阅读说明：本技术 一种光致变色板材及其制作工艺 (Photochromic plate and manufacturing process thereof ) 是由 姜吉旺 郑寿平 于 2019-10-10 设计创作，主要内容包括：本发明涉及一种板材制作工艺技术领域,更具体地说它涉及一种光致变色板材及其制作工艺；由以下重量配比的原料制成：TPU30-45份、触变剂3-5份和光致变色有机聚合物涂料70-90份；本发明中的光致变色有机聚合物涂料中的光致变色材料由有机光致变色材料和无机光致变色材料复配而成,其中无机光致变色材料的光生电子空穴有很强的氧化-还原性能,其与有机光致变色材料之间相互配合不仅能显著地提高板材对光的敏感度,增大板材的变色范围；还能充分利用太阳光中丰富的可见光的光谱能量激发光致变色效应,从而显著增强本发明制备的光致变色板材的变色效应；再者,本发明制备的光致变色板材变色的的稳定性好,抗疲劳性优而且变色时的灵敏度也比较高。(The invention relates to the technical field of a plate manufacturing process, in particular to a photochromic plate and a manufacturing process thereof; the feed is prepared from the following raw materials in parts by weight: 30-45 parts of TPU, 3-5 parts of thixotropic agent and 70-90 parts of photochromic organic polymer coating; the photochromic material in the photochromic organic polymer coating is prepared by compounding an organic photochromic material and an inorganic photochromic material, wherein a photoproduction electron hole of the inorganic photochromic material has strong oxidation-reduction performance, and the photochromic material and the organic photochromic material are matched with each other, so that the sensitivity of the plate to light can be obviously improved, and the color change range of the plate is enlarged; the photochromic effect can be excited by fully utilizing the spectral energy of abundant visible light in sunlight, so that the photochromic effect of the photochromic plate prepared by the method is obviously enhanced; in addition, the photochromic sheet prepared by the invention has good stability of color change, excellent fatigue resistance and higher sensitivity in color change.)

1. The photochromic plate is characterized by being prepared from the following raw materials in parts by weight: 30-45 parts of TPU, 3-5 parts of thixotropic agent and 70-90 parts of photochromic organic polymer coating;

wherein: the photochromic organic polymer coating is prepared from modified acrylic resin, a photochromic material and an organic solvent according to a mass ratio of 6-8: 0.3-0.6: 6-8, mixing and stirring.

2. The photochromic sheet material of claim 1, wherein: the thixotropic agent is hydrogenated castor oil or polyamide wax.

3. The photochromic sheet material of claim 1, wherein: the photochromic material is prepared from an organic photochromic material and an inorganic photochromic material according to a mass ratio of 1: 2-3, mixing; wherein:

the organic photochromic material is selected from quinolopyran or phenoxazine;

MoO is selected as inorganic photochromic material₃Or WO₃。

4. The photochromic sheet material of claim 1, wherein: the preparation method of the modified polyacrylic resin comprises the following steps:

a. accurately weighing cerium oxide powder with the mass of 2-4% of polyacrylic resin, transferring the cerium oxide powder into a high-speed mixer with the temperature of 55-65 ℃, spraying an ethanol solution containing 10-15% of silane coupling agent into the cerium oxide powder, and simultaneously mixing and stirring the cerium oxide powder uniformly at the speed of 300-400 r/min; wherein the dosage of the silane coupling agent is 2-4% of the mass of the cerium oxide powder;

b. uniformly stirring, carrying out spray treatment for 20-30min, taking out the activated cerium oxide powder from a high-speed mixer, placing the activated cerium oxide powder in a constant-temperature drying oven, and drying at 80-90 ℃ to obtain modified cerium oxide powder;

c. b, transferring the modified cerium oxide powder obtained in the step b and polyacrylic resin into a high-speed mixer, and adding an auxiliary agent with the mass 0.8-1.3 times that of the cerium oxide powder into the high-speed mixer; under the condition of 60-70 ℃, uniformly mixing and stirring at the speed of 200-300r/min, and granulating the mixture by a double-screw extruder to obtain modified polyacrylic resin;

wherein the auxiliary agent is prepared by mixing phosphite composite antioxidant, hindered phenol light stabilizer and the like.

5. The photochromic sheet material of claim 1, wherein: the organic solvent is one of BCS, EAC and IBA.

6. The manufacturing process of the photochromic plate material as claimed in claim 1, which comprises the following steps:

s1, accurately weighing the TPU, the thixotropic agent and the photochromic organic polymer coating according to the weight ratio, uniformly mixing and stirring the TPU and the thixotropic agent, transferring the mixture into a charging barrel of an injection molding machine for injection molding, and cooling to obtain a plate substrate;

s2, soaking the plate substrate obtained in the step S1 in photochromic organic polymer paint, raising the temperature of the photochromic organic polymer paint to 60-70 ℃, soaking for 4-8h at the constant temperature, and ultrasonically oscillating for 3-5min every 30-50min in the soaking process;

s3, taking the plate substrate out of the photochromic organic polymer coating, uniformly spreading the photochromic organic polymer coating on the surface of the plate substrate, fixing the plate substrate under the irradiation of an ultraviolet lamp, and trimming the plate substrate to obtain a finished photochromic plate;

and S4, performing quality inspection on the photochromic plate finished product obtained in the S3, discarding defective products with unqualified quality, and reserving qualified photochromic plate finished products.

7. The photochromic sheet material of claim 6, wherein: the cooling pressure in the S1 is 35-50bar, and the cooling time is 3-5S.

8. The photochromic sheet material of claim 6, wherein: and the frequency of the ultrasonic oscillation in the S2 is 20-28 KHz.

9. The photochromic sheet material of claim 6, wherein: the power of the ultraviolet lamp in the S3 is 500W.

Technical Field

The invention relates to the technical field of a plate manufacturing process, in particular to a photochromic plate and a manufacturing process thereof.

Background

Photochromic refers to a compound A, which can perform a specific chemical reaction or physical effect under the irradiation of light with a proper wavelength to obtain a product B, wherein the absorption spectrum (color) of the product B is obviously changed due to the change of the structure, and the product B can be restored to the original form under the irradiation of light with another wavelength or under the action of heat.

With the rapid development of photochromic materials, more and more photochromic materials are applied to the construction aspect, such as industrial plants and the like. At present, a chinese patent with application number 201610215895. X discloses a novel photochromic transparent plate, which is made of the following materials by weight percent: 50-80% of unsaturated polyester resin, 10-60% of reinforcing material, 0.5-3% of methyl ethyl ketone peroxide, 1-8% of cyclohexanone peroxide, 1-8% of cobalt naphthenate or cobalt isooctanoate and 0.5-5% of photochromic compound. When the sun is too strong, the plate can be changed from transparent to semitransparent or opaque to control the transmittance of light, and when the ultraviolet rays are weakened, the plate is changed into pure transparent to increase the transmittance.

Although the transparent plate provided by the above patent document has a certain color change performance, the color change rate is relatively slow, i.e. the color change sensitivity is relatively poor. Moreover, the fatigue resistance of the material itself is relatively poor, so that the service life of the material is correspondingly shortened.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide a photochromic plate and a manufacturing process thereof, and the photochromic plate has the advantages that: not only has higher sensitivity to light, but also has wider color change range. But also has the advantages of good stability, excellent fatigue resistance and high color change sensitivity.

In order to achieve the purpose, the invention provides the following technical scheme:

a photochromic plate is prepared from the following raw materials in parts by weight: 30-45 parts of TPU, 3-5 parts of thixotropic agent and 70-90 parts of photochromic organic polymer coating;

wherein: the photochromic organic polymer coating is prepared from modified acrylic resin, a photochromic material and an organic solvent according to a mass ratio of 6-8: 0.3-0.6: 6-8, mixing and stirring.

By adopting the technical scheme, the photochromic material in the photochromic organic polymer coating is formed by compounding the organic photochromic material and the inorganic photochromic material, wherein the photoproduction electron hole of the inorganic photochromic material has strong oxidation-reduction performance, and the mutual matching of the inorganic photochromic material and the organic photochromic material can not only obviously improve the sensitivity of the plate to light, but also enlarge the photochromic range of the plate.

The invention is further configured to: the thixotropic agent is hydrogenated castor oil or polyamide wax.

By adopting the technical scheme, the thixotropic agent enables the TPU to have higher consistency when being static and to become a low-consistency fluid substance under the action of external force, so that the subsequent injection molding process can be carried out smoothly.

The invention is further configured to: the photochromic material is prepared from an organic photochromic material and an inorganic photochromic material according to a mass ratio of 1: 2-3, mixing; wherein:

the organic photochromic material is selected from quinolopyran or phenoxazine;

MoO is selected as inorganic photochromic material₃Or WO₃。

By adopting the technical scheme, the photo-generated electron hole of the inorganic photochromic material has strong oxidation-reduction performance, and the mutual matching of the inorganic photochromic material and the organic photochromic material can not only obviously improve the sensitivity of the plate to light, but also enlarge the color change range of the plate. The photochromic effect can be excited by fully utilizing the spectral energy of abundant visible light in sunlight, so that the photochromic effect of the photochromic plate prepared by the method is obviously enhanced.

The invention is further configured to: the preparation method of the modified polyacrylic resin comprises the following steps:

a. accurately weighing cerium oxide powder with the mass of 2-4% of polyacrylic resin, transferring the cerium oxide powder into a high-speed mixer with the temperature of 55-65 ℃, spraying an ethanol solution containing 10-15% of silane coupling agent into the cerium oxide powder, and simultaneously mixing and stirring the cerium oxide powder uniformly at the speed of 300-400 r/min; wherein the dosage of the silane coupling agent is 2-4% of the mass of the cerium oxide powder;

b. uniformly stirring, carrying out spray treatment for 20-30min, taking out the activated cerium oxide powder from a high-speed mixer, placing the activated cerium oxide powder in a constant-temperature drying oven, and drying at 80-90 ℃ to obtain modified cerium oxide powder;

c. b, transferring the modified cerium oxide powder obtained in the step b and polyacrylic resin into a high-speed mixer, and adding an auxiliary agent with the mass 0.8-1.3 times that of the cerium oxide powder into the high-speed mixer; under the condition of 60-70 ℃, uniformly mixing and stirring at the speed of 200-300r/min, and granulating the mixture by a double-screw extruder to obtain modified polyacrylic resin;

wherein the auxiliary agent is prepared by mixing phosphite composite antioxidant, hindered phenol light stabilizer and the like.

By adopting the technical scheme, the polyacrylic resin is modified, so that the modified polyacrylic resin can be subjected to a crosslinking reaction with the TPU, and the modified polyacrylic resin can be firmly fixed on the surface of the TPU. The photo-generated electron hole of the modified cerium oxide on the surface of the modified polyacrylic resin has strong oxidation-reduction performance, and the photo-generated electron hole is matched with the inorganic photochromic material and the organic photochromic material, so that the sensitivity of the plate to light can be obviously improved, and the color change effect of the photochromic plate prepared by the method can be obviously enhanced.

The invention is further configured to: the organic solvent is one of BCS, EAC and IBA.

By adopting the technical scheme, the photochromic material and the modified acrylic resin can be better dissolved in the organic solvent, so that a uniform and stable dispersion system is formed, the subsequent plate matrix can be ensured to be uniformly coated on the surface of the plate matrix when being soaked and dyed, and the photochromic performance of the manufactured photochromic plate is ensured.

The invention is further configured to: a manufacturing process of a photochromic plate comprises the following steps:

s1, accurately weighing the TPU, the thixotropic agent and the photochromic organic polymer coating according to the weight ratio, uniformly mixing and stirring the TPU and the thixotropic agent, transferring the mixture into a charging barrel of an injection molding machine for injection molding, and cooling to obtain a plate substrate;

s2, soaking the plate substrate obtained in the step S1 in photochromic organic polymer paint, raising the temperature of the photochromic organic polymer paint to 60-70 ℃, soaking for 4-8h at the constant temperature, and ultrasonically oscillating for 3-5min every 30-50min in the soaking process;

s3, taking the plate substrate out of the photochromic organic polymer coating, uniformly spreading the photochromic organic polymer coating on the surface of the plate substrate, fixing the plate substrate under the irradiation of an ultraviolet lamp, and trimming the plate substrate to obtain a finished photochromic plate;

and S4, performing quality inspection on the photochromic plate finished product obtained in the S3, discarding defective products with unqualified quality, and reserving qualified photochromic plate finished products.

By adopting the technical scheme, the obtained plate substrate is soaked in the photochromic organic polymer coating with the temperature of 60-70 ℃, and intermittent ultrasonic vibration treatment is adopted in the soaking process. Finally, under the irradiation of ultraviolet light, the small molecules in the photochromic materials are firmly confined in the plate substrate, so that the prepared photochromic plate has stable and durable color change effect.

The invention is further configured to: the cooling pressure in the S1 is 35-50bar, and the cooling time is 3-5S.

By adopting the technical scheme, the injection-molded plate base body is cooled for 3-5s under the sub-cooling pressure, so that the cooling effect on the plate base body can be ensured, and the defect of the quality of the plate base body in the cooling process can be avoided, thereby ensuring the quality of the plate base body.

The invention is further configured to: and the frequency of the ultrasonic oscillation in the S2 is 20-28 KHz.

By adopting the technical scheme, the photochromic organic polymer coating is subjected to ultrasonic vibration at the frequency, so that photochromic molecules in the photochromic organic polymer coating can be increased to enter molecular intervals of the plate matrix, and the photochromic performance of the prepared photochromic plate is ensured.

The invention is further configured to: the power of the ultraviolet lamp in the S3 is 500W.

By adopting the technical scheme, the speed of the photochromic organic polymer coating solidified on the surface of the plate substrate can be accelerated under the condition, and the phenomenon of coating aging caused by overlarge illumination intensity can be effectively avoided.

In summary, the invention has the following advantages:

1. the invention adopts photochromic organic polymer coating and TPU as raw materials for preparing photochromic plates. The photochromic material in the photochromic organic polymer coating is formed by compounding an organic photochromic material and an inorganic photochromic material, wherein a photoproduction electron hole of the inorganic photochromic material has strong oxidation-reduction performance, and the photochromic material and the organic photochromic material are matched with each other, so that the sensitivity of the plate to light can be obviously improved, and the photochromic range of the plate is enlarged. And the spectral energy of abundant visible light in sunlight can be fully utilized to excite the photochromic effect, so that the photochromic effect of the photochromic plate prepared by the method is obviously enhanced. Moreover, the photochromic sheet prepared by the method has good stability of color change, excellent fatigue resistance and higher sensitivity in color change;

2. soaking the obtained plate substrate in photochromic organic polymer coating at the temperature of 60-70 ℃, and adopting intermittent ultrasonic oscillation treatment in the soaking process. At the temperature, the distance between molecules between the plate substrates is increased, so that small molecules in the photochromic organic polymer coating can enter molecular gaps of the photochromic organic polymer coating, and then ultrasonic oscillation treatment is matched, so that the small molecules in the photochromic materials can fully enter the gaps on the surface of the plate substrates, and finally, under the irradiation of ultraviolet lamp light, the small molecules in the photochromic materials are firmly confined in the plate substrates, so that the prepared photochromic plate has a stable and lasting color change effect.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention.