Antistatic optical-grade hydrophobic material and preparation method thereof

文档序号:750 发布日期:2021-09-17 浏览:70次 中文

1. An antistatic optical grade hydrophobic material, comprising:

the hydrophobic functional layer is arranged on one side or both sides of the substrate layer through a thermoplastic adhesive;

the base layer comprises the following raw material components in parts by weight: 80-120 parts of first resin matrix, 10-20 parts of antistatic master batch and 5-15 parts of auxiliary agent;

the hydrophobic functional layer comprises the following raw material components in parts by weight: 20-30 parts of a second resin matrix, 8 parts of nano silicon dioxide particles, 1% of a silane coupling agent component and 5 parts of a curing agent.

2. The antistatic optical grade hydrophobic material of claim 1, wherein: the first resin matrix is polycarbonate and the second resin matrix is epoxy resin, preferably epoxy resin (E-51).

3. The antistatic optical grade hydrophobic material of claim 1, wherein: the antistatic master batch comprises the following raw material components in parts by weight: 40-60 parts of antistatic agent and 3 parts of auxiliary crosslinking agent.

4. An antistatic optical grade hydrophobic material according to claim 3, wherein: the antistatic agent is a permanent antistatic agent NC6321, and the auxiliary crosslinking agent is one or more of styrene-acrylonitrile grafted maleic anhydride resin, acrylonitrile-butadiene-styrene grafted maleic anhydride resin and polystyrene grafted maleic anhydride resin.

5. The antistatic optical grade hydrophobic material of claim 1, wherein: the auxiliary agent comprises the following components in parts by weight: 2 parts of antioxidant and 4 parts of ultraviolet resistant additive.

6. The antistatic optical grade hydrophobic material of claim 5, wherein: the antioxidant is antioxidant 168 or antioxidant 1010, the ultraviolet resistant additive is a compound of a light stabilizer and an ultraviolet absorber, the light stabilizer is light stabilizer 622, and the ultraviolet absorber is UV-328 or UV-531.

7. The antistatic optical grade hydrophobic material of claim 1, wherein: the curing agent is triethanolamine.

8. The antistatic optical grade hydrophobic material of claim 1, wherein: the thermoplastic adhesive is epoxy resin type adhesive

9. The antistatic optical grade hydrophobic material of claim 1, wherein: it is applied to lens, glass, lamp ornaments or plastic products.

10. A preparation method of an antistatic optical-grade hydrophobic material comprises the following steps:

step 1: preparing a substrate layer: taking the raw materials according to the parts by weight, extruding, cooling and granulating through a melt blending antistatic agent and an auxiliary crosslinking agent to obtain antistatic master batches, grinding a first resin matrix, continuously adding the antistatic master batches into the first resin matrix for mixing and grinding until the antistatic master batches are completely added, placing a mixture of the first resin matrix and the antistatic master batches after full grinding and an auxiliary agent in a 70-75 ℃ water bath, stirring at a high speed for 30min, controlling the water bath temperature to 65 ℃, performing ultrasonic treatment for 1h by adopting 40KHz to form a viscous colloid, performing dehydration and drying to form a mixed material, introducing the mixed material into an extruder for pressurization and extrusion, controlling the melting temperature to be 230-250 ℃, and then cooling and cutting to form a transparent flaky substrate layer;

step 2: preparation of a hydrophobic functional layer: preparing the hydrophobic functional layer by a sol-gel method, heating and mixing a second resin matrix and a silane coupling agent at the mixing temperature of 85 ℃, reacting for 2 hours, cooling to 65 ℃, adding tetraethoxysilane and tetrabutyl titanate serving as a composite sol precursor, stirring, reacting and mixing for 1 hour, adding nano-silica particles, continuously dropwise adding ammonia water at the temperature of 65 ℃, stirring and mixing for 1 hour, adding a defoaming agent and a curing agent at the temperature of 120 ℃, stirring and mixing for 2 hours, and dehydrating to obtain the hydrophobic functional layer formed by the transparent modified silica/epoxy resin hybrid material;

and step 3: compounding the hydrophobic functional layer obtained in the step 2 on one side or two sides of the substrate layer obtained in the step 1 through a thermoplastic adhesive, wherein the hot melting temperature of the thermoplastic adhesive is 180-200 ℃, keeping the temperature at 90-95 ℃ for 30-60 min after adhesion and compounding, and slowly cooling to room temperature to finish the process.

Background

The static dissipative material refers to a material with the surface resistivity of 106-1012 ohms, wherein the material with the surface resistivity of 1010-1012 ohms has the function of preventing static from being accumulated locally, and can effectively avoid static dust collection; the material with the surface resistivity of 106-109 ohms has the function of quickly dissipating static electricity, and can effectively prevent potential safety hazards such as electric shock and fire caused by static discharge. In the field of optics and electronics/electrical appliance manufacturing, the antistatic performance of antistatic materials is often generated by the action of macromolecular antistatic agents, and the antistatic agents are unevenly distributed in the materials due to the high surface area ratio, for example, the patent number CN106189167A discloses 'an efficient antistatic PC/ABS composite material and a preparation method thereof', the antistatic agents, compatilizers and dispersing agents are evenly mixed in proportion, and the processing temperature is controlled to 190-; and blending the prepared high-efficiency antistatic master batch with polycarbonate and ABS, extruding by using a double screw, controlling the processing temperature to be 220-. But the internal components of the antistatic material are not well formed, so that the consistency of the whole product is poor.

The wettability of the surface of the material is a complex property, generally, a contact angle of more than 90 degrees is hydrophobic, a contact angle of more than 150 degrees is super-hydrophobic, and when the material has functional requirements for antifouling, self-cleaning and the like, the corresponding hydrophobic layer is adopted, in the prior art, a hydrophobic coating is usually compounded on a substrate layer, although the method is simple, convenient and easy to implement, the composite hydrophobic coating is easily scratched, washed off and loses effectiveness after being influenced by external high temperature, impact and other adverse factors for a long time, for example, the composite hydrophobic coating is prepared by the method for preparing the high-transparency wear-resistant super-hydrophobic composite coating disclosed in the patent No. CN107022279B, modified epoxy resin glue is coated on the surface of a substrate to be used as an adhesive layer, then hydrophobic nano silica dispersion liquid is coated on the surface, the nano silica dispersion liquid is dried at room temperature to obtain the high-transparency wear-resistant epoxy resin/silica super-hydrophobic composite coating, and the coated nano silica dispersion liquid can be peeled off in adverse environments for a long time, separated from the substrate.

Disclosure of Invention

In order to solve the problems in the background art and meet the requirements of higher quality and stability, the invention provides the antistatic optical hydrophobic material and the preparation method thereof.

The invention provides the following technical scheme:

in a first aspect, the present invention provides an antistatic optical-grade hydrophobic material comprising:

the hydrophobic functional layer is arranged on one side or both sides of the substrate layer through a thermoplastic adhesive;

the base layer comprises the following raw material components in parts by weight: 80-120 parts of first resin matrix, 10-20 parts of antistatic master batch and 5-15 parts of auxiliary agent;

the hydrophobic functional layer comprises the following raw material components in parts by weight: 20-30 parts of a second resin matrix, 8 parts of nano silicon dioxide particles, 1% of a silane coupling agent component and 5 parts of a curing agent.

Preferably, the first resin matrix is polycarbonate, the second resin matrix is epoxy resin, preferably epoxy resin (E-51), the polycarbonate has good high light transmittance and a high refractive index, and is suitable for optical light transmission components, and the epoxy resin (E-51) is a thermosetting polymer synthetic material with good corrosion resistance, insulation, high strength and other properties, and can effectively overcome the influence of the external environment on the material.

Preferably, the antistatic master batch comprises the following raw material components in parts by weight: 40-60 parts of antistatic agent and 3 parts of auxiliary crosslinking agent.

Preferably, the antistatic agent is a permanent antistatic agent NC6321, which has small particle size and good dispersibility and can promote subsequent homogenization; the auxiliary crosslinking agent is one or more of styrene-acrylonitrile grafted maleic anhydride resin, acrylonitrile-butadiene-styrene grafted maleic anhydride resin and polystyrene grafted maleic anhydride resin, and the adhesion of the first resin matrix is promoted by utilizing the molecular viscosity of the auxiliary crosslinking agent, so that the strength of the matrix layer is enhanced.

Preferably, the auxiliary agent comprises the following components in parts by weight: 2 parts of antioxidant and 4 parts of ultraviolet resistant additive.

Preferably, the antioxidant is antioxidant 168 or antioxidant 1010, which is safe and reliable, and can protect the polymer in the matrix layer for a long time and effectively slow down the decomposition of the polymer, the ultraviolet resistance additive is a compound of a light stabilizer and an ultraviolet absorber, the light stabilizer is light stabilizer 622, which has good compatibility and thermal stability, and the ultraviolet absorber is UV-328 or UV-531, which is not only safe and environment-friendly, but also can ensure high transmittance of the material.

Preferably, the curing agent is triethanolamine, which is slightly alkaline and facilitates neutralization of acidic substances generated by polymerization and hydrolysis reactions.

Preferably, the thermoplastic adhesive is an epoxy resin type adhesive, and has excellent adhesive property and good compatibility with the hydrophobic functional layer.

Preferably, an antistatic optical grade hydrophobic material is applied to lenses, glass, lamp ornaments or plastic products.

In a second aspect, the present invention provides a method for preparing an antistatic optical-grade hydrophobic material, comprising the following steps:

step 1: preparing a substrate layer: taking the raw materials according to the parts by weight, extruding, cooling and granulating through a melt blending antistatic agent and an auxiliary crosslinking agent to obtain antistatic master batches, grinding a first resin matrix, continuously adding the antistatic master batches into the first resin matrix for mixing and grinding until the antistatic master batches are completely added, placing a mixture of the first resin matrix and the antistatic master batches after full grinding and an auxiliary agent in a 70-75 ℃ water bath, stirring at a high speed for 30min, controlling the water bath temperature to 65 ℃, performing ultrasonic treatment for 1h by adopting 40KHz to form a viscous colloid, performing dehydration and drying to form a mixed material, introducing the mixed material into an extruder for pressurization and extrusion, controlling the melting temperature to be 230-250 ℃, and then cooling and cutting to form a transparent flaky substrate layer;

step 2: preparation of a hydrophobic functional layer: preparing the hydrophobic functional layer by a sol-gel method, thermally mixing a second resin matrix with a silane coupling agent at 85 ℃, reacting for 2 hours, cooling to 65 ℃, adding tetraethoxysilane and tetrabutyl titanate serving as a composite sol precursor, stirring, reacting and mixing for 1 hour, adding nano-silica particles, continuously dropwise adding ammonia water at 65 ℃, stirring and mixing for 1 hour, adding a defoaming agent and a curing agent at 120 ℃, stirring and mixing for 2 hours, and dehydrating to obtain the hydrophobic functional layer formed by the transparent modified silica/epoxy resin hybrid material;

and step 3: compounding the hydrophobic functional layer obtained in the step 2 on one side or two sides of the substrate layer obtained in the step 1 through a thermoplastic adhesive, wherein the hot melting temperature of the thermoplastic adhesive is 180-200 ℃, after the adhesion is finished, keeping the temperature at 90-95 ℃ for 30-60 min, and slowly cooling to room temperature.

The invention has the beneficial effects that:

(1): the material has good antistatic capacity and hydrophobic capacity by matching the substrate layer with the hydrophobic functional layer, the substrate layer and the hydrophobic functional layer are compounded by utilizing the thermoplastic binder, the hydrophobic functional layer is combined with the second resin substrate and the nano-silica particles by utilizing the silane coupling agent to form mixed gel, the molecular bonding force of the mixed gel is strong, the gaps among the molecules are small, the thermoplastic binder is an epoxy resin type binder, the compatibility with the hydrophobic functional layer is good, the promotion of the bonding is facilitated, the peeling failure of the hydrophobic layer can be effectively avoided, the hydrophobic functional layer has good tensile resistance, the mechanical property is strong, and the service life of the material is effectively prolonged;

(2): the antistatic master batch is continuously added into the first resin matrix for mixing and grinding, and is subjected to ultrasonic treatment for 1 hour at 40KHz to form a viscous colloid, so that the reduction of the size of agglomerated particles in the material and the separation of tangled or bonded filler particles can be effectively promoted, the material is densely filled, the material is good in consistency and compatibility, antistatic agent particles are uniformly distributed, and the antistatic performance of the material is excellent;

(3): the epoxy resin forming the second resin matrix has stronger wear resistance, heat resistance and chemical resistance compared with polycarbonate forming the first resin matrix, the hydrophobic functional layer is arranged on one side or two sides of the matrix layer and protects the matrix layer, so that the phenomenon that excessive water molecules enter the matrix layer to cause failure of antistatic capacity is avoided, the light transmittance of the epoxy resin and the polycarbonate is good, the epoxy resin is not easy to color, the transparency of the material is facilitated, and the material can be easily made into materials such as lenses, glass, lamp ornaments, plastic products and the like.

Detailed Description

The present invention will be described in further detail with reference to the following examples, but it should not be construed that the scope of the above-described subject matter of the present invention is limited to the following examples, and that all the technologies that can be realized based on the above-described matters of the present invention belong to the scope of the present invention.

Example 1:

the embodiment provides an antistatic optical-grade hydrophobic material, which comprises:

the hydrophobic functional layer is arranged on one side or both sides of the substrate layer through a thermoplastic adhesive;

the base layer comprises the following raw material components in parts by weight:

80-120 parts of a first resin matrix,

10-20 parts of antistatic master batch,

5-15 parts of an auxiliary agent;

the hydrophobic functional layer comprises the following raw material components in parts by weight:

20-30 parts of a second resin matrix,

8 parts of nano silicon dioxide particles, namely,

the silane coupling agent component is 1 percent of the second resin matrix component,

5 parts of curing agent.

Wherein, preferably, the first resin matrix is polycarbonate;

the antistatic master batch comprises the following raw material components in parts by weight:

40-60 parts of an antistatic agent,

3 parts of an auxiliary crosslinking agent;

wherein, preferably, the antistatic agent is a permanent antistatic agent NC6321, and the auxiliary crosslinking agent is one or more of styrene-acrylonitrile grafted maleic anhydride resin, acrylonitrile-butadiene-styrene grafted maleic anhydride resin and polystyrene grafted maleic anhydride resin;

the auxiliary agent comprises the following components in parts by weight:

2 parts of an antioxidant;

4 parts of an anti-ultraviolet additive;

wherein, preferably, the antioxidant is antioxidant 168 or antioxidant 1010, the ultraviolet resistant additive is a compound of a light stabilizer and an ultraviolet absorber, the light stabilizer is light stabilizer 622, and the ultraviolet absorber is UV-328 or UV-531;

the second resin matrix is epoxy resin, preferably epoxy resin (E-51);

the silane coupling agent is H2N-silane coupling agent;

the curing agent is triethanolamine;

the thermoplastic adhesive is an epoxy resin type adhesive, has good compatibility with a second resin matrix in the hydrophobic functional layer, is beneficial to promoting adhesion, and can effectively avoid the peeling failure of the hydrophobic layer.

The preparation method comprises the following steps:

step 1: preparing a substrate layer: taking the raw materials according to the parts by weight, extruding, cooling and granulating through a melt blending antistatic agent and an auxiliary crosslinking agent to obtain antistatic master batches, grinding a first resin matrix, continuously adding the antistatic master batches into the first resin matrix for mixing and grinding until the antistatic master batches are completely added, placing a mixture of the first resin matrix and the antistatic master batches after full grinding and an auxiliary agent in a 70-75 ℃ water bath, stirring at a high speed for 30min, controlling the water bath temperature to 65 ℃, performing ultrasonic treatment for 1h by adopting 40KHz to form a viscous colloid, performing dehydration and drying to form a mixed material, introducing the mixed material into an extruder for pressurization and extrusion, controlling the melting temperature to be 230-250 ℃, and then cooling and cutting to form a transparent flaky substrate layer;

table 1 shows the composition of the three antistatic masterbatches of the invention

Step 2: preparation of a hydrophobic functional layer: preparing the hydrophobic functional layer by a sol-gel method, heating and mixing a second resin matrix and a silane coupling agent at the mixing temperature of 85 ℃, reacting for 2 hours, cooling to 65 ℃, adding tetraethoxysilane and tetrabutyl titanate serving as a composite sol precursor, stirring, reacting and mixing for 1 hour, adding nano-silica particles, continuously dropwise adding ammonia water at the temperature of 65 ℃, stirring and mixing for 1 hour, adding a defoaming agent and a curing agent at the temperature of 120 ℃, stirring and mixing for 2 hours, and dehydrating to obtain the hydrophobic functional layer formed by the transparent modified silica/epoxy resin hybrid material;

and step 3: compounding the hydrophobic functional layer obtained in the step 2 on one side or two sides of the substrate layer obtained in the step 1 through a thermoplastic adhesive, wherein the hot melting temperature of the thermoplastic adhesive is 180-200 ℃, after the adhesion is finished, keeping the temperature at 90-95 ℃ for 30-60 min, and slowly cooling to room temperature.

Table 2 is a table of the composition of the antistatic optical grade hydrophobic material of the present invention

Wherein: the antioxidant is antioxidant 168, the ultraviolet absorbent is UV-328, and the nanometer silicon dioxide particles are particles with particle size of 100 nm-300 nm.

Table 3 shows the performance test of the materials of examples 1 to 5 and comparative examples 1 to 4

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4
Tensile Strength (MPa) 14 16 18 20 18 18 18 18 18
Surface resistance (. OMEGA.) (temperature: 23 ℃ C.) 1015 1014 1015 1015 1010 1012 1010 1014 1015
Light transmittance (%) 93 90 88 85 84 82 83 86 90
Haze (%) 1.9 2.0 2.2 2.5 2.9 3.0 2.9 3.2 2.8
Static contact Angle with Water (°) 106 103 102 98 96 96 96 102 106

Table 3 the performance test results show that:

(1): the examples 1-5 show that except the example 5, the surface impedance of the material is 1014-1015, the antistatic performance of the material is good, the size reduction of agglomerated particles in the material and the separation of tangled or bonded filler particles can be effectively promoted by continuously adding the antistatic master batch into the first resin matrix for mixing and grinding and performing 40KHz ultrasonic treatment for 1h to form a viscous colloid, so that the material is densely filled, has good consistency and compatibility, the antistatic agent particles are uniformly distributed, and the antistatic performance is excellent;

(2): examples 1-5 and comparative examples 1-4 show that the hydrophobic functional layer prepared by the sol-gel method has static contact angles of 96 degrees and above, and can be effectively hydrophobic;

(3): the examples 3-5 and the comparative examples 1-4 show that the tensile strength of the material is more than or equal to 18MPa, the hydrophobic functional layer is combined with the second resin matrix and the nano-silica particles by using the silane coupling agent to form mixed gel, the molecular bonding force is strong, the gaps among the molecules are small, the hydrophobic functional layer has good tensile resistance, the mechanical property of the material is strong, and the service life of the material can be effectively prolonged;

(4): the examples 1 to 5 and the comparative examples 1 to 4 show that the antistatic optical-grade hydrophobic material obtained through the steps from the first step to the third step has the transmittance of more than 80% and the haze of less than 3.0, has excellent transmittance and haze and high light transmittance, is beneficial to the uniform passing of parallel light and promotes the capture of optical vision.

As can be observed from table 3: the components in the embodiments 3 and 4 have good antistatic property, tensile property, light transmittance and hydrophobic property, and the comprehensive performance is good, and the component proportion corresponding to the components in the embodiments 3 and 4 is optimized.

In the invention, the abrasion resistance, heat resistance and chemical resistance of the epoxy resin forming the second resin matrix are stronger than those of polycarbonate forming the first resin matrix, the polycarbonate has weak decomposition resistance, the hydrophobic functional layer is arranged on one side or two sides of the matrix layer, the hydrophobic functional layer protects the matrix layer and avoids the failure of antistatic ability caused by the fact that excessive water molecules enter the matrix layer, and the epoxy resin and the polycarbonate have good light transmittance and are not easy to color, thereby being beneficial to the transparency of materials and being easy to prepare materials such as lenses, glass, lamp ornaments, plastic products and the like.

Although the preferred embodiments of the present patent have been described in detail, the present patent is not limited to the above embodiments, and various changes and modifications can be made without departing from the spirit of the present patent within the knowledge of those skilled in the art.

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