CN115490901B - Scratch-resistant silica gel film and preparation method thereof - Google Patents
Scratch-resistant silica gel film and preparation method thereof Download PDFInfo
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Abstract
The application relates to a scratch-resistant silica gel film and a preparation method thereof. The method comprises the following preparation steps: 1) Coating the substrate with organosilicon film-forming glue, wherein the thickness of the coated wet glue is 200-220 mu m, the curing temperature is 50-90 ℃, the curing time is 3-4min, and a silica gel layer is formed on the substrate; 2) Coating a bridging agent on the surface of the silica gel layer, wherein the thickness of the coated wet gel is 15-20 mu m, the curing temperature is 90-120 ℃, the curing time is 4-5min, and a bridging layer is formed on the silica gel layer; 3) Coating scratch-resistant glue on the surface of the bridging layer, wherein the thickness of the coated wet glue is 60-70 mu m, the curing temperature is 3-4min, the curing temperature is 90-150 ℃, forming a scratch-resistant layer on the bridging layer, and stripping the film from the substrate to obtain the composite film which is the scratch-resistant silica gel film. The preparation method has the advantages of simple operation and high production efficiency, and the prepared scratch-resistant silica gel film has a good scratch-resistant effect.
Description
Technical Field
The application relates to the technical field of silica gel products, in particular to a scratch-resistant silica gel film and a preparation method thereof.
Background
Silica gel can be divided into two major classes of organic silica gel and inorganic silica gel according to its properties and components, and organic silica gel is an organosilicon compound, which is a compound containing Si-C bond and at least one organic group is directly connected with silicon atom, and polysiloxane composed of silicon-oxygen bond (-Si-O-Si-) as skeleton is common, and has the greatest number, the deepest research and the widest application.
The silica gel product is a processing product taking the organic silicon compound as a main raw material, is stable in performance, difficult to deform, soft and comfortable, excellent in thermal stability, high and low temperature resistant, environment-friendly, nontoxic, easy to dye and the like after being subjected to vulcanization reaction, and can be used in the range of-40 ℃ to 230 ℃, so that the silica gel product is widely applied to the fields of electronic products, apparel ornaments, daily necessities and the like.
The silica gel product can be prepared into corresponding forms according to the requirements, such as a film for decorating shoes, clothes and the like, and is favored by people because the silica gel product is environment-friendly, nontoxic, recyclable, soft in hand feeling and the like. However, the film made of the silica gel is difficult to self-cure and repair by scratching, so that the silica gel product is easy to scratch in the using process, and scratches which are difficult to self-cure are formed on the surface of the silica gel product, so that the surface appearance of the silica gel product is influenced.
Disclosure of Invention
In order to reduce and improve the scratch resistance of the silica gel film, the application provides a scratch-resistant silica gel film and a preparation method thereof.
In a first aspect, the preparation method of the scratch-resistant silica gel film provided by the application adopts the following technical scheme:
a preparation method of a scratch-resistant silica gel film comprises the following steps:
1) Coating the substrate with organosilicon film-forming glue, wherein the thickness of the coated wet glue is 200-220 mu m, the curing temperature is 50-90 ℃, the curing time is 3-4min, and a silica gel layer is formed on the substrate;
2) Coating a bridging agent on the surface of the silica gel layer, wherein the thickness of the coated wet gel is 15-20 mu m, the curing temperature is 90-120 ℃, the curing time is 4-5min, and a bridging layer is formed on the silica gel layer;
3) Coating scratch-resistant glue on the surface of the bridging layer, wherein the thickness of the coated wet glue is 60-70 mu m, the curing temperature is 3-4min, the curing temperature is 90-150 ℃, forming a scratch-resistant layer on the bridging layer, and stripping the film from the substrate to obtain the composite film which is the scratch-resistant silica gel film.
The preparation method is simple to operate and high in production efficiency, and the prepared silica gel film has a good scratch-resistant effect, so that when the silica gel film is used for decorating shoes or clothes, the surface scratch of the silica gel film can be reduced, and the practicability of the silica gel film is improved. Meanwhile, the silica gel film is environment-friendly, nontoxic and free of environmental pollution, and can be recycled after being abandoned, so that the environment friendliness is improved.
1) The middle base material is release paper, can play a role in shaping, when the silicone film forming glue is used for coating, a silica gel layer is formed on a base layer after solidification, the solidification time is selected to be 3-4min, the solidification temperature is selected to be 50-90 ℃, the formed silica gel layer is in a semi-dry state (the surface humidity is 40-60 ℃) within the time and temperature range, the surface of the formed silica gel layer is somewhat sticky, so that the formed silica gel layer is convenient to adhere to a bridging agent in the follow-up process, furthermore, the coated wet glue (the thickness formed on the base material after the silicone film forming glue is coated) is selected to be 200-220 mu m, and the thickness range can enable the prepared silica gel film to have good toughness and softness, and can be easily attached to shoes and clothes for middle decoration.
2) The bridging agent is coated on the surface of the silica gel layer in a semi-dry state, plays a role in bridging, can enable the silica gel layer to be stably bonded with the scratch-resistant layer, reduces the possibility of cracking of a layer structure of a silica gel film, enables the silica gel layer to be stably bonded with the scratch-resistant layer due to the formed silica gel layer within the thickness range to be 15-20 mu m, and further, the bridging agent which is cured and coated at the temperature range of 90-120 ℃ and the time range of 4-5min is preferably selected, so that the rapidly cured bridging agent (fully cured) and the further cured silica gel layer can be formed, and the stable bridging layer is formed on the surface of the silica gel layer.
And 3) through utilizing scratch-resistant glue to coat on the surface of the bridging layer, form on the face of bridging layer after the solidification and imitate the scraping layer, this scratch-resistant layer has better scratch-resistant effect, when the silica gel membrane was scraped, the silica gel membrane was difficult to damage and the scratch can disappear in 3s, makes the shoes or the dress surface that the silica gel membrane was decorated remain pleasing to the eye, improves the practicality of silica gel membrane. The scratch-resistant glue has a scratch-resistant effect, and after the scratch-resistant glue is coated, the scratch-resistant layer formed by curing has a good scratch-resistant effect.
In summary, because the surface of the existing silica gel film is easy to scratch, the surface of the existing silica gel film is easy to scratch in the use process of shoes and clothes for decoration, the attractiveness is affected, and the practicability of the silica gel film is reduced, therefore, under the basis of ensuring the flexibility of the silica gel film, the application firstly adopts the organosilicon film forming glue to coat with a certain wet glue thickness, then cures at a specific time temperature to form a semi-dry silica gel layer, and then coats a bridging agent on the semi-dry silica gel layer. Therefore, the silica gel film prepared by the method has the advantages of environmental protection and no toxicity of organic silicon, better scratch resistance effect and practicability.
After the silica gel membrane production of this application is accomplished generally, can cover 50umPET protection film at its both sides, be convenient for carry out the rolling with the silica gel membrane, transportation etc. reduce the silica gel membrane and receive the damage in the transportation. When the anti-scratch protective film is used for decorating shoes or clothes, the PET protective film on the surface is torn, one surface of the silica gel film silica gel layer is attached to the surface of the shoes or clothes, so that when the anti-scratch protective film is scratched, the scratch of the surface of the silica gel film is reduced, and the practicability of the silica gel film is improved.
Further, the curing temperatures mentioned in 1) to 3) are divided into six sections, specifically as follows:
1) Curing temperature of (a): the temperature of the first section is 45-55 ℃, and the drying temperature of the second section is 55-65 ℃; the temperature of the third section is 70-85 ℃, and the temperatures of the fourth section to the fifth section are 85-95 ℃; the sixth section is at 50-70 deg.c.
2) Curing temperature of (a): the temperature of the first section is 70-90 ℃, and the drying temperature of the second section is 80-100 ℃; the temperature of the third section to the fifth section is 110-130 ℃; the sixth section is at 90-110 ℃.
3) Curing temperature of (a): the temperature of the first section is 80-100 ℃, and the drying temperature of the second section is 110-130 ℃; the temperature of the third section is 125-140 ℃, and the temperatures of the fourth section to the fifth section are 145-160 ℃; the sixth section is at 110-130 deg.c.
In the step 1), the temperature is reduced from the first stage curing temperature to the sixth stage curing temperature, the temperature in the whole curing process is not higher than 100 ℃, and the curing temperature is mostly 50-85 ℃, so that the formed silica gel layer can be stabilized on the base material by the curing mode, the surface of the silica gel layer is in a semi-dry state (with certain humidity and easy to adhere), and when the bridging agent is coated, the bridging agent is easy to adhere to the surface of the silica gel layer, so that the formed bridging layer is tightly connected with the organic silicon layer, and the structural stability of the scratch-resistant silica gel film is improved.
The curing temperature of one to six sections in the step 2) is higher than the curing temperature of one to six sections corresponding to the step 1), so that the bridging agent coated on the silica gel layer is rapidly cured to form a bridging layer, and the curing temperature is higher than 100 ℃, so that the diluent in the bridging agent can be completely volatilized, the environmental protection performance of the scratch-resistant silica gel film is improved, the silica gel layer is further cured in the temperature setting range, and the tight connectivity between the bridging layer and the organic silicon layer is further improved.
The curing temperature of one to six sections in the above 3) is higher than the curing temperature of one to six sections corresponding to 2), and the effect is that the scratch-resistant glue can be rapidly cured, stable scratch-resistant glue can be formed on the bridging layer, and the silica gel layer and the bridging layer can be further cured, so that the layer structure of the scratch-resistant silica gel film is stable. In addition, in the fifth stage of solidification, the temperature is up to 145-160 ℃, and in the temperature range, the diluent (solvent) entrained in the surface silica gel layer, the bridging layer and the scratch-resistant layer is completely volatilized, so that the environment-friendly scratch-resistant silica gel film is obtained.
The sectional solidification is selected, so that the prepared silica gel film has stable layer structure and high production effect.
Preferably, the scratch-resistant glue is prepared by mixing the following raw materials in parts by weight:
scratch-resistant main adhesive 100 parts
Scratch-resistant auxiliary agent 38-42 parts
65-75 parts of diluent.
Preferably, the scratch-resistant auxiliary agent is a cyanate ester curing agent, and the scratch-resistant main adhesive is polyester polyurethane resin.
The weight parts of the raw materials and the selection of the raw materials are the preferred selection of the application, wherein the scratch-resistant main adhesive has a good scratch-resistant effect, the scratch-resistant auxiliary agent plays a role in curing, and can improve the scratch-resistant effect, so that the prepared scratch-resistant layer is not easy to scratch, the diluent plays a role in dilution, and the scratch-resistant adhesive is convenient to coat. The diluent is preferably ethyl butyl ester and/or butyl acetate.
The scratch-resistant auxiliary agent is preferably a cyanate ester curing agent, the NCO content of which is 16-17%, the viscosity of which is 130-300mPa.s and the solid content of which is 74-76%. The cyanate curing agent has better yellowing resistance and weather resistance,
the polyol polyurethane emulsion is polyester polyurethane resin, the solid content is 35-45%, and the viscosity is 500-1000mPa.s. Has better water resistance, toughness and adhesiveness, etc. The formed scratch-resistant layer has better scratch-resistant effect.
Preferably, the scratch-resistant main adhesive consists of the following raw materials in parts by weight:
35-38 parts of polyester polyol
5-15 parts of polycarbonate diol
5-10 parts of modified organosilicon
0.1 to 0.3 percent of organic tin catalyst.
The modified organic silicon is polyester modified organic silicon resin, the solid content is 65+/-2 percent (%), and the viscosity is 800-1000mPa.s; good adhesion, moisture resistance and aging resistance.
The polycarbonate diol is called PCDL for short, has excellent weather resistance, good elasticity and flexibility, and is used for preparing the soft hand feeling coating, thereby having the functions of low gloss, anti-dazzle and sound absorption, and also having special elastic touch feeling, impact resistance, scratch resistance and high weather resistance. The viscosity is 600-2400mPa.s, the average molecular weight is 500-1000, and the hydroxyl is 100-250kOHmg/g.
The hydroxyl value of the polyester polyol is 53-59mgKOH/g, the viscosity is 300-800 viscosity (75 ℃/cps). The polyurethane polyol is a polycaprolactone polyol.
The scratch-resistant main adhesive obtained by polyester polyol, polycarbonate diol, modified organic silicon and the like has good adhesiveness, toughness, tear resistance, scratch resistance and the like, and when the scratch-resistant main adhesive is compounded with scratch-resistant auxiliary agents, the obtained scratch-resistant adhesive has good adhesion, toughness, tear resistance, scratch resistance and the like, and further the scratch-resistant layer obtained by coating has good scratch resistance and tear resistance, so that the possibility of scratching a silica gel film is reduced.
Preferably, the scratch-resistant glue is prepared by the following method:
step one: according to the weight parts, the method comprises the following steps: and (3) weighing polyester polyol and polycarbonate diol, uniformly mixing, heating to 125-135 ℃, cooling to 80-90 ℃, adding modified organic silicon, stirring for 0.5-1h, vacuumizing, dehydrating for 3-5h, cooling to 65-75 ℃, adding an organotin catalyst, and uniformly stirring to obtain the scratch-resistant main adhesive.
Step two: and (2) weighing the scratch-resistant auxiliary agent according to parts by weight, uniformly mixing the scratch-resistant auxiliary agent with the scratch-resistant main adhesive obtained in the step (1), adding a diluent, and stirring for 20-25min to obtain the scratch-resistant adhesive.
The scratch-resistant layer formed after the scratch-resistant glue prepared by the preparation method is cured has a good scratch-resistant effect, the scratch of the prepared silica gel film can be reduced, and the practicability of the silica gel film is provided.
Preferably, the solid content of the organosilicon film-forming glue is 55-65%.
The organic silicon film forming glue with the solid content range has good adhesiveness, is easy to adhere to a substrate to form a silica gel layer, and ensures that the prepared silica gel layer glue has good toughness and softness, and improves the softness and toughness of the silica gel film.
Preferably, the organosilicon film-forming glue is prepared by the following method: the weight ratio of the components is (1-2): 100, weighing the catalyst and the main adhesive, and stirring for 20-25min to obtain the organosilicon film-forming glue.
The main component of the main adhesive is silicon resin, the silicon resin is environment-friendly organic silicon resin, and the viscosity is 1200-1400 Pa.s. The environment-friendly organic silicon resin has good adhesiveness, and can enable the organic silicon film-forming glue to be easy to form a film. And the environmental protection of the silica gel film is improved.
Preferably, the main component of the main adhesive is silicone resin, and the solid content of the main adhesive is 73-77%.
The solid content of the main adhesive can be adjusted by adding ethyl acetate, so that the obtained organic silicon film-forming adhesive is easy to form a film and good in adhesiveness, and is further stably adhered to a bridging layer, so that the structural system of a silica gel film is stable, and cracking and other phenomena are not easy to occur.
Preferably, the bridging agent is obtained by mixing a bridging main agent and a bridging curing agent in a weight ratio of 100:4.5-5.5.
Wherein the bridging curing agent is polyisocyanate HDI curing agent, the viscosity is 2500-4000 Pa.s, and the NCO content is 21.5-22.5%.
Preferably, the main component of the bridging main agent is polyester polyurethane. The solid content of the bridging main agent is 38-42%, and the viscosity is 700-900mPa.s.
The bridging agent prepared by compounding the polyisocyanate HDI curing agent with the polyester polyurethane has good adhesiveness, and can be stably connected with a silica gel layer when being coated on the silica gel layer, so that the possibility of separating a silica gel film layer structure is reduced.
In a second aspect, the present application provides a scratch resistant silicone film made by a method of making the scratch resistant silicone film of the claims.
The scratch-resistant silica gel film has better scratch resistance, and reduces the scratch of the silica gel film.
In summary, the present application has the following beneficial effects:
1. according to the method, the silica gel layer, the bridging layer and the scratch-resistant layer are sequentially formed, so that the silica gel film with a stable layer structure is formed. The scratch-resistant layer has good scratch-resistant effect, the surface of the silica gel film is reduced from being scratched, the practicability of the silica gel film is improved, and when the silica gel film is used for decoration of shoes or clothes, the surface of the silica gel film can be attractive, and the possibility of scratching is reduced.
2. The anti-scratch glue prepared by compounding the polyester polyol, the polycarbonate diol, the modified organic silicon and the like has good adhesion, and when the anti-scratch glue is coated on the surface of the bridging layer, the anti-scratch glue can be stably bonded with the bridging layer, a scratch-resistant layer with good scratch resistance effect is formed, and the possibility of scratching the prepared silica gel film is reduced.
Detailed Description
The present application is described in further detail below with reference to examples.
The parameters of some of the raw materials according to the examples of the present application are as follows:
the scratch-resistant auxiliaries of examples 1 to 10 are preferably cyanate ester curing agents having NCO contents of 16 to 17%, viscosities of 130 to 300mPa.s and solids contents of 74 to 76%.
The scratch-resistant main adhesive of examples 1-7 is a polyol polyurethane emulsion, which is a polyester polyurethane resin, has a solid content of 35-45% and a viscosity of 500-1000mpa.s.
The modified silicones of examples 8-10 were polyester modified silicone resins with a solids content of 65.+ -.2% (%) and a viscosity of 800-1000mPa.s.
The polycarbonate diols of examples 8-10 have a viscosity of 600-2400 Pa.s, an average molecular weight of 500-1000, and a hydroxyl group of 100-250kOHmg/g.
The polyester polyols of examples 8-10 had hydroxyl numbers of 53-59mgKOH/g, viscosities of 300-800 viscosity (75 ℃/cps). The polyurethane polyol is a polycaprolactone polyol.
The main component of the main glue of examples 1-10 was silicone resin, which was an environmentally friendly silicone resin with a viscosity of 1200-1400mpa.s.
The bridging curing agent of examples 1-10 is polyisocyanate HDI curing agent, the viscosity is 2500-4000 Pa.s, and the NCO content is 21.5-22.5%.
The main component of the bridging main agent of examples 1-10 is polyester polyurethane, the solid content of the bridging main agent is 38-42%, and the viscosity is 700-900mPa.s.
Examples
Example 1
A preparation method of a scratch-resistant silica gel film comprises the following steps:
1) Placing the organosilicon film-forming glue into a roller coater, setting the thickness of wet glue to be 200 mu m, coating the organosilicon film-forming glue on the surface of a substrate, and entering drying equipment for curing after coating, wherein the drying equipment has six drying sections, the temperature of the first section is 50 ℃, and the drying temperature of the second section is 60 ℃; the temperature of the third section is 80 ℃, and the temperatures of the fourth section to the fifth section are 90 ℃; the sixth stage of drying temperature is 60 ℃, and the curing time is 3min in total, so that a silica gel layer is formed on the surface of the substrate (the silica gel layer is in a semi-dry state at the moment, and the humidity is 50 ℃).
2) Coating bridging agent on the surface of the silica gel layer by a roller coater, wherein the thickness of the coated wet gel is 15 mu m, and feeding the wet gel into a drying device for curing, wherein the drying device has six drying sections, the temperature of the first section is 80 ℃, and the drying temperature of the second section is 90 ℃; the temperatures of the third section to the fifth section are 120 ℃; and the sixth section of drying temperature is 100 ℃, the curing time is 4min in total, and a bridging layer is formed on the silica gel layer.
3) Putting scratch-resistant glue into a corresponding coating machine, setting the thickness of wet glue to be 60 mu m, and when the bridging layer in the step 2) is conveyed to the coating machine, coating the scratch-resistant glue on the surface of the bridging layer by the coating machine, and then entering a drying device for curing, wherein the drying device has six drying sections, the temperature of the first section is 90 ℃, and the drying temperature of the second section is 120 ℃; the temperature of the third section is 130 ℃, and the temperatures of the fourth section to the fifth section are 150 ℃; and the sixth section of drying temperature is 120 ℃ and curing temperature is 3min, an anti-scratch layer is formed on the bridging layer, and the film and the base material are peeled off, so that the obtained composite film is the anti-scratch silica gel film.
Wherein the scratch-resistant auxiliary agent is a cyanate ester curing agent, and the scratch-resistant main adhesive is polyester polyurethane resin. The organosilicon film-forming glue is prepared by the following method: the weight (kg) ratio is 1:100, weighing a catalyst (platinum catalyst) and main glue (solid content is 75%), stirring for 20min to obtain a mixture, and adding ethyl acetate into the mixture to adjust the solid content to 60%, so as to obtain the organosilicon film-forming glue.
The bridging agent is prepared by the following method: weighing the bridging main agent and the bridging curing agent according to the weight (kg) ratio of 100:4.5, and uniformly mixing to obtain the bridging agent.
The scratch-resistant glue is prepared by the following steps of weighing 100kg of scratch-resistant main glue and 40kg of scratch-resistant auxiliary agent, uniformly mixing, adding 70kg of ethyl acetate for dilution, and stirring for 20min to obtain the scratch-resistant glue.
Examples 2 to 3
Examples 2-3 differ from example 1 in that: the amounts of the raw materials used are different, and are shown in Table 1;
TABLE 1 amounts of raw materials (kg) for examples 1 to 5
Examples 4 to 5
Examples 4-5 differ from example 1 in that: the curing time, curing temperature and thickness of the coated wet glue are different, and are shown in table 2;
TABLE 2 curing time, curing temperature for examples 1, 4-5
Examples 6 to 7
Examples 6-7 differ from example 1 in that: the thickness of the coated wet glue is different, and is shown in table 3;
TABLE 3 thickness of wet glue coated in example 1, examples 6-7
Example 8
Example 8 differs from example 1 in that the scratch resistant glue is made by the following steps:
step one: weighing 35kg of polyester polyol and 5kg of polycarbonate diol, putting into a reaction kettle, uniformly mixing, heating to 125 ℃, cooling to 80 ℃, adding modified organic silicon, stirring for 0.5h, vacuumizing to 100Kpa, dehydrating for 3h, cooling to 65 ℃, adding 0.1kg of organic tin catalyst, and uniformly stirring to obtain scratch-resistant main adhesive;
step two: weighing 38kg of scratch-resistant auxiliary agent, uniformly mixing with 100kg of scratch-resistant main glue obtained in the step 1, adding 65kg of ethyl acetate, and stirring for 20-25min to obtain the scratch-resistant glue.
Examples 9 to 10
Examples 9-10 differ from example 8 in that: the amounts of scratch-resistant glue materials are different, and are shown in table 4;
TABLE 4 raw materials used (kg) for examples 8-9
Comparative example
Comparative example 1
Comparative example 1 differs from example 1 in a method for producing a scratch-resistant silicone film, comprising the steps of: placing the organosilicon film-forming glue into a roller coater, setting the thickness of wet glue to 275 mu m, coating the organosilicon film-forming glue on the surface of a substrate, and entering drying equipment after coating, wherein the temperature of the first section is 90 ℃ and the drying temperature of the second section is 120 ℃; the temperature of the third section is 130 ℃, and the temperatures of the fourth section to the fifth section are 150 ℃; the sixth section of drying temperature is 120 ℃, and the total curing time is 15min, so that a silica gel layer is formed on the surface of the base material; and stripping the film from the substrate to obtain the composite film which is the scratch-resistant silica gel film.
Comparative example 2
Comparative example 2 is different from example 1 in that: and (3) heating the silica gel layer obtained in the step (1) to 150 ℃ again, and curing for 1min to obtain the completely dried silica gel layer.
Comparative example 3
Comparative example 3 is different from example 1 in that a method for producing a scratch-resistant silicone film includes the steps of:
1) Placing the organosilicon film-forming glue into a roller coater, setting the thickness of wet glue to be 200 mu m, coating the organosilicon film-forming glue on the surface of a substrate, and entering drying equipment for curing after coating, wherein the drying equipment has six drying sections, the temperature of the first section is 50 ℃, and the drying temperature of the second section is 60 ℃; the temperature of the third section is 80 ℃, and the temperatures of the fourth section to the fifth section are 90 ℃; the sixth stage of drying temperature is 60 ℃, and the curing time is 3min in total, so that a silica gel layer is formed on the surface of the substrate (the silica gel layer is in a semi-dry state at the moment, and the humidity is 50 ℃).
2) Putting scratch-resistant glue into a corresponding coating machine, setting the thickness of wet glue to be 75 mu m, and when the silica gel layer in the step 1) is conveyed to the coating machine, coating the scratch-resistant glue on the surface of a bridging layer by the coating machine, and then entering a drying device for curing, wherein the drying device has six drying sections, the temperature of the first section is 90 ℃, and the drying temperature of the second section is 120 ℃; the temperature of the third section is 130 ℃, and the temperatures of the fourth section to the fifth section are 150 ℃; and the sixth section of drying temperature is 120 ℃ and curing temperature is 3min, an anti-scratch layer is formed on the silica gel layer, and the film and the substrate are peeled off, so that the obtained composite film is the anti-scratch silica gel film.
Comparative example 4
Comparative example 4 differs from example 1 in that: the wet glue thickness of the scratch-resistant glue coating was 20 μm.
Comparative example 5
Comparative example 5 differs from example 8 in that: the modified silicone in example 8 was replaced with polycarbonate diol in equal amounts.
Performance test
Detection method/test method
1. Scratch resistance test
The silica gel films obtained in examples 1 to 10 and comparative examples 1 to 5 were cut into test pieces (length: 10cm, width: 10 cm), the test pieces were flatly attached to a substrate (wood board or plastic), the surfaces of scratch-resistant layers of the test pieces were scratched back and forth (scratch strength: 5N) with a copper brush having a copper wire diameter of 0.1mm, a timer was started, the time for scratch disappearance was recorded, the test was repeated 3 times, and the average value (note: comparative example 1 was scratched back and forth directly on the surfaces thereof) was taken, and specific data were shown in Table 5.
2. Water resistance test
The silica gel films obtained in examples 1 to 10 and comparative examples 1 to 5 were put into an electric pan at 80℃and boiled in water for 30 minutes, and whether or not the surface of the silica gel film had the phenomenon of bubbles, discoloration, etc., were recorded, as shown in Table 5.
3. Tear resistance test
The silica gel films obtained in examples 1 to 10 and comparative examples 1 to 5 were subjected to tearing strength detection by using a XLW-L intelligent electronic tensile tester with reference to the national standard GBT 529-2008, and specific data are shown in Table 5;
TABLE 5 Experimental data for examples 1-10 and comparative examples 1-5
As can be seen from the combination of example 1 and comparative example 1 and table 5, the scratch resistance (scratch resistance and tear strength) of example 1 is better than that of comparative example 1, which shows that the silica gel film has better toughness and/or scratch resistance by coating the scratch resistance layer on the silica gel layer, and the possibility of scratching the silica gel film is reduced.
As can be seen from the combination of example 1 and comparative example 2 and table 5, the comparative example 2 shows bubbles, but the example 1 does not show bubbles, which means that the layer structure of the silica gel film is unstable in connection, and moisture is easy to permeate to generate bubbles, and further means that the silica gel layer is in a semi-dry state and then coated with the bridging agent, so that the bridging agent completely permeates the surface of the silica gel layer, and the silica gel layer and the bridging layer are stably connected, so that the layer structure of the silica gel film is stably connected.
As can be seen from the combination of example 1 and comparative example 3 and the combination of table 5, the comparative example 3 has bubbles, but the example 1 has no bubbles, which indicates that the layer structure of the silica gel film is unstable in connection, further indicates that the bridging agent can stably adhere to the silica gel layer, and after curing, a stable bridging layer can be formed on the silica gel layer, and the bridging layer can stably adhere to the scratch-resistant glue, and after curing, the surface of the bridging layer forms a stable scratch-resistant layer, so that the layer structure of the silica gel film is stable in adhesion.
As can be seen from the combination of example 1 and comparative example 4 and the combination of table 5, the scratch resistance effect of comparative example 4 is inferior to that of example 1, indicating that the scratch resistance effect is significantly reduced when the coated moisture amount is less than the moisture amount range of the present application.
As can be seen from the combination of example 8 and comparative example 5 and table 5, when the modified silicone was not added, the scratch resistance test time was increased, which indicates that the added modified silicone had a better toughening effect and was able to reduce the possibility of scratching the silica gel film.
As can be seen from the combination of examples 1 to 7 and examples 8 to 10 and the combination of table 5, when the polyester polyol, the polycarbonate diol, the modified organic silicon and the like are adopted for compounding, the obtained scratch-resistant main glue is used for producing scratch-resistant glue, and further the scratch-resistant layer prepared after the scratch-resistant glue is coated and cured has better toughness and scratch resistance, so that the scratch-resistant effect of the silica gel film is optimal.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (3)
1. The preparation method of the scratch-resistant silica gel film is characterized by comprising the following steps of:
1) Coating the substrate with organosilicon film-forming glue, wherein the thickness of the coated wet glue is 200-220 mu m, the curing temperature is 50-90 ℃, the curing time is 3-4min, and a silica gel layer is formed on the substrate;
2) Coating a bridging agent on the surface of the silica gel layer, wherein the thickness of the coated wet gel is 15-20 mu m, the curing temperature is 90-120 ℃, the curing time is 4-5min, and a bridging layer is formed on the silica gel layer;
3) Coating scratch-resistant glue on the surface of the bridging layer, wherein the thickness of the coated wet glue is 60-70 mu m, the curing temperature is 3-4min, the curing temperature is 90-150 ℃, the scratch-resistant layer is formed on the bridging layer, and the film and the substrate are peeled off to obtain a composite film which is a scratch-resistant silica gel film;
the scratch-resistant glue is prepared by mixing the following raw materials in parts by weight:
scratch-resistant main adhesive 100 parts
Scratch-resistant auxiliary agent 38-42 parts
65-75 parts of diluent;
the scratch-resistant auxiliary agent is a cyanate ester curing agent, and the scratch-resistant main adhesive is polyester polyurethane resin;
the scratch-resistant main adhesive consists of the following raw materials in parts by weight:
35-38 parts of polyester polyol
5-15 parts of polycarbonate diol
5-10 parts of modified organosilicon
0.1 to 0.3 percent of organotin catalyst;
the scratch-resistant glue is prepared by the following method:
step one: weighing polyester polyol and polycarbonate diol, uniformly mixing, heating to 125-135 ℃, cooling to 80-90 ℃, adding modified organic silicon, stirring for 0.5-1h, vacuumizing, dehydrating for 3-5h, cooling to 65-75 ℃, adding an organotin catalyst, and uniformly stirring to obtain scratch-resistant main adhesive;
step two: weighing scratch-resistant auxiliary agent according to parts by weight, uniformly mixing the auxiliary agent with the scratch-resistant main adhesive obtained in the step 1, adding a diluent, and stirring for 20-25min to obtain the scratch-resistant adhesive;
the solid content of the organosilicon film-forming glue is 55-65%;
the organosilicon film-forming glue is prepared by the following method: the weight ratio of the components is (1-2): 100, weighing the catalyst and the main adhesive, and stirring for 20-25min to obtain the organosilicon film-forming glue;
the main component of the main adhesive is silicone resin, and the solid content of the main adhesive is 73-77%.
2. The method for preparing the scratch-resistant silica gel film according to claim 1, wherein the method comprises the following steps: the bridging agent is obtained by mixing a bridging main agent and a bridging curing agent in a weight ratio of 100:4.5-5.5.
3. A scratch resistant silicone film, characterized by: a method for producing a scratch-resistant silicone film as set forth in any one of claims 1 to 2.
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