Heat-curable carrier-free organosilicone adhesive film and preparation method thereof

Abstract

The invention discloses a thermosetting carrier-free organosilicon adhesive film and a preparation method thereof, and the carrier-free organosilicon adhesive film comprises the following components by weight: 100 parts of side chain acrylate modified vinyl-terminated methyl silicone oil; 2 to 10 parts of side chain acrylate modified methyl-terminated hydrogen-containing silicone oil; 10 to 30 parts of vinyl MQ resin; 5-30 parts of a reinforcing filler; 2-5 parts of a photoinitiator; 0.05 to 0.3 part of a single-component platinum catalyst; 0.05 to 0.2 part of an inhibitor; and 0.5 to 3 parts of a boron-containing tackifier. The organic silica gel film does not need to provide an additional carrier as a support, the film forming process and the semi-curing degree are controllable, raw materials needed in the preparation process are cheap and easy to obtain, the production process is simple and easy to operate, meanwhile, reaction conditions are mild, no special requirements for equipment exist, and industrialization is easy to achieve.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic silicone film preparation, and in particular, relates to a heat-curable carrier-free organic silicone adhesive film and a preparation method thereof. Background Art

[0002] Organic silicon materials have excellent resistance to high and low temperatures, electrical insulation, oxidation stability, weather resistance, flame retardancy, water repellency, corrosion resistance, non-toxicity, tastelessness, and physiological inertness, and are widely used in aerospace, electrical and electronic, automotive, medical and other fields. Organic silicon adhesive is a siloxane composition with bonding and sealing functions. It is an important category of organic silicon materials with a wide range of applications. It is mostly in the form of pastes and liquids, and is prone to problems such as uneven glue coating, glue overflow, and glue flow during use. If it is prepared in the form of a film, it has the advantages of easy transportation, storage, and use, and uniform thickness of the adhesive layer. When used, it can achieve stable bonding of the substrate through further curing reaction.

[0003] The adhesive films available on the market are mainly hot melt adhesive films, and the main materials are ethylene-vinyl acetate copolymer (EVA), polyolefin (PO), thermoplastic polyurethane (TPU), nylon (PA) and epoxy (EP). With the rapid development of electronics, new energy and other fields, the requirements for the construction processability of materials are getting higher and higher. The use of semi-cured silicone adhesive films with simple processes and easy operation will become an important direction for future development. However, due to the poor cohesion of silicone, it is difficult to form a carrier-free semi-cured adhesive film with certain viscosity and strength at the same time. In addition, how to control the semi-cured state of silicone materials and finally achieve the bonding function through post-curing is a problem that needs to be solved urgently. Summary of the invention

[0004] In order to solve the above problems, the present invention provides a heat-curable carrier-free silicone adhesive film and a preparation method thereof. The silicone adhesive film contains silicone oil with UV-curable and heat-curable groups, has certain strength and viscosity, and does not require additional carriers as support. The film-forming process and semi-curing degree are controllable.

[0005] In order to achieve the above object, the present invention provides the following technical solutions:

[0006] A heat-curable carrier-free organic silicone adhesive film, characterized in that it comprises the following components in parts by weight:

[0007] 100 parts of side chain acrylate-modified vinyl methyl silicone oil;

[0008] 2 to 10 parts of side chain acrylate-modified methyl-terminated hydrogen-containing silicone oil;

[0009] 10-30 parts of vinyl MQ resin;

[0010] 5 to 30 parts of reinforcing filler;

[0011] 2 to 5 parts of photoinitiator;

[0012] 0.05-0.3 parts of single component platinum catalyst;

[0013] Inhibitor 0.05-0.2 parts;

[0014] Contains 0.5 to 3 parts of boron thickener.

[0015] According to an embodiment of the present invention, the following components are included in parts by weight:

[0016] 100 parts of side chain acrylate-modified vinyl methyl silicone oil;

[0017] 4-5 parts of side chain acrylate modified methyl-terminated hydrogen-containing silicone oil;

[0018] 10-20 parts of vinyl MQ resin;

[0019] 20-30 parts of reinforcing filler;

[0020] 2-3 parts of photoinitiator;

[0021] 0.08-0.1 parts of single component platinum catalyst;

[0022] Inhibitor 0.05-0.1 part;

[0023] Contains 1 to 2 parts of boron thickener.

[0024] According to an embodiment of the present invention, the general structural formula of the side chain acrylate-modified vinyl methyl silicone oil is as follows:

[0025]

[0026] Among them, R is

[0027] m is an integer between 150 and 2000, preferably m is an integer between 200 and 1500;

[0028] n is an integer between 1 and 8.

[0029] According to an embodiment of the present invention, the general structural formula of the side chain acrylate-modified methyl-terminated hydrogen-containing silicone oil is as follows:

[0030]

[0031] Among them, R is

[0032] a is an integer between 50 and 250, preferably between 80 and 200;

[0033] b is an integer between 70 and 180;

[0034] c is an integer between 1 and 8.

[0035] According to an embodiment of the present invention, the M / Q ratio of the vinyl MQ resin is 0.6-0.9, and the vinyl content is 1.5%-4.0%; wherein M is a monofunctional siloxane chain segment in the vinyl MQ resin, and Q is a tetrafunctional siloxane chain segment in the vinyl MQ resin.

[0036] Preferably, the vinyl MQ resin has an M / Q ratio of 0.7 to 0.8 and a vinyl content of 2.0% to 3.5%.

[0037] According to an embodiment of the present invention, the reinforcing filler is hydrophobic fumed silica, and the specific surface area of ​​the hydrophobic fumed silica is greater than 100m 2 / g.

[0038] According to an embodiment of the present invention, the photoinitiator is one or more of 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173), 1-hydroxycyclohexyl phenyl ketone (184) or 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone.

[0039] According to an embodiment of the present invention, the concentration of the single-component platinum catalyst is 1000 ppm to 6000 ppm, preferably 2000 ppm to 5000 ppm.

[0040] According to an embodiment of the present invention, the inhibitor is selected from alcohols and / or siloxanes.

[0041] For example, one or more of acetylene cyclohexanol, methyl butynol, tetramethyldivinyldisiloxane or tetramethyltetravinylcyclotetrasiloxane.

[0042] According to an embodiment of the present invention, the general structural formula of the boron-containing tackifier is as follows:

[0043]

[0044] Among them, R1 is The present invention also provides a method for preparing a heat-curable carrier-free organic silicone adhesive film, comprising:

[0045] S1, preparing a side chain acrylate-modified terminal vinyl methyl silicone oil and a side chain acrylate-modified terminal methyl hydrogen silicone oil, adding or preparing a boron-containing tackifier; mixing them evenly according to the raw material ratio of the carrier-free organic silicone adhesive film, vacuum degassing, and preparing an organic silicone mixed adhesive solution in advance;

[0046] S2, uniformly coating the organic silicon mixed adhesive prepared in step S1 on a release film by slit coating, and forming a layer of adhesive of a predetermined thickness on the release paper by scraping;

[0047] S3, vacuum ultraviolet light curing the adhesive solution to form a carrier-free organic silicone adhesive film with initial adhesion.

[0048] In the present invention, in the process of preparing the carrier-free organic silicone adhesive film, the organic silicone adhesive material is prepared in advance, and a layer of adhesive liquid with a predetermined thickness is formed on the isolation paper by a scraping method, and a carrier-free organic silicone film with initial adhesion is formed by ultraviolet light curing, thereby avoiding the problems of insufficient adhesive, overflow of adhesive, and uneven bonding that are easy to occur during the adhesive bonding process.

[0049] According to an embodiment of the present invention, in step S2, the thickness of the glue formed is 20 to 300 microns, preferably 30 to 200 microns.

[0050] According to an embodiment of the present invention, the carrier-free organic silicone adhesive film is further cured by a hydrosilylation reaction by heating in a later application to achieve a bonding effect; preferably, the heating curing temperature is 100 to 150° C. and the time is 20 to 60 minutes.

[0051] According to an embodiment of the present invention, the method for preparing the raw material side chain acrylate-modified terminal vinyl methyl silicone oil comprises:

[0052] Octamethylcyclotetrasiloxane, dialkoxysilane, 1,5-divinylhexamethyltrisiloxane, acidic substance and acid catalyst are added to the reaction kettle in sequence, and after being evenly mixed, the temperature of the reaction kettle is raised to 40-70°C, and the reaction is carried out for 3-8 hours. The vacuum degree is controlled at 100-600Pa, and after vacuuming for 2-5 hours, the temperature is lowered to room temperature, a weak alkaline substance is added, stirring is continued, and filter pressing is performed to obtain a colorless and transparent side chain acrylate modified terminal vinyl methyl silicone oil.

[0053] According to an embodiment of the present invention, the reaction equation of the side chain acrylate-modified terminal vinyl methyl silicone oil is as follows:

[0054]

[0055] Among them, R is

[0056] R' is methyl or ethyl, R" is ethyl;

[0057] m is an integer between 150 and 2000, preferably m is an integer between 200 and 1500;

[0058] n is an integer between 1 and 8.

[0059] According to an embodiment of the present invention, the molar ratio of the octamethylcyclotetrasiloxane (D4) to the dialkoxysilane is (180-210):1; the molar ratio of the octamethylcyclotetrasiloxane (D4) to 1,5-divinylhexamethyltrisiloxane is (200-1500):1.

[0060] According to an embodiment of the present invention, the acidic substance is acetic acid, and the molar ratio of the amount of the acidic substance added to the total amount of alkoxy groups in the dialkoxysilane is 0.5 to 1.1:1, preferably 0.7 to 1:1.

[0061] According to an embodiment of the present invention, the acidic catalyst is trifluoromethanesulfonic acid, and the added amount is 1‰ to 3‰ of the total reaction raw material mass.

[0062] According to an embodiment of the present invention, the dialkoxysilane is selected from one or more of 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane and 3-acryloxypropylmethyldimethoxysilane.

[0063] According to an embodiment of the present invention, the weak alkaline substance is sodium bicarbonate; the added molar number of the weak alkaline substance is 1 to 1.5 times the molar number of trifluoromethanesulfonic acid, preferably 1.05 to 1.2 times.

[0064] According to the embodiment of the present invention, the preparation method of the raw material side chain acrylate modified terminal methyl hydrogen silicone oil in step S1 is basically the same as the preparation method of the side chain acrylate modified terminal vinyl methyl silicone oil, the specific difference is that the end-capping agent is changed from 1,5-divinylhexamethyltrisiloxane to hexamethyldisiloxane, and tetramethylcyclotetrasiloxane (D4 H ).

[0065] Specifically, the preparation method of the raw material side chain acrylate-modified terminal vinyl methyl silicone oil comprises:

[0066] Octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane (D4 H), dialkoxysilane, hexamethyldisiloxane, acidic substance and acid catalyst, after mixing evenly, the temperature of the reactor is raised to 40-70°C, and the reaction is carried out for 3-8 hours. The vacuum degree is controlled at 100-600Pa, and the temperature is lowered to room temperature after vacuuming for 2-5 hours. A weak alkaline substance is added, and stirring is continued. Filter pressure is performed to obtain a colorless and transparent side chain acrylate modified terminal methyl hydrogen-containing silicone oil.

[0067] According to an embodiment of the present invention, the reaction equation for preparing the side chain acrylate-modified methyl-terminated hydrogen-containing silicone oil is as follows:

[0068]

[0069] Among them, R is

[0070] R' is methyl or ethyl, R" is ethyl;

[0071] a is an integer between 50 and 250, preferably between 80 and 200;

[0072] b is an integer between 70 and 180; c is an integer between 1 and 8.

[0073] According to an embodiment of the present invention, the octamethylcyclotetrasiloxane (D4), tetramethylcyclotetrasiloxane (D4 H ) and dialkoxysilane is 100:90:(0.9-2.6); the molar ratio of octamethylcyclotetrasiloxane (D4) and hexamethyldisiloxane is (80-200):1.

[0074] According to an embodiment of the present invention, the boron-containing adhesion promoter is prepared by the following method.

[0075] Specifically, the preparation method includes: first, adding trimethoxysilane into a flask, stirring and raising the temperature to 40-70°C, preferably 45-65°C, adding boric acid into the flask in 5 batches, and after the addition is completed, continuing the reaction for 2-5 hours, and then controlling the vacuum degree at 200-800Pa, preferably 300-600Pa, and cooling to room temperature after vacuuming for 2-5 hours to obtain a colorless, transparent, viscous liquid, which is a boron-containing thickener.

[0076] The present invention can prepare the boron-containing adhesion promoter by directly reacting boric acid and trimethoxysilane at a certain temperature, and the reaction process is as follows:

[0077]

[0078] Among them, R1 is One of them.

[0079] The molar ratio of the total amount of boric acid added to trimethoxysilane is 1:(3-3.5).

[0080] According to an embodiment of the present invention, the trimethoxysilane is selected from one of γ-methacryloxypropyltrimethoxysilane (KH-570), γ-glycidyloxypropyltrimethoxysilane (KH-560) or vinyltrimethoxysilane (A-171).

[0081] Compared with the prior art, the present invention has the following beneficial effects:

[0082] 1) The present invention has designed and prepared silicone oil containing both UV-curable and heat-curable groups. First, a partial cross-linking reaction occurs through UV irradiation to form an organic silicone film with a certain strength and at the same time retains viscosity, thereby avoiding the problems of adhesive shortage, adhesive overflow, and uneven bonding during the adhesive bonding process. In later applications, it can be further cured by heating, and the bonding effect is achieved by post-curing through a hydrosilylation reaction, thereby achieving the purpose of bonding. The organic silicone film does not need to provide an additional carrier as a support, and the film-forming process and the degree of semi-curing are controllable.

[0083] 2) The raw materials required in the preparation process of the present invention are cheap and easily available, the production process is simple and easy to operate, and the reaction conditions are mild and there are no special requirements for equipment, so it is easy to realize industrialization. BRIEF DESCRIPTION OF THE DRAWINGS

[0084] Figure 1 The side chain acrylate-modified terminal vinyl methyl silicone oil prepared by the present invention is 1 H NMR spectrum;

[0085] Figure 2 The side chain acrylate-modified methyl-terminated hydrogen-containing silicone oil prepared by the present invention is 1 H NMR spectrum; DETAILED DESCRIPTION

[0086] The technical scheme of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only exemplary descriptions and explanations of the present invention and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are included in the scope that the present invention is intended to protect.

[0087] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available.

[0088] Example 1

[0089] a) preparing side chain acrylate modified terminal vinyl methyl silicone oil (VPMAS), the specific steps are as follows:

[0090] Octamethylcyclotetrasiloxane (D4), dialkoxysilane, 1,5-divinylhexamethyltrisiloxane, acetic acid and trifluoromethanesulfonic acid are added to the reaction kettle in sequence and mixed evenly. The temperature of the reaction kettle is raised to 40-70°C. After reacting for 3-8 hours, the vacuum degree is controlled at 100-600 Pa. After vacuuming for 2-5 hours, the temperature is lowered to room temperature. A weak alkaline substance, sodium bicarbonate, is added. After stirring for 2 hours, pressure filtration is performed to obtain a colorless and transparent side chain acrylate modified terminal vinyl methyl silicone oil.

[0091] Different dialkoxysilanes are numbered: dialkoxysilane-1 represents 3-methacryloxypropylmethyldimethoxysilane; dialkoxysilane-2 represents 3-methacryloxypropylmethyldiethoxysilane; and dialkoxysilane-3 represents 3-acryloxypropylmethyldimethoxysilane.

[0092] The raw materials and specific parameters in the preparation process are shown in Table 1 below.

[0093] The viscosity test was conducted using the single cylinder rotation viscometer method in accordance with GB / T 2794 for the determination of adhesive viscosity.

[0094] Table 1

[0095]

[0096]

[0097] b) The method for preparing side chain acrylate modified methyl-terminated hydrogen-containing silicone oil (MPHMAS) is as follows:

[0098] Octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane (D4 H ), dialkoxysilane, hexamethyldisiloxane, acidic substance and acid catalyst, after mixing evenly, the temperature of the reactor is raised to 40-70°C, and the reaction is carried out for 3-8 hours. The vacuum degree is controlled at 100-600Pa, and the temperature is lowered to room temperature after vacuuming for 2-5 hours. A weak alkaline substance is added, and stirring is continued. Filter pressure is performed to obtain a colorless and transparent side chain acrylate modified terminal methyl hydrogen-containing silicone oil.

[0099] The raw materials and specific parameters in the preparation process are shown in Table 2 below.

[0100] Table 2

[0101]

[0102]

[0103] The boron-containing tackifier may be a commercially available product, or may be prepared by the following method:

[0104] First, add trimethoxysilane into a flask, stir and raise the temperature to 40-70°C, preferably 45-65°C, add boric acid into the flask in 5 batches, and after the addition is completed, continue the reaction for 2-5 hours, then control the vacuum degree at 200-800Pa, preferably 300-600Pa, evacuate for 2-5 hours, then cool to room temperature to obtain a colorless, transparent, viscous liquid, which is the boron-containing thickener.

[0105] The preparation examples of boron-containing viscosity enhancers are shown in Table 3.

[0106] Table 3

[0107]

[0108] Example 2

[0109] The specific ratio of the adhesive solution for preparing adhesive film-1 is shown in Table 4.

[0110] Table 4

[0111] Components Weight parts (parts) VPMAS-1 50 VPMAS-4 50 MPHMAS-1 4 Vinyl MQ resin (vinyl content 2.5%) 30 Hydrophobic Fumed Silica 5 Photoinitiator(1173) 2 Single component platinum catalyst (2000ppm) 0.2 Inhibitor (Tetramethyldivinyldisiloxane) 0.1 Boron-containing viscosity enhancer-1 1

[0112] In the boron-containing thickener-1, R1 is

[0113] Stir the above components evenly and vacuum degas. Use slit coating to evenly coat the mixed adhesive on a release film with a coating thickness of 100μm. Then, 2 The resulting film was irradiated with an ultraviolet lamp (365 nm) for 90 s to obtain a carrier-free organic silicone adhesive film.

[0114] Example 3

[0115] The specific ratio of the adhesive solution for preparing adhesive film-2 is shown in Table 5.

[0116] Table 5

[0117]

[0118]

[0119] In the boron-containing thickener-2, R1 is

[0120] The above components were stirred evenly and vacuum degassed. The mixed adhesive was evenly coated on a release film with a thickness of 150 μm by slit coating, and then subjected to a 20 mW / cm 2 The organic silicon adhesive film without carrier was obtained by irradiating the organic silicon adhesive film with ultraviolet light (365 nm) for 100 s.

[0121] Example 4

[0122] The specific ratio of the adhesive solution for preparing adhesive film-3 is shown in Table 6.

[0123] Table 6

[0124] Components Weight VPMAS-5 100 MPHMAS-3 5 Vinyl MQ resin (vinyl content 3.0%) 15 Hydrophobic Fumed Silica 25 Photoinitiator(184) 2.5 Single component platinum catalyst (5000ppm) 0.1 Inhibitor (methylbutynol) 0.05 Boron-containing viscosity enhancer-3 1.5

[0125] In the boron-containing thickener-2, R1 is

[0126] Stir the above components evenly and vacuum degas. Use slit coating to evenly coat the mixed glue on a release film with a thickness of 100μm, and then pass through a 20mW / cm 2 The resultant organic silicone adhesive film was irradiated with an ultraviolet lamp (365 nm) for 60 s to obtain a carrier-free organic silicone adhesive film.

[0127] Example 5

[0128] The specific ratio of the adhesive solution for preparing adhesive film-4 is shown in Table 7.

[0129] Table 7

[0130]

[0131] In the boron-containing thickener-2, R1 is

[0132] Stir the above components evenly and vacuum degas. Use slit coating to evenly coat the mixed adhesive on a release film with a thickness of 200μm, and then pass through a 20mW / cm 2 The organic silicon adhesive film without carrier was obtained by irradiating the organic silicon adhesive film with ultraviolet light (365 nm) for 120 s.

[0133] Example 6

[0134] The specific ratio of the adhesive solution for preparing adhesive film-5 is shown in Table 8.

[0135] Table 8

[0136]

[0137]

[0138] In the boron-containing thickener-2, R1 is

[0139] Stir the above components evenly and vacuum degas. Use slit coating to evenly coat the mixed glue on a release film with a thickness of 50μm, and then pass it through a 20mW / cm 2 The resultant organic silicone adhesive film was irradiated with an ultraviolet lamp (365 nm) for 60 s to obtain a carrier-free organic silicone adhesive film.

[0140] The organic silicone adhesive films prepared in Examples 2-6 were tested:

[0141] The silicone adhesive film prepared in the above embodiment was respectively pasted between two stainless steel sheets and two PI films to prepare stainless steel shear specimens and PI film peeling specimens, and then cured at 100°C for 1 hour and tested. The test results are shown in Table 9.

[0142] Table 9

[0143]

[0144] It can be seen from the results in Table 9 that the adhesive film prepared by the present invention can be further cured by heating to achieve the purpose of bonding. The organic silicone film has good bonding properties to the stainless steel sheet and the PI film, especially the adhesive film-2, adhesive film-3 and adhesive film-4 prepared in Examples 3-5, which have better bonding properties to the stainless steel sheet and the PI film.

[0145] The above is only a preferred application implementation of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the technical principles of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A heat-curable carrier-free organic silicone adhesive film, characterized in that: The invention comprises the following components in parts by weight: 100 parts of terminal vinyl methyl silicone oil modified by side chain acrylate; 2 to 10 parts of terminal methyl hydrogen silicone oil modified by side chain acrylate; 10 to 30 parts of vinyl MQ resin; 5 to 30 parts of reinforcing filler; 2 to 5 parts of photoinitiator; 0.05 to 0.3 parts of single-component platinum catalyst; 0.05 to 0.2 parts of inhibitor; and 0.5 to 3 parts of boron-containing tackifier.

2. The carrier-free organic silicone adhesive film according to claim 1, characterized in that: The invention comprises the following components in parts by weight: 100 parts of terminal vinyl methyl silicone oil modified by side chain acrylate; 4-5 parts of terminal methyl hydrogen silicone oil modified by side chain acrylate; 10-20 parts of vinyl MQ resin; 20-30 parts of reinforcing filler; 2-3 parts of photoinitiator; 0.08-0.1 parts of single-component platinum catalyst; 0.05-0.1 parts of inhibitor; and 1-2 parts of boron-containing tackifier.

3. The carrier-free organic silicone adhesive film according to claim 1 or 2, characterized in that: The general structural formula of the side chain acrylate-modified vinyl methyl silicone oil is as follows: Among them, R is m is an integer between 150 and 2000, preferably m is an integer between 200 and 1500; n is an integer between 1 and 8.

4. The carrier-free organic silicone adhesive film according to claim 1 or 2, characterized in that: The general structural formula of the side chain acrylate-modified methyl-terminated hydrogen-containing silicone oil is as follows: Among them, R is a is an integer between 50 and 250, preferably between 80 and 200; b is an integer between 70 and 180; c is an integer between 1 and 8.

5. The carrier-free organic silicone adhesive film according to claim 1 or 2, characterized in that: The M / Q ratio of the vinyl MQ resin is 0.6-0.9, and the vinyl content is 1.5%-4.0%. M is a monofunctional siloxane chain segment in the vinyl MQ resin, and Q is a tetrafunctional siloxane chain segment in the vinyl MQ resin. Preferably, the vinyl MQ resin has an M / Q ratio of 0.7 to 0.8 and a vinyl content of 2.0% to 3.5%.

6. The carrier-free organic silicone adhesive film according to claim 1 or 2, characterized in that: The reinforcing filler is hydrophobic fumed silica, and the specific surface area of ​​the silica is greater than 100 m 2 / g; Preferably, the photoinitiator is selected from one or more of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone or 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone; Preferably, the concentration of the single-component platinum catalyst is 1000ppm to 6000ppm, preferably 2000ppm to 5000ppm; Preferably, the inhibitor is selected from alcohols and / or siloxanes; For example, acetylene cyclohexanol, methyl butynol, tetramethyldivinyldisiloxane or tetramethyltetravinylcyclotetrasiloxane.

7. The method for preparing the heat-curable carrier-free organic silicone adhesive film according to any one of claims 1 to 6, characterized in that: include: S1, preparing a side chain acrylate modified terminal vinyl methyl silicone oil, a side chain acrylate modified terminal methyl hydrogen silicone oil, and adding a boron-containing tackifier; mixing the raw materials according to the ratio of claims 1 to 6, vacuum degassing, and preparing a silicone mixed glue in advance; S2, using a slit coating method to evenly apply the mixed adhesive prepared in step S1 on a release film, and using a scraping method to form a layer of adhesive with a predetermined thickness on the release paper; S3, vacuum ultraviolet light curing to form a carrier-free organic silicone adhesive film with initial adhesion.

8. The preparation method according to claim 7, characterized in that: The method for preparing the side chain acrylate-modified terminal vinyl methyl silicone oil in step S1 comprises: Octamethylcyclotetrasiloxane, dialkoxysilane, 1,5-divinylhexamethyltrisiloxane, an acidic substance and an acid catalyst are sequentially added to a reaction kettle, and after being uniformly mixed, the temperature of the reaction kettle is raised to 40-70° C., and after reacting for 3-8 hours, the vacuum degree is controlled at 100-600 Pa, and after vacuuming for 2-5 hours, the temperature is lowered to room temperature, a weak alkaline substance is added, stirring is continued, and filter pressing is performed to obtain a colorless and transparent side chain acrylate modified terminal vinyl methyl silicone oil; Preferably, the reaction equation of the side chain acrylate-modified vinyl methyl silicone oil is as follows: Among them, R is R' is methyl or ethyl; R" is ethyl; m is an integer between 150 and 2000, preferably m is an integer between 200 and 1500; n is an integer between 1 and 8. Preferably, the molar ratio of the octamethylcyclotetrasiloxane to the dialkoxysilane is (180-210):1; the molar ratio of the octamethylcyclotetrasiloxane to the 1,5-divinylhexamethyltrisiloxane is (200-1500):

1. Preferably, the acidic substance is acetic acid, and the molar ratio of the amount added to the total amount of alkoxy groups in the dialkoxysilane is 0.5 to 1.1:1, more preferably 0.7 to 1:1; Preferably, the catalyst is trifluoromethanesulfonic acid, and the added mass is 1‰ to 3‰ of the total reaction raw material mass; Preferably, the dialkoxysilane is selected from one or more of 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane and 3-acryloxypropylmethyldimethoxysilane; Preferably, the weak alkaline substance is selected from sodium bicarbonate; the added molar number of the weak alkaline substance is 1 to 1.5 times the molar number of trifluoromethanesulfonic acid, preferably 1.05 to 1.2 times.

9. The preparation method according to claim 7, characterized in that: The method for preparing the side chain acrylate-modified methyl-terminated hydrogen-containing silicone oil in step S1 comprises: Octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane (D4 H ), dialkoxysilane, hexamethyldisiloxane, acidic substance and acid catalyst, after being evenly mixed, the temperature of the reactor is raised to 40-70°C, reacted for 3-8 hours, the vacuum degree is controlled at 100-600Pa, vacuumed for 2-5 hours, then cooled to room temperature, weak alkaline substance is added, stirring is continued, filter pressing is performed, and colorless and transparent side chain acrylate modified terminal methyl hydrogen-containing silicone oil is obtained; Preferably, the reaction equation of the side chain acrylate-modified methyl-terminated hydrogen-containing silicone oil is as follows: Among them, R is R' is methyl or ethyl, R" is ethyl; a is an integer between 50 and 250, preferably between 80 and 200; b is an integer between 70 and 180; c is an integer between 1 and 8; Preferably, the molar ratio of octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane and dialkoxysilane is 100:90:(0.9-2.6); the molar ratio of octamethylcyclotetrasiloxane and hexamethyldisiloxane is (80-200):

1.

10. The preparation method according to claim 7, characterized in that: In the step S2, the thickness of the formed glue is 20 to 300 microns, preferably 30 to 200 microns; Preferably, the adhesive is further cured by heating in later applications to achieve the purpose of bonding; the temperature of heating curing is 100-150° C. and the time is 20-60 minutes.

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