阅读说明：本技术 光致变色膜及其制备方法 (Photochromic film and preparation method thereof ) 是由 甘家安 王卓 宋熊荣 尤韦霖 杨德鹏 于 2020-11-30 设计创作，主要内容包括：本发明揭示了一种光致变色膜,包括以下原料组分,按重量百分比组成：脂肪族聚酯齐聚物40～65％；邻苯基苯氧乙基丙烯酸酯25～45％；磷酸甲基丙烯酸酯3～16％；光致变色染料0.1～8％；苯甲酰甲酸甲酯0.1～3％；表面活性剂0.1～5％；抗氧化剂0.2～5％；其中,脂肪族聚酯齐聚物由聚氨酯丙烯酸酯和2(2-乙氧基乙氧基)乙基丙烯酸酯以1:(0.1～0.2)的质量比混合形成。本发明还提供了一种光致变色膜的制备方法。本发明提供的光致变色膜具有收缩率低和附着力强优点,收率低可以避免因光固化过程中光致变色染料变色使产品未固化完全,而在后期因自然固化造成大的尺寸变化和表面缺陷；并且该光致变色膜具有优异的耐候性,能够广泛应用于交通工具和建筑物上。(The invention discloses a photochromic film which comprises the following raw material components in percentage by weight: 40-65% of aliphatic polyester oligomer; 25-45% of o-phenyl phenoxyethyl acrylate; 3-16% of phosphoric acid methacrylate; 0.1-8% of photochromic dye; 0.1-3% of methyl benzoylformate; 0.1-5% of a surfactant; 0.2-5% of an antioxidant; the aliphatic polyester oligomer is formed by mixing urethane acrylate and 2 (2-ethoxy) ethyl acrylate according to the mass ratio of 1 (0.1-0.2). The invention also provides a preparation method of the photochromic film. The photochromic film provided by the invention has the advantages of low shrinkage rate and strong adhesive force, and the low yield can avoid the problems that the product is not completely cured due to the color change of the photochromic dye in the photocuring process, and large size change and surface defects are caused by natural curing at the later stage; and the photochromic film has excellent weather resistance and can be widely applied to vehicles and buildings.)

1. The photochromic film is characterized by comprising the following raw material components in percentage by weight:

the aliphatic polyester oligomer is formed by mixing urethane acrylate and 2 (2-ethoxyethoxy) ethyl acrylate according to the mass ratio of 1 (0.1-0.2).

2. The photochromic film of claim 1, comprising the following raw material components in percentage by weight:

3. the photochromic film according to claim 1, wherein the aliphatic polyester oligomer is formed by mixing urethane acrylate and 2 (2-ethoxyethoxy) ethyl acrylate in a mass ratio of 1 (0.12 to 0.16).

4. The photochromic film of claim 1 wherein the urethane acrylate has a functionality of 2 to 3.

5. The photochromic film of claim 1 wherein the photochromic dye comprises one or more of naphthopyran photochromic compounds, dithienylethylene photochromic compounds, azobenzene photochromic compounds, fulgide photochromic compounds, spiropyran photochromic compounds, and spirooxazine photochromic compounds.

6. The photochromic film of claim 1 wherein the surfactant is a non-ionic surfactant.

7. The photochromic film according to claim 6, wherein the nonionic surfactant is one or more selected from the group consisting of sorbitan fatty acid ester, polyoxyethylene sorbitol fatty glycerol fatty acid ester, decaglycerol fatty acid ester, propylene glycol-pentaerythritol fatty acid ester, polyoxyethylene glycerol fatty acid ester, polyethylene glycol fatty acid ester, and polyoxyethylene alkyl ether.

8. The photochromic film of claim 1 wherein the antioxidant is one or more of secondary aromatic amine, hindered phenol, butylated hydroxytoluene, 2, 6-di-t-butyl-4-methylphenol.

9. The photochromic film according to any one of claims 1 to 8, wherein the raw material composition of the photochromic film further comprises an ultraviolet stabilizer, and the ultraviolet stabilizer is one or more of 2-hydroxybenzophenone, 2-hydroxyphenylbenzotriazole and an organic nickel compound.

10. A method for preparing a photochromic film is characterized by comprising the following steps:

step 1: uniformly mixing the raw material components of the photochromic film at the temperature of 50-100 ℃ to obtain a photochromic composition;

step 2: uniformly coating the photochromic composition obtained by mixing on the surface of a substrate, wherein the coating thickness is 0.05-0.5 mm;

and step 3: placing the photochromic composition coating surface of the substrate at a wavelength of 250-360 nm and an illumination of 1-20J/cm²Curing for 2-30 minutes under the illumination condition to obtain the photochromic film.

Technical Field

The invention belongs to the technical field of photochromic materials, and particularly relates to a photochromic film and a preparation method thereof.

Background

A phenomenon of discoloration in response to a specific light is called Photochromic, and a material causing such Photochromic is called Photochromic material (photo-reversible Photochromic compound or Photochromic compound). Photochromic compounds are broadly classified into a pigment form and a dye form or an inorganic form and an organic form. Photochromic compounds in the form of solutions or dispersions change from colorless to a particular color when exposed to sunlight or ultraviolet light and return to the original color when exposed to the dark or in the absence of intense ultraviolet radiation. Although the phenomenon of photochromism was discovered around 1840, commercial research has recently begun.

For example, a photochromic composition containing a photochromic compound as a pigment is applied to a transparent substrate such as glass or plastic and cured to form a photochromic film, and the photochromic film is used as a light-black film for vehicles or buildings. However, in this case, there is a problem in that wrinkles are easily formed or a micro-pore defect is easily formed on the surface of the existing photochromic film due to a large shrinkage rate during the curing process to form the photochromic film.

Therefore, in view of the above technical problems, it is necessary to provide a novel photochromic film and a method for preparing the same.

Disclosure of Invention

The invention aims to provide a photochromic film with simple preparation process and small curing shrinkage rate and a preparation method thereof, which aim to solve the problems in the prior art.

In order to achieve the purpose, the technical scheme provided by the invention is as follows:

the photochromic film comprises the following raw material components in percentage by weight:

the aliphatic polyester oligomer is formed by mixing urethane acrylate and 2 (2-ethoxyethoxy) ethyl acrylate according to the mass ratio of 1 (0.1-0.2).

Further, the photochromic film comprises the following raw material components in percentage by weight:

further, the aliphatic polyester oligomer is formed by mixing urethane acrylate and 2 (2-ethoxyethoxy) ethyl acrylate according to the mass ratio of 1 (0.12-0.16).

Further, the functionality of the polyurethane acrylate is 2-3.

Further, the photochromic dye comprises one or more of naphthopyran photochromic compounds, dithienylethene photochromic compounds, azobenzene photochromic compounds, fulgide photochromic compounds, spiropyran photochromic compounds and spirooxazine photochromic compounds.

Further, the surfactant is a nonionic surfactant.

Further, the nonionic surfactant is one or more of sorbitan fatty acid ester, polyoxyethylene sorbitol fatty glycerol fatty acid ester, decaglycerol fatty acid ester, propylene glycol-pentaerythritol fatty acid ester, polyoxyethylene glycerol fatty acid ester, polyethylene glycol fatty acid ester, and polyoxyethylene alkyl ether.

Further, the antioxidant is one or more of aromatic secondary amine, hindered phenol, butylated hydroxytoluene and 2, 6-di-tert-butyl-4-methylphenol.

Further, the raw material components of the photochromic film also comprise an ultraviolet stabilizer, wherein the ultraviolet stabilizer is one or more of 2-hydroxybenzophenone, 2-hydroxyphenyl benzotriazole and an organic nickel compound.

A method for preparing a photochromic film, comprising the steps of:

step 1: uniformly mixing the raw material components of the photochromic film at the temperature of 50-100 ℃ to obtain a photochromic composition;

step 2: uniformly coating the photochromic composition obtained by mixing on the surface of a substrate, wherein the coating thickness is 0.05-0.5 mm;

and step 3: placing the photochromic composition coating surface of the substrate at a wavelength of 250-360 nm and an illumination of 1-20J/cm²Curing for 2-30 minutes under the illumination condition to obtain the photochromic film.

The invention has the beneficial effects that:

compared with the prior art, the photochromic film provided by the invention has the advantages of low shrinkage rate and strong adhesive force, and the low yield can avoid the problems that the product is not completely cured due to the color change of the photochromic dye in the photocuring process, and the large size change and surface defects are caused by natural curing in the later period; the photochromic film has excellent weather resistance and can be widely applied to vehicles and buildings; meanwhile, the photochromic film is simple in preparation process, high in curing speed and suitable for large-scale batch production.

Detailed Description

In order to more fully understand the technical contents of the present invention, the technical solutions of the present invention will be further described and illustrated by the following specific examples.

In the following description, "%" and "part" representing amounts are based on weight unless otherwise specified. Unless otherwise indicated, all numbers expressing feature sizes, quantities, and physical characteristics used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can be suitably varied by those skilled in the art in seeking to obtain the desired properties utilizing the teachings disclosed herein. The use of numerical ranges by endpoints includes all numbers within that range and any range within that range, for example, 1 to 5 includes 1, 1.2, 1.4, 1.55, 2, 2.75, 3, 3.80, 4, and 5, and the like.

It is also noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus; the term "preferred" refers to a preferred alternative, but is not limited to only the selected alternative.

The invention provides a photochromic film, which comprises the following raw material components in percentage by weight: 40-65% of aliphatic polyester oligomer; 25-45% of o-phenyl phenoxyethyl acrylate; 3-16% of phosphoric acid methacrylate; 0.1-8% of photochromic dye; 0.1-3% of methyl benzoylformate; 0.1-5% of a surfactant; 0.2-5% of antioxidant. The aliphatic polyester oligomer is formed by mixing urethane acrylate and 2 (2-ethoxyethoxy) ethyl acrylate according to the mass ratio of 1 (0.1-0.2).

Preferably, the photochromic film comprises the following raw material components in percentage by weight: 50-60% of aliphatic polyester oligomer; 30-40% of o-phenylphenoxyethyl acrylate; 6-10% of phosphoric methacrylate; 0.5-5% of photochromic dye; 0.5-2% of methyl benzoylformate; 0.5-3% of a surfactant; 0.5-3% of antioxidant. The aliphatic polyester oligomer is formed by mixing urethane acrylate and 2 (2-ethoxyethoxy) ethyl acrylate according to the mass ratio of 1 (0.12-0.16).

The polyurethane acrylate has a functionality of 2-3, and for example, the polyurethane acrylate may be selected from one or more of Miramer PU210, Miramer PU217, Miramer PU2030I, Miramer PU2061, Miramer PU320, Miramer PU3200, Miramer PU340, and CN8007 NS, CN8881 NS, CN8884 NS, and CN9021 NS of Sandoma chemical Co.

The photochromic dye can be one or more of the existing known photochromic dyes, for example, the photochromic dye can be one or more of naphthopyran photochromic compounds, dithiophene ethylene photochromic compounds, azobenzene photochromic compounds, fulgide photochromic compounds, spiropyran photochromic compounds and spirooxazine photochromic compounds. Among these photochromic compounds, naphthopyran-based photochromic compounds are preferably used in consideration of fading conditions after discoloration and color development concentration and discoloration speed; for example, one or more of the compounds Nip-Me, Nip-Bu, Nip-Ph and Nip-HyEt described in Chinese patent publication No. CN101974002B may be used.

The surfactant is preferably a nonionic surfactant, and may be one or more selected from sorbitan fatty acid esters, polyoxyethylene sorbitol fatty glycerol fatty acid esters, decaglycerol fatty acid esters, propylene glycol-pentaerythritol fatty acid esters, polyoxyethylene glycerol fatty acid esters, polyethylene glycol fatty acid esters, and polyoxyethylene alkyl ethers, and the solubility of the surfactant in the resin base material can be improved by using these nonionic surfactants.

Photochromic compounds are colored by absorbing ultraviolet rays and changing the molecular structure, and are restored to their original state by absorbing heat or visible light. In this change, energy is transferred to oxygen due to the presence of oxygen, and oxygen radicals having a strong oxidizing power are generated. Therefore, by trapping the oxygen radicals with an antioxidant having a radical trapping ability, oxidation of the photochromic film can be effectively prevented. The antioxidant can be one or more of aromatic secondary amine, hindered phenol, butylated hydroxytoluene and 2, 6-di-tert-butyl-4-methylphenol. The antioxidant is preferably one or more of bis (1,2,2,6, 6-pentamethyl-4-piperidyl) sebacate and 1,2,2,6, 6-pentamethyl-4-piperidinol in hindered amine.

The raw material components of the photochromic film also comprise an ultraviolet stabilizer which can be one or more of 2-hydroxybenzophenone, 2-hydroxyphenyl benzotriazole and organic nickel compounds.

The invention also provides a preparation method of the photochromic film, which comprises the following steps:

step 1: uniformly mixing the raw material components of the photochromic film at the temperature of 50-100 ℃ to obtain a photochromic composition;

step 2: uniformly coating the photochromic composition obtained by mixing on the surface of a substrate, wherein the coating thickness is 0.05-0.5 mm;

and step 3: placing the photochromic composition coating surface of the substrate at a wavelength of 250-360 nm and an illumination of 1-20J/cm²Curing for 2-30 minutes under the illumination condition to obtain the photochromic film.

The material of the above substrate is not particularly limited as long as it is known in the art. For example, glass, metal, plastic substrates may be used, but glass is most preferred. Further, the substrate preferably has a flat surface, but may have a special shape on its surface if necessary. The thickness of the substrate depends on the size and kind of the substrate so that it should have a thickness sufficient to prevent the substrate from being bent.

The photochromic film may also be disposed between two substrates to form a sandwich structure, in which case the substrates are made of transparent glass or plastic. For example, the photochromic composition can be coated on one substrate, and then the other substrate is pressed on the coating surface of the first substrate, and then the photochromic composition is cured to form a photochromic film; the photochromic composition can also be injected between two substrates by adopting a pouring mode, and then the photochromic composition is cured to form the photochromic film.

Example 1

55 parts by weight of an aliphatic polyester oligomer (formed by mixing 48 parts by weight of urethane acrylate (CN8884 NS, functionality 2, Saedoma chemical Co., Ltd.) and 7 parts by weight of 2 (2-ethoxyethoxy) ethyl acrylate) at 75 ℃, 33 parts by weight of o-phenylphenoxyethyl acrylate (Miraner M1142, Meiyuan Special chemical Co., Ltd.), 8 parts by weight of phosphomethacrylate (Miraner SC1400, Meiyuan Special chemical Co., Ltd.), 1.5 parts by weight of a photochromic dye (Nip-Bu described in Chinese patent document having an authorization publication of CN 101974002B), 0.8 part by weight of methyl benzoylformate (Micure MBF, Meiyuan Special chemical Co., Ltd.), 0.7 part by weight of a surfactant (sorbitan fatty acid ester), 0.6 part by weight of an antioxidant (bis (1,2,2,6, 6-pentamethyl-4-piperidinyl) sebacate) and 0.4 part by weight of an ultraviolet light stabilizer (2-hydroxybis light stabilizer) Benzophenone) is uniformly mixed and stirred to obtain the photochromic composition.

The photochromic composition obtained by mixing was uniformly coated on the surfaces of a smooth glass substrate, a plastic (polycarbonate) substrate and a metal (aluminum) substrate, respectively, to a coating thickness of 0.1mm and a coating area of 20X 20cm²(ii) a The coated surface of each substrate was exposed to light having a wavelength of 325nm and an illuminance of 5J/cm²Curing for 5 minutes under the illumination condition to obtain the photochromic film.

Example 2

50 parts by weight of an aliphatic polyester oligomer (formed by mixing 45 parts by weight of urethane acrylate (CN8884 NS, functionality 2, Saedoma chemical Co., Ltd.) and 5 parts by weight of 2 (2-ethoxyethoxy) ethyl acrylate) at 75 ℃, 40 parts by weight of o-phenylphenoxyethyl acrylate (Miraner M1142, Meiyuan Special chemical Co., Ltd.), 6 parts by weight of phosphomethacrylate (Miraner SC1400, Meiyuan Special chemical Co., Ltd.), 1.5 parts by weight of a photochromic dye (Nip-Bu described in Chinese patent document having an authorization publication of CN 101974002B), 0.8 part by weight of methyl benzoylformate (Micure MBF, Meiyuan Special chemical Co., Ltd.), 0.7 part by weight of a surfactant (sorbitan fatty acid ester), 0.6 part by weight of an antioxidant (bis (1,2,2,6, 6-pentamethyl-4-piperidinyl) sebacate) and 0.4 part by weight of an ultraviolet light stabilizer (2-hydroxybis light stabilizer) Benzophenone) is uniformly mixed and stirred to obtain the photochromic composition.

The photochromic composition obtained by mixing was uniformly coated on the surfaces of a smooth glass substrate, a plastic (polycarbonate) substrate and a metal (aluminum) substrate, respectively, to a coating thickness of 0.1mm and a coating area of 20X 20cm²(ii) a The coated surface of each substrate was exposed to light having a wavelength of 325nm and an illuminance of 5J/cm²Curing for 5 minutes under the illumination condition to obtain the photochromic film.

Example 3

60 parts by weight of an aliphatic polyester oligomer (formed by mixing 50 parts by weight of urethane acrylate (CN8884 NS, functionality 2, Saedoma chemical Co., Ltd.) and 10 parts by weight of 2 (2-ethoxyethoxy) ethyl acrylate) at 75 ℃, 30 parts by weight of o-phenylphenoxyethyl acrylate (Miraner M1142, Meiyuan Special chemical Co., Ltd.), 6 parts by weight of phosphomethacrylate (Miraner SC1400, Meiyuan Special chemical Co., Ltd.), 1.5 parts by weight of a photochromic dye (Nip-Bu described in Chinese patent document having an authorization publication of CN 101974002B), 0.8 part by weight of methyl benzoylformate (Micure MBF, Meiyuan Special chemical Co., Ltd.), 0.7 part by weight of a surfactant (sorbitan fatty acid ester), 0.6 part by weight of an antioxidant (bis (1,2,2,6, 6-pentamethyl-4-piperidinyl) sebacate) and 0.4 part by weight of an ultraviolet light stabilizer (2-hydroxybis light stabilizer) Benzophenone) is uniformly mixed and stirred to obtain the photochromic composition.

The photochromic composition obtained by mixing was uniformly coated on the surfaces of a smooth glass substrate, a plastic (polycarbonate) substrate and a metal (aluminum) substrate, respectively, to a coating thickness of 0.1mm and a coating area of 20X 20cm²(ii) a The coated surface of each substrate was exposed to light having a wavelength of 325nm and an illuminance of 5J/cm²Curing for 5 minutes under the illumination condition to obtain the photochromic film.

Example 4

45 parts by weight of an aliphatic polyester oligomer (formed by mixing 40 parts by weight of urethane acrylate (CN8884 NS, functionality 2, Saedoma chemical Co., Ltd.) and 5 parts by weight of 2 (2-ethoxyethoxy) ethyl acrylate) at 75 ℃, 41 parts by weight of o-phenylphenoxyethyl acrylate (Miraner M1142, Meiyuan Special chemical Co., Ltd.), 10 parts by weight of phosphomethacrylate (Miraner SC1400, Meiyuan Special chemical Co., Ltd.), 1.5 parts by weight of a photochromic dye (Nip-Bu described in Chinese patent document having an authorization publication of CN 101974002B), 0.8 part by weight of methyl benzoylformate (Micure MBF, Meiyuan Special chemical Co., Ltd.), 0.7 part by weight of a surfactant (sorbitan fatty acid ester), 0.6 part by weight of an antioxidant (bis (1,2,2,6, 6-pentamethyl-4-piperidinyl) sebacate) and 0.4 part by weight of an ultraviolet light stabilizer (2-hydroxybis light stabilizer) Benzophenone) is uniformly mixed and stirred to obtain the photochromic composition.

The photochromic composition obtained by mixing was uniformly coated on the surfaces of a smooth glass substrate, a plastic (polycarbonate) substrate and a metal (aluminum) substrate, respectively, to a coating thickness of 0.1mm and a coating area of 20X 20cm²(ii) a The coated surface of each substrate was exposed to light having a wavelength of 325nm and an illuminance of 5J/cm²Curing for 5 minutes under the illumination condition to obtain the photochromic film.

Example 5

65 parts by weight of an aliphatic polyester oligomer (formed by mixing 55 parts by weight of urethane acrylate (CN8884 NS, functionality 2, Saedoma chemical Co., Ltd.) and 10 parts by weight of 2 (2-ethoxyethoxy) ethyl acrylate) at 75 ℃, 25 parts by weight of o-phenylphenoxyethyl acrylate (Miraner M1142, Meiyuan Special chemical Co., Ltd.), 3 parts by weight of phosphomethacrylate (Miraner SC1400, Meiyuan Special chemical Co., Ltd.), 1.5 parts by weight of a photochromic dye (Nip-Bu described in Chinese patent document having an authorization publication of CN 101974002B), 3 parts by weight of methyl benzoylformate (Micure MBF, Meiyuan Special chemical Co., Ltd.), 1 part by weight of a surfactant (sorbitan fatty acid ester), 1 part by weight of an antioxidant (bis (1,2,2,6, 6-pentamethyl-4-piperidyl) sebacate) and 0.5 part by weight of an ultraviolet light stabilizer (2-hydroxydipicolinate) Benzophenone) is uniformly mixed and stirred to obtain the photochromic composition.

The photochromic composition obtained by mixing was uniformly coated on the surfaces of a smooth glass substrate, a plastic (polycarbonate) substrate and a metal (aluminum) substrate, respectively, to a coating thickness of 0.1mm and a coating area of 20X 20cm²(ii) a The coated surface of each substrate was exposed to light having a wavelength of 325nm and an illuminance of 5J/cm²Curing for 5 minutes under the illumination condition to obtain the photochromic film.

Example 6

45 parts by weight of an aliphatic polyester oligomer (formed by mixing 39 parts by weight of urethane acrylate (CN8884 NS, functionality 2, Saedoma chemical Co., Ltd.) and 6 parts by weight of 2 (2-ethoxyethoxy) ethyl acrylate) at 75 ℃, 35 parts by weight of o-phenylphenoxyethyl acrylate (Miraner M1142, Meiyuan Special chemical Co., Ltd.), 16 parts by weight of phosphomethacrylate (Miraner SC1400, Meiyuan Special chemical Co., Ltd.), 1.5 parts by weight of a photochromic dye (Nip-Bu described in Chinese patent document having an authorization publication of CN 101974002B), 0.8 part by weight of methyl benzoylformate (Micure MBF, Meiyuan Special chemical Co., Ltd.), 0.7 part by weight of a surfactant (sorbitan fatty acid ester), 0.6 part by weight of an antioxidant (bis (1,2,2,6, 6-pentamethyl-4-piperidinyl) sebacate) and 0.4 part by weight of an ultraviolet light stabilizer (2-hydroxybis light stabilizer) Benzophenone) is uniformly mixed and stirred to obtain the photochromic composition.

The photochromic composition obtained by mixing was uniformly coated on the surfaces of a smooth glass substrate, a plastic (polycarbonate) substrate and a metal (aluminum) substrate, respectively, to a coating thickness of 0.1mm and a coating area of 20X 20cm²(ii) a The coated surface of each substrate was exposed to light having a wavelength of 325nm and an illuminance of 5J/cm²Curing for 5 minutes under the illumination condition to obtain the photochromic film.

Example 7

40 parts by weight of an aliphatic polyester oligomer (formed by mixing 35 parts by weight of urethane acrylate (Miramer PU320, functionality 3, Meiyuan Special chemical Co., Ltd.) and 5 parts by weight of 2 (2-ethoxyethoxy) ethyl acrylate), 45 parts by weight of o-phenylphenoxyethyl acrylate (Miraner M1142, Meiyuan Special chemical Co., Ltd.), 13 parts by weight of phosphomethacrylate (Miraner SC1400, Meiyuan Special chemical Co., Ltd.), 1.5 parts by weight of a photochromic dye (Nip-Bu described in the Chinese patent document having an authorization notice of CN 101974002B), 0.1 part by weight of methyl benzoylformate (Micure MBF, Meiyuan Special chemical Co., Ltd.), 0.1 part by weight of a surface active agent (sorbitan fatty acid ester), 0.2 part by weight of an antioxidant (bis (1,2,2,6, 6-pentamethyl-4-piperidinyl) sebacate) and 0.1 part by weight of an ultraviolet light stabilizer (2, 2-ethoxyethoxy) at a temperature of 75 ℃ Hydroxybenzophenone) and uniformly mixing and stirring to obtain the photochromic composition.

Uniformly coating the mixed photochromic compositionsThe surface of a smooth glass substrate, plastic (polycarbonate) substrate and metal (aluminum) substrate was coated with a coating having a thickness of 0.1mm and a coating area of 20X 20cm²(ii) a The coated surface of each substrate was exposed to light having a wavelength of 325nm and an illuminance of 5J/cm²Curing for 5 minutes under the illumination condition to obtain the photochromic film.

Comparative example 1

55 parts by weight of urethane acrylate (CN8884 NS, functionality 2, Saedoma chemical Co.), 33 parts by weight of o-phenylphenoxyethyl acrylate (Miraner M1142, Meiyuan Special chemical Co., Ltd.), 8 parts by weight of methyl phosphate (Miraner SC1400, Meiyuan Special chemical Co., Ltd.), 1.5 parts by weight of a photochromic dye (Nip-Bu described in the Chinese patent document having been granted under CN 101974002B), 0.8 part by weight of methyl benzoylformate (Micure MBF, Meiyuan Special chemical Co., Ltd.), 0.7 part of a surfactant (sorbitan fatty acid ester), 0.6 part by weight of an antioxidant (bis (1,2,2,6, 6-pentamethyl-4-piperidyl) sebacate) and 0.4 part by weight of an ultraviolet light stabilizer (2-hydroxybenzophenone) were mixed and stirred at 75 ℃ to be uniform, a photochromic composition was obtained.

The photochromic composition obtained by mixing was uniformly coated on the surfaces of a smooth glass substrate, a plastic (polycarbonate) substrate and a metal (aluminum) substrate, respectively, to a coating thickness of 0.1mm and a coating area of 20X 20cm²(ii) a The coated surface of each substrate was exposed to light having a wavelength of 325nm and an illuminance of 5J/cm²Curing for 5 minutes under the illumination condition to obtain the photochromic film.

Comparative example 2

55 parts by weight of an aliphatic polyester oligomer (formed by mixing 40 parts by weight of urethane acrylate (CN8884 NS, functionality 2, Saedoma chemical Co., Ltd.) and 15 parts by weight of 2 (2-ethoxyethoxy) ethyl acrylate) at 75 ℃, 33 parts by weight of o-phenylphenoxyethyl acrylate (Miraner M1142, Meiyuan Special chemical Co., Ltd.), 8 parts by weight of phosphomethacrylate (Miraner SC1400, Meiyuan Special chemical Co., Ltd.), 1.5 parts by weight of a photochromic dye (Nip-Bu described in Chinese patent document having an authorization publication of CN 101974002B), 0.8 part by weight of methyl benzoylformate (Micure MBF, Meiyuan Special chemical Co., Ltd.), 0.7 part by weight of a surfactant (sorbitan fatty acid ester), 0.6 part by weight of an antioxidant (bis (1,2,2,6, 6-pentamethyl-4-piperidinyl) sebacate) and 0.4 part by weight of an ultraviolet light stabilizer (2-hydroxybis light stabilizer) Benzophenone) is uniformly mixed and stirred to obtain the photochromic composition.

The photochromic composition obtained by mixing was uniformly coated on the surfaces of a smooth glass substrate, a plastic (polycarbonate) substrate and a metal (aluminum) substrate, respectively, to a coating thickness of 0.1mm and a coating area of 20X 20cm²(ii) a The coated surface of each substrate was exposed to light having a wavelength of 325nm and an illuminance of 5J/cm²Curing for 5 minutes under the illumination condition to obtain the photochromic film.

Comparative example 3

55 parts by weight of an aliphatic polyester oligomer (formed by mixing 48 parts by weight of urethane acrylate (CN8884 NS, functionality 2, Saedoma chemical Co., Ltd.) and 7 parts by weight of 2 (2-ethoxyethoxy) ethyl acrylate) at 75 ℃, 20 parts by weight of o-phenylphenoxyethyl acrylate (Miraner M1142, Meiyuan Special chemical Co., Ltd.), 21 parts by weight of phosphomethacrylate (Miraner SC1400, Meiyuan Special chemical Co., Ltd.), 1.5 parts by weight of a photochromic dye (Nip-Bu described in Chinese patent document having an authorization publication of CN 101974002B), 0.8 part by weight of methyl benzoylformate (Micurer MBF, Meiyuan Special chemical Co., Ltd.), 0.7 part by weight of a surfactant (sorbitan fatty acid ester), 0.6 part by weight of an antioxidant (bis (1,2,2,6, 6-pentamethyl-4-piperidinyl) sebacate) and 0.4 part by weight of an ultraviolet light stabilizer (2-hydroxydiphenyl acid ester) (2-hydroxydiphenyl light stabilizer) Ketone) and uniformly mixing and stirring to obtain the photochromic composition.

The photochromic composition obtained by mixing was uniformly coated on the surfaces of a smooth glass substrate, a plastic (polycarbonate) substrate and a metal (aluminum) substrate, respectively, to a coating thickness of 0.1mm and a coating area of 20X 20cm²(ii) a The coated surface of each substrate was exposed to light having a wavelength of 325nm and an illuminance of 5J/cm²Curing for 5 minutes under the illumination condition to obtain the photochromic film.

Comparative example 4

55 parts by weight of an aliphatic polyester oligomer (formed by mixing 48 parts by weight of urethane acrylate (CN8884 NS, functionality 2, Saedoma chemical Co., Ltd.) and 7 parts by weight of 2 (2-ethoxyethoxy) ethyl acrylate) at 75 ℃, 40 parts by weight of o-phenylphenoxyethyl acrylate (Miraner M1142, Meiyuan Special chemical Co., Ltd.), 1 part by weight of phosphomethacrylate (Miraner SC1400, Meiyuan Special chemical Co., Ltd.), 1.5 parts by weight of a photochromic dye (Nip-Bu described in Chinese patent document having an authorization publication of CN 101974002B), 0.8 part by weight of methyl benzoylformate (Micure R MBF, Meiyuan Special chemical Co., Ltd.), 0.7 part by weight of a surfactant (sorbitan fatty acid ester), 0.6 part by weight of an antioxidant (bis (1,2,2,6, 6-pentamethyl-4-piperidinyl) sebacate) and 0.4 part by weight of an ultraviolet light stabilizer (2-hydroxyethoxy) were measured at 75 ℃ Benzophenone), and mixing and stirring uniformly to obtain the photochromic composition.

The photochromic composition obtained by mixing was uniformly coated on the surfaces of a smooth glass substrate, a plastic (polycarbonate) substrate and a metal (aluminum) substrate, respectively, to a coating thickness of 0.1mm and a coating area of 20X 20cm²(ii) a The coated surface of each substrate was exposed to light having a wavelength of 325nm and an illuminance of 5J/cm²Curing for 5 minutes under the illumination condition to obtain the photochromic film.

Comparative example 5

55 parts by weight of an aliphatic polyester oligomer (formed by mixing 48 parts by weight of urethane acrylate (CN8884 NS, functionality 2, Saedoma chemical Co., Ltd.) and 7 parts by weight of 2 (2-ethoxyethoxy) ethyl acrylate) at 75 ℃, 33 parts by weight of o-phenylphenoxyethyl acrylate (Miraner M1142, Meiyuan Special chemical Co., Ltd.), 8 parts by weight of phosphomethacrylate (Miraner SC1400, Meiyuan Special chemical Co., Ltd.), 1.5 parts by weight of a photochromic dye (Nip-Bu described in Chinese patent document having an authorization publication of CN 101974002B), 0.8 part by weight of benzildimethylketal (Micure BK-6, Meiyuan Special chemical Co., Ltd.), 0.7 part by weight of a surfactant (sorbitan fatty acid ester), 0.6 part by weight of an antioxidant (bis (1,2,2,6, 6-pentamethyl-4-piperidinyl) sebacate) and 0.4 part by weight of an ultraviolet light stabilizer (2.4 parts by weight of a UV light stabilizer) (2, 2,6, 6-pentamethyl-4-piperidinyl) were measured at 75 ℃ Hydroxy benzophenone) and uniformly mixing and stirring to obtain the photochromic composition.

The photochromic composition obtained by mixing was uniformly coated on the surfaces of a smooth glass substrate, a plastic (polycarbonate) substrate and a metal (aluminum) substrate, respectively, to a coating thickness of 0.1mm and a coating area of 20X 20cm²(ii) a The coated surface of each substrate was exposed to light having a wavelength of 325nm and an illuminance of 5J/cm²Curing for 5 minutes under the illumination condition to obtain the photochromic film.

Comparative example 6

55 parts by weight of an aliphatic polyester oligomer (formed by mixing 48 parts by weight of urethane acrylate (CN8884 NS, functionality 2, Saedoma chemical Co., Ltd.) and 7 parts by weight of 2 (2-ethoxyethoxy) ethyl acrylate), 33 parts by weight of o-phenylphenoxyethyl acrylate (Miraner M1142, Meiyuan specialty Chemicals Co., Ltd.), 8 parts by weight of phosphomethacrylate (Miraner SC1400, Meiyuan specialty Chemicals Co., Ltd.), 1.5 parts by weight of a photochromic dye (Nip-Bu described in Chinese patent document having an authorization publication of CN 101974002B), 0.8 part by weight of methyl benzoylformate (Micure MBF, Meiyuan specialty Chemicals Co., Ltd.), 0.7 part by weight of a surfactant (sorbitan fatty acid ester) and 0.4 part by weight of an ultraviolet light stabilizer (2-hydroxybenzophenone) were mixed and stirred at a temperature of 75 ℃ and then stirred uniformly, a photochromic composition was obtained.

The photochromic composition obtained by mixing was uniformly coated on the surfaces of a smooth glass substrate, a plastic (polycarbonate) substrate and a metal (aluminum) substrate, respectively, to a coating thickness of 0.1mm and a coating area of 20X 20cm²(ii) a The coated surface of each substrate was exposed to light having a wavelength of 325nm and an illuminance of 5J/cm²Curing for 5 minutes under the illumination condition to obtain the photochromic film.

Performance testing

And (3) shrinkage testing: the specific gravity of the photochromic composition prior to curing was measured and recorded as gamma₁The specific gravity of the photochromic composition after completion of curing (test sample formed on the glass substrate in each example) was measured and recorded as γ₂(ii) a Calculated according to the following formulaShrinkage rate: shrinkage rate ═ y₂-γ₁)/γ₂×100％。

And (3) testing the peeling force: the photochromic films cured and formed on the respective substrates were cut to prepare test strips having a width of 25mm and a length of 150mm, 10 test strips were prepared on each substrate, and the test strips on each substrate were equally divided into A, B groups to perform the peel force test. Wherein, group A was measured for a load value (kgf/25mm) when the test strip was peeled from the substrate at 180 ℃ at a rate of 150 mm/min using a Universal Testing Machine (UTM) at room temperature; and then taking the average value as the test result. After exposing group B to 70 ℃ and 95% relative humidity for 120 hours, the load value (kgf/25mm) when the test strip was peeled from the substrate at 180 ℃ at a rate of 150 mm/min was measured using a Universal Test Machine (UTM); and then taking the average value as the test result.

Surface defect testing: in the test samples formed on the glass substrates in the respective examples, it was observed whether the surface of the produced photochromic film was wrinkled or microporous, and if not, it was marked with "o", otherwise, it was marked with "x".

And (3) weather resistance test: the obtained photochromic glass film was left to stand at 50 ℃ and 90% relative humidity for 7 days, and then it was visually observed whether or not the photochromic film was yellowed, and a case where no yellowing occurred was marked as "o", a case where a slight yellowing occurred only at the edge of the photochromic glass film was marked as "Δ", and a case where a yellowing occurred was marked as "x".

The test results are shown in the following table:

from the table above, it can be seen that, in combination with each of examples and comparative examples 1 and 2: when 2 (2-ethoxy) ethyl acrylate is not added into the aliphatic polyester oligomer, the shrinkage rate of the photochromic film is obviously increased, and the adhesion to the substrate is reduced; when the content of 2 (2-ethoxyethoxy) ethyl acrylate in the aliphatic polyester oligomer is too high, surface defects of the photochromic film increase and weatherability decreases.

Combining the examples with comparative examples 3 and 4, it can be seen that: when the content of the phosphomethacrylate is excessively high, the shrinkage rate of the photochromic film is significantly increased and surface defects are increased; when the content of the phosphoric acid methacrylate is excessively low, the adhesion of the photochromic film substrate is significantly reduced.

Combining the examples and comparative example 5, it can be seen that: when methyl benzoylformate is replaced with benzildimethylketal, surface defects of the photochromic film increase and weather resistance decreases; this is probably due to the ability of methyl benzoylformate to cure the surface of the photochromic composition rapidly in the present invention compared to benzildimethyl ketal.

Combining the examples and comparative example 6, it can be seen that: when the antioxidant is not used, the photochromic film provided by the invention still has better weather resistance.

In conclusion, the photochromic film provided by the invention has the advantages of low shrinkage rate and strong adhesion, and the low yield can avoid the problem that the product is not completely cured due to the photochromic dye changing color in the photocuring process, and large size change and surface defects are caused by natural curing in the later period; the photochromic film can obtain good surface effect without adding auxiliary agents such as a leveling agent and the like; the photochromic film has excellent weather resistance, especially has excellent adhesive force to glass materials, and can be widely applied to vehicles and buildings; meanwhile, the photochromic film is simple in preparation process, high in curing speed and suitable for large-scale batch production.

It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.