silicone resin composition is uniformly coated on the surface of the substrate by a roller coater, and a mold with a special texture is pressed on the surface, and the coating thickness does not exceed 1 mm. After irradiation with a 365nm ultraviolet lamp, the UV energy is 1000-1200mJ / cm 2 , curing, demoulding, and obtaining the product.

10. A product prepared from the high-strength flexible UV-curable silicone resin composition according to claim 9, characterized in that: The invention is prepared by the application method described in claim 9.

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