TWI464205B - Ultraviolet light absorber and method of manufacturing same - Google Patents

Description

Ultraviolet light absorber and method of manufacturing same

This invention relates to an ultraviolet light absorber, and more particularly to a reactive ultraviolet light absorber.

Resin materials are widely used in various fields because of their light weight and low cost. However, the resin material is liable to be cracked by irradiation of ultraviolet light, and the characteristics of the resin material are degraded. Further, when the resin material is irradiated with ultraviolet light, the resin material may yellow, which affects the appearance of the material and lowers the weather resistance of the resin material, so that the resin material is easily broken.

In order to solve the above problems, the ultraviolet light absorber can be generally added to the resin material by means of physical blending, and the ultraviolet light absorber is used to absorb the ultraviolet light to reduce the influence of the ultraviolet light on the resin material.

However, the conventional ultraviolet light absorber is a solid powder. When blended with a resin material, uneven mixing tends to occur, and the ultraviolet light absorber cannot effectively reduce the influence of ultraviolet light on the resin material.

In view of the above, it is not necessary to provide an ultraviolet light absorber to improve the above disadvantages of the conventional ultraviolet light absorber added to the resin material.

Accordingly, one aspect of the present invention provides an ultraviolet light absorber wherein the ultraviolet light absorber is a liquid material. It can be directly added or reacted with a resin material to produce a chemical bond to overcome the conventional addition of ultraviolet light absorption. Defects of the agent.

Another aspect of the present invention provides a method for synthesizing an ultraviolet light absorber by first providing an aromatic compound, a high molecular polymer and a catalyst, and optionally reacting with or without adding maleic anhydride. To form an ultraviolet light absorber having the above structure.

According to the above aspect of the invention, an ultraviolet light absorber is proposed. In one embodiment, the ultraviolet light absorber has the structure shown by the following formula (I):

In the formula (I), X ₁ represents a structure represented by the following formula (II) or formula (III), and X ₂ represents a hydrogen group, an alkyl group, a phenyl group, a halogen or an alkanocarboxylic acid group, and X ₃ may include but not It is limited to the structure of any one of the following formulas (IV) to (VI). X ₄ represents a methyl group, a propenyl group, a methacryl group or a methylbutenyl group, and a is an integer of from 2 to 50. When X ₃ represents the formula (IV) or the formula (V), Z ₁ represents a structure represented by the following formula (VII), and when X ₃ represents the formula (VI), Z ₁ represents a single bond.

In the formulae (II) and (III), R ₁ , R ₂ and R ₃ each represent a hydrogen group, an alkyl group, a phenyl group, a halogen, a hydroxyl group or an alkanocarboxylic acid group, wherein each of R ₁ and R ₂ may be equal. Or not equal.

In formula (IV), formula (V) and formula (VI), Z ₂ and Z ₄ are each a straight or branched alkyl group having 2 to 4 and 1 to 3 carbon atoms, and Z ₃ is a single bond or a linear or branched alkyl group having 1 to 9 carbon atoms, wherein the oxygen atom of the formula (IV) is bonded to the aromatic ring of the formula (I) and the alkyl group of the formula (VI) and the aromatic ring of the formula (I) Bonding.

According to an embodiment of the present invention, when X ₄ represents a methyl group, a is an integer of 4 to 10.

According to another embodiment of the present invention, when X ₄ represents a propenyl group, a methacryl group or a methylbutenyl group, a is an integer of from 5 to 9.

According to another aspect of the present invention, there is provided an ultraviolet light absorber having a structure represented by the following formula (VIII), wherein e is an integer of from 4 to 10.

According to still another aspect of the present invention, there is provided an ultraviolet light absorber having a structure represented by the following formula (IX), wherein e is an integer of 4 to 10.

According to still another aspect of the present invention, there is provided an ultraviolet light absorber having a structure represented by the following formula (X), wherein f is an integer of from 5 to 9.

According to still another aspect of the present invention, there is provided an ultraviolet light absorber having a structure represented by the following formula (XI), wherein f is an integer of from 5 to 9.

According to still another aspect of the present invention, there is provided an ultraviolet light absorber having a structure represented by the following formula (XII), wherein f is an integer of from 5 to 9.

According to still another aspect of the present invention, a method of producing an ultraviolet light absorber is provided. In one embodiment, a reactant is first provided wherein the reactant is from 28.5 mole percent to 57 mole% aromatic compound, 28.5 mole% to 57 mole% polymer, and 14.25 mole% to 42.75. Mole% of maleic anhydride. The above aromatic compound contains a structure represented by the following formula (XIII):

In the formula (XIII), X ₅ represents a structure represented by the following formula (XIV) or formula (XV), and X ₆ represents a hydrogen group, an alkyl group, a phenyl group, a halogen or an alkylcarboxylic acid group, and X ₇ represents the following formula ( Structure shown by XVI) or (XVII):

In the formulae (XIV) and (XV), R ₄ , R ₅ and R ₆ represent a hydrogen group, an alkyl group, a phenyl group, a halogen, a hydroxyl group or an alkanocarboxylic acid group, wherein R ₄ and R ₅ are each equal or not. equal.

In the formula (XVI), Z ₅ may be a linear or branched alkyl group having a carbon number of 2 to 4, and in the formula (XVII), Z ₆ may be a single bond or a linear chain having a carbon number of 1 to 9. Or branched alkyl.

The above polymer is polyethylene glycol methyl ether, polyethylene glycol propylene ether, polyethylene glycol methyl propylene ether or polyethylene glycol methyl butylene ether. The aforementioned polyethylene glycol methyl ether has a molecular weight of 120 to 2232, the polyethylene glycol propylene ether has a molecular weight of 146 to 2258, the polyethylene glycol methyl propylene ether has a molecular weight of 158 to 2270, and the polyethylene glycol methyl group. The molecular weight of the butenyl ether is 174 to 2,286.

Then, based on 100 parts by weight of the total reactants, 0.1 parts by weight to 1 part by weight of the catalyst is added to the reactants, and the reaction is carried out in the presence of an inert gas until the acid value of the reactants is less than or Equal to 10 to form an intermediate product in which the aforementioned catalyst is an acid catalyst or a base catalyst.

Next, a neutralizing agent is added to the above intermediate product, and a neutralization reaction is carried out to obtain an ultraviolet light absorber, wherein the ultraviolet light absorber has the formula (I), formula (VIII) or formula (IX) as described above. The structure shown.

According to an embodiment of the present invention, the amount of the aromatic compound used is 32.2 mole% to 35.5 mole%, and the amount of the polymer used is 32.2 mole% to 35.5 mole%, and the use of the aforementioned maleic anhydride is used. The amount is from 32.2 mole% to 35.5 mole%.

According to another embodiment of the present invention, the catalyst is used in an amount of from 0.5 part by weight to 0.7 parts by weight based on 100 parts by weight based on the total mass of the reactant.

According to still another embodiment of the present invention, the polyethylene glycol methyl ether has a molecular weight of 208 to 472, the polyethylene glycol propylene ether has a molecular weight of 278 to 454, and the polyethylene glycol methyl propylene ether has a molecular weight of 292 to 468. And the molecular weight of the polyethylene glycol methyl butylene ether is 306 to 482.

According to still another embodiment of the present invention, the acid catalyst may include, but is not limited to, sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, and any combination of the foregoing.

According to still another embodiment of the present invention, the alkali catalyst may include, but is not limited to, an alkali gold metal catalyst, an alkaline earth metal catalyst, and any combination of the above materials.

According to still another embodiment of the present invention, the neutralizing agent may be an acid agent, an alkali agent or an adsorbent.

According to still another aspect of the present invention, a method of producing an ultraviolet light absorber is provided. In one embodiment, first, a reactant is provided wherein the reactant consists of 33.3 mole% to 66.6 mole% of the aromatic compound and 33.3 mole% to 66.6 mole% of the high molecular polymer. The above aromatic compound contains a structure represented by the following formula (XVIII):

In the formula (XVIII), X ₈ represents a structure represented by the following formula (XIX) or formula (XX), and X ₉ represents a hydrogen group, an alkyl group, a phenyl group, a halogen or an alkylcarboxylic acid group, and X ₁₀ represents the following formula: Structure shown by (XXI):

In the formula (XIX) and formula (XX), R ₇ , R ₈ and R ₉ represent a hydrogen group, an alkyl group, a phenyl group, a halogen, a hydroxyl group or an alkanocarboxylic acid group, wherein each of R ₇ and R ₈ may be equal or not equal.

In the formula (XXI), Z ₇ may be a linear or branched alkyl group having 1 to 3 carbon atoms.

The above polymer is polyethylene glycol methyl ether, polyethylene glycol propylene ether, polyethylene glycol methyl propylene ether or polyethylene glycol methyl butyl ether, and the molecular weight of the above polyethylene glycol methyl ether The molecular weight of the polyethylene glycol propylene ether is from 146 to 2,258, the molecular weight of the polyethylene glycol methyl propylene ether is from 158 to 2,270, and the molecular weight of the polyethylene glycol methyl butylene ether is from 174 to 2,286.

Then, based on 100 parts by weight of the total reactants, 0.1 parts by weight to 1 part by weight of the catalyst is added to the reactants, and the reaction is carried out in the presence of an inert gas until the acid value of the reactants is less than or Equal to 10 to form an intermediate product in which the aforementioned catalyst is an acid catalyst or a base catalyst.

Next, a neutralizing agent is added to the intermediate product, and a neutralization reaction is performed to obtain an ultraviolet light absorber, wherein the ultraviolet light absorber has any one of the above formula (I) or formula (X) to formula (XII). The structure shown.

According to an embodiment of the present invention, the aromatic compound is used in an amount of 47.6 mole% to 52.4 mole% and the polymer is used in an amount of 47.6 mole% to 52.4 mole%.

According to another embodiment of the present invention, the catalyst is used in an amount of from 0.5 part by weight to 0.7 parts by weight based on 100 parts by weight based on the total mass of the reactant.

According to still another embodiment of the present invention, the polyethylene glycol methyl ether has a molecular weight of 208 to 472, the polyethylene glycol propylene ether has a molecular weight of 278 to 454, and the polyethylene glycol methyl propylene ether has a molecular weight of 292 to 468. And the molecular weight of the polyethylene glycol methyl butylene ether is 306 to 468.

In accordance with still another embodiment of the present invention, the acid catalyst may include, but is not limited to, sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, and any combination of the foregoing.

According to still another embodiment of the present invention, the alkali catalyst may include, but is not limited to, an alkali gold metal catalyst, an alkaline earth metal catalyst, and any combination of the above materials.

According to still another embodiment of the present invention, the mixture may be an acid agent, an alkali agent or an adsorbent.

The ultraviolet light absorber of the present invention is used to enhance the characteristics of the ultraviolet light absorber by changing the functional group of the reactant and the kind of the reactant, so that the ultraviolet light absorber is a liquid material, thereby making the ultraviolet light absorber It is uniformly mixed with the resin material, so the manufacturing cost can be reduced.

Furthermore, the ultraviolet light absorbing agent of the present invention can form a chemical bond with a resin material to polymerize into a resin material having an ultraviolet light absorbing group, and can enhance the protection of the ultraviolet light absorbing group for the resin material.

The making and using of the embodiments of the invention are discussed in detail below. However, it will be appreciated that the embodiments provide many applicable inventive concepts that can be implemented in a wide variety of specific content. The specific embodiments discussed are illustrative only and are not intended to limit the scope of the invention.

The present invention provides an ultraviolet light absorber having a structure represented by the following formula (I):

In the formula (I), X ₁ represents a structure represented by the following formula (II) or formula (III), and X ₂ represents a hydrogen group, an alkyl group, a phenyl group, a halogen or an alkanocarboxylic acid group, and X ₃ may include but not The structure is limited to any one of the following formulas (IV) to (VI), and X ₄ represents a methyl group, a propenyl group, a methacryl group or a methylbutenyl group, and a is an integer of from 2 to 50. If X ₄ represents a methyl group, a may be an integer of 4 to 10; and when X ₄ represents a propylene group, a may be an integer of 5 to 9.

When X ₃ represents the formula (IV) or the formula (V), Z ₁ represents a structure represented by the following formula (VII). When X ₃ represents the formula (VI), Z ₁ represents a single bond.

In formula (II) and formula (III), R ₁ , R ₂ and R ₃ each independently represent a hydrogen group, an alkyl group, a phenyl group, a halogen, a hydroxyl group or an alkanocarboxylic acid group, wherein each of R ₁ and R ₂ may be Equal or unequal functional groups.

In formula (IV), formula (V) and formula (VI), Z ₂ and Z ₄ are each a straight or branched alkyl group having 2 to 4 and 1 to 3 carbon atoms, and Z ₃ is a single bond or a linear or branched alkyl group having 1 to 9 carbon atoms, wherein the oxygen atom of the formula (IV) is bonded to the aromatic ring of the formula (I) and the alkyl group of the formula (VI) and the aromatic ring of the formula (I) Bonding.

In one embodiment, the above Z ₂ may be an ethane group, a propane group, a butane group, an isopropyl group, a methylpropyl group or a dimethylethane group. Z ₃ may be a single bond, a methyl group, an ethane group, a propane group, a butane group, a pentylene group, a hexane group, a heptyl group, an octyl group or a decyl group. Z ₄ may be a methyl group, an ethane group, a propane group or an isopropyl group.

Specific examples of the ultraviolet light absorber described above may be a structure represented by any one of the following formulae (VIII) to (XII):

Wherein the aforementioned e is an integer from 4 to 10 and f is an integer from 5 to 9.

The above method for producing an ultraviolet light absorber is to provide a reactant. This reactant is composed of an aromatic compound (A-1), a high molecular polymer (B), and maleic anhydride (C) and does not contain an organic solvent.

The above aromatic compound (A-1) has a structure represented by the following formula (XIII):

In the formula (XIII), X ₅ represents a structure represented by the following formula (XIV) or formula (XV), and X ₆ represents a hydrogen group, an alkyl group, a phenyl group, a halogen or an alkylcarboxylic acid group, and X ₇ represents the following formula ( XVI) or the structure shown by formula (XVII).

In the formulae (XIV) and (XV), R ₄ , R ₅ and R ₆ represent a hydrogen group, an alkyl group, a phenyl group, a halogen, a hydroxyl group or an alkanocarboxylic acid group, wherein each of R ₄ and R ₅ may be equal or not equal.

In the formula (XVI) and the formula (XVII), Z ₅ may be a linear or branched alkyl group having 2 to 4 carbon atoms, and Z ₆ may be a single bond or a linear chain having a carbon number of 1 to 9 or Branched alkyl. In one embodiment, the above Z ₅ may be an ethane group, a propane group, a butane group, an isopropyl group, a methylpropyl group or a dimethylethane group. Z ₆ may be a single bond, a methyl group, an ethane group, a propane group, a butane group, a pentyl group, a hexane group, a heptyl group, an octyl group or a decyl group.

In one embodiment, the aromatic compound (A-1) may be 2-hydroxy-4-(β-hydroxy-ethoxy)benzophenone. (hereinafter referred to as BP1) or 2-[2-hydroxy-4-(hydroxy-ethoxy)phenyl]benzotriazole (hereinafter referred to as 2-[2-hydroxy-4-(β-hydroxy-ethoxy)phenyl]benzotriazole; BT1).

The structure of the aromatic compound (A-1) has the property of absorbing ultraviolet light, so that the ultraviolet light absorbing agent of the present invention can effectively absorb ultraviolet light, thereby making the resin material free from ultraviolet light.

The amount of the above aromatic compound (A-1) used is from 28.5 mole% to 57 mole%. If the amount of the aromatic compound (A-1) used is less than 28.5 mole%, the absorption effect of the ultraviolet light absorber on ultraviolet light is lowered. When the amount of the aromatic compound (A-1) used is more than 57 mole%, the ultraviolet light absorber is solid at room temperature (for example, 20 ° C to 35 ° C), and is not easily mixed uniformly with the resin material. In another embodiment, the aromatic compound (A-1) is used in an amount of from 32.2 mole% to 35.5 mole%.

The amount of the above polymer (B) used is from 28.5 mole% to 57 mole%. Since the high molecular polymer (B) has an alkoxy chain, the ultraviolet light absorber can be liquefied, and the hydrophilicity of the ultraviolet light absorber can be enhanced, so that the ultraviolet light absorber can be uniformly mixed with the resin material. If the amount of the polymer (B) used is less than 28.5 mole%, the reactivity of the synthesis reaction is not good. If the amount of the polymer (B) used is more than 57 mole%, the ability of the ultraviolet light absorber to absorb ultraviolet light is not good, and the effect of protecting the resin material cannot be effectively achieved. In another embodiment, the high molecular weight polymer (B) is used in an amount of from 32.2 mole% to 35.5 mole%.

The above polymer (B) may be Methoxy polyethylene glycol (MPEG) or Allyloxy polyethylene glycol (APEG) or polyethylene glycol methyl propylene ether (Methyl-). Allyloxy polyethylene glycol; VPEG) or Methyl-Butenyloxy polyethylene glycol (TPEG), wherein MPEG has a molecular weight of 120 to 2232, APEG has a molecular weight of 146 to 2258, and VPEG has a molecular weight of 158 to 2270. And TPEG has a molecular weight of 174 to 2286. In another embodiment, the molecular weight of MPEG is 208 to 472, and the molecular weight of APEG is 278 to 454. The molecular weight of VPEG It is 292 to 468, and the molecular weight of TPEG is 306 to 482.

If the molecular weight of MPEG is less than 120, the ultraviolet light absorber is solid at room temperature (for example, 20 ° C to 35 ° C). If the molecular weight of MPEG exceeds 2232, the effect of the ultraviolet light absorber to absorb ultraviolet light is lowered, and the resin material is cracked by ultraviolet light irradiation. Similarly, when the molecular weight of APEG is lower than 146 or the molecular weight is higher than 2258, the molecular weight of VPEG is less than 158 or greater than 2270, or the molecular weight of TPEG is less than 174 or greater than 2286, respectively, ultraviolet light absorption synthesized by using the above high molecular polymers respectively The effect of the agent to absorb ultraviolet light is not good, and the effect of protecting the resin material cannot be achieved.

The aforementioned maleic anhydride (C) may be used in an amount of from 14.25 mole% to 42.75 mole%. In the above-mentioned synthesis reaction, maleic anhydride (C) undergoes a ring-opening reaction and forms an esterification reaction with the aromatic compound (A-1) and the high molecular polymer (B), and an aromatic compound (A- 1) Both the high molecular polymer (B) and the polymer (B) are bonded. If the amount of maleic anhydride (C) used is less than 14.25 mole%, the appearance of the synthesized ultraviolet light absorber is a solid-containing heterogeneous phase, and a clear liquid cannot be formed. If the amount of maleic anhydride (C) used is higher than 42.75 mole%, the acid value of the synthesis reaction is not easily reduced to 10 or less, thereby increasing the manufacturing cost. In another embodiment, the maleic anhydride (C) can be used in an amount from 32.2 mole% to 35.5 mole%.

Then, based on 100 parts by weight based on the total weight of the reactants described above, 0.1 part by weight to 1 part by weight of the catalyst (D) is added to the above reactant, and the reaction is carried out in the presence of an inert gas to form an intermediate portion. product. At the time of the reaction, the quantitative reactant was taken at intervals, and the acid-base titration was carried out with potassium hydroxide, and the acid value of the reactant was measured. The acid value referred to herein refers to the amount of potassium hydroxide required to achieve acid-base neutralization per gram of reactant. number. When the acid value is greater than 10, the reaction is continued. When the acid value is less than or equal to 10, the reaction is terminated.

The above inert gas may be nitrogen, helium or other suitable inert gas, and the aforementioned catalyst (D) may be an acid catalyst or a base catalyst. The above acid catalysts may include, but are not limited to, sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, other suitable acid catalysts, and any combination of the foregoing. The foregoing base catalyst may include, but is not limited to, an alkali gold metal catalyst, an alkaline earth metal catalyst, other suitable base catalysts, and any combination of the above.

The catalyst (D) can increase the reactivity of the synthesis reaction and reduce the manufacturing cost. When the amount of the catalyst (D) used is less than 0.1 part by weight, the reaction rate of the synthesis reaction is too slow, thereby increasing the production cost. When the amount of the catalyst (D) used is more than 1 part by weight, the appearance of the formed ultraviolet light absorber is turbid, which makes the subsequent filtration process difficult to carry out, thereby increasing the manufacturing cost. In another embodiment, the catalyst (D) may be used in an amount of 0.5 parts by weight to 0.7 parts by weight based on 100 parts by weight of the total of the reactants described above.

Next, the temperature of the aforementioned intermediate product is lowered to 50 ° C, and a neutralizing agent is added to the intermediate product to carry out an acid-base neutralization reaction, and the pH of the intermediate product is 4.0 to 6.0, thereby obtaining ultraviolet light absorption. The ultraviolet light absorber having the structure represented by the above formula (I). The aforementioned neutralizing agent can neutralize the intermediate product. In one embodiment, the neutralizing agent can be an acid agent (eg, acetic acid, phosphoric acid or fruit acid), an alkaline agent (eg potassium carbonate, sodium hydroxide or potassium hydroxide) or an adsorbent (eg aluminum magnesium oxide) ). When the neutralizing agent is an adsorbent of aluminum-magnesium oxide, the adsorbent selects aluminum-magnesium oxides of different composition ratios according to the acid-base condition of the intermediate product, so that the pH of the intermediate product is 4.0 to 6.0. . The selection of the above aluminum magnesium oxide is the technology of the present invention Anyone with ordinary knowledge in the field of surgery is well known and will not be described here. In another embodiment, the neutralizing agent can be potassium carbonate.

In another embodiment, the reactants are composed of an aromatic compound (A-2) and a high molecular polymer (B) and do not contain an organic solvent, wherein the aromatic compound (A-2) comprises the following formula ( Structure shown in XVIII):

In the formula (XVIII), X ₈ represents a structure represented by the following formula (XIX) or formula (XX), and X ₉ represents a hydrogen group, an alkyl group, a phenyl group, a halogen or an alkylcarboxylic acid group, and X ₁₀ represents the following formula: Structure shown by (XXI):

In the formula (XIX) and the formula (XX), R ₇ , R ₈ and R ₉ represent a hydrogen group, an alkyl group, a phenyl group, a halogen or an alkanocarboxylic acid group, wherein each of R ₇ and R ₈ may be equal or unequal. .

In the formula (XXI), Z ₇ may be a linear or branched alkyl group having 1 to 3 carbon atoms. In one embodiment, Z ₇ may be a group of methane, ethane diyl, propane-alkyl group or an isopropyl group.

In one embodiment, the aromatic compound (A-2) may be 3-hydroxy-4-(benzoyl)benzenepropanoic acid (hereinafter referred to as BP2) or 3 -[3-(2-Benzatriazolyl)-5-isobutyl-4-hydroxyphenyl]-propionic acid (3-[3-(2H-benzotriazole-2-yl)-5-tert-butyl- 4-hydroxyphenyl]-propionic acid; hereinafter referred to as BT2).

In the above reactant, the aromatic compound (A-2) is used in an amount of from 33.3 mole% to 66.6 mole%. When the amount of the aromatic compound (A-2) used is less than 33.3 mole%, the ultraviolet light absorbing effect of the ultraviolet light absorber is lowered. When the amount of the aromatic compound (A-2) used is more than 66.6 mole%, the synthesized ultraviolet light absorber is a solid-containing heterogeneous phase, and a clear liquid cannot be formed. In another embodiment, the aromatic compound (A-2) may be used in an amount of 47.6 mole% to 52.4 mole%.

The polymer (B) is used in an amount of 33.3 mole% to 66.6 mole%. If the amount of the polymer (B) used is less than 33.3 mole%, the ultraviolet absorber is a solid-containing heterogeneous phase, and a clear liquid cannot be formed. If the amount of the polymer (B) used is higher than 66.6 mole%, the effect of the ultraviolet light absorber to absorb ultraviolet light is lowered. In another embodiment, the high molecular polymer (B) may be used in an amount of 47.6 mole% to 52.4 mole%.

According to the above-mentioned method for synthesizing the ultraviolet light absorber, in the case of adding maleic anhydride (C), when the aromatic compound (A-1) is BP1 (as shown by the following formula (XXII)) and the polymer (B) In the case of MPEG, the synthesized ultraviolet light absorber has a structure represented by the following formula (VIII), wherein e may be an integer of 4 to 10.

In the formula (VIII), the double bond between the carbon atom k and the carbon atom m can be copolymerized with the resin material, thereby forming a chemical bond, and a resin material having an ultraviolet light absorbing group can be synthesized, and further Increase ultraviolet light The protection of the absorbent material to the resin material.

In the case where maleic anhydride (C) is not added, when the aromatic compound (A-2) is BT2 (as shown in the following formula (XXIII)) and the high molecular polymer (B) is APEG, the synthesized ultraviolet light The absorbent has a structure represented by the following formula (X), wherein f may be an integer of from 5 to 9.

Similarly, in the formula (X), a double bond between the carbon atom n and the carbon atom p can form a chemical bond with the resin material, and a resin material having an ultraviolet light absorbing group can be synthesized.

Further, when the aromatic compound (A-2) is BT2 and the high molecular polymer (B) is VPEG or TPEG, the carbon atom double bond of the terminal group of the synthesized ultraviolet light absorber may also form a chemical bond with the resin material. A resin material having an ultraviolet light absorbing group can be synthesized.

Preparation of ultraviolet light absorber

Hereinafter, the ultraviolet light absorbers of Synthesis Examples S-1 and S-2 and Comparative Synthesis Examples AS-1 and AS-2 were prepared according to Table 1.

Synthesis Example S-1

First, 33 mole% of BP1, 33 mole% of MPEG and 34 mole% of maleic anhydride were added to the reaction tank. Then, based on the foregoing The total weight of BP1, MPEG and maleic anhydride was 100 parts by weight, 0.6 parts by weight of an acid catalyst was added to the above reactant, and nitrogen gas was introduced to discharge the air in the reaction tank. After the above materials were dissolved, stirring was started and nitrogen gas was continuously supplied. After the temperature was raised to 100 ° C, stirring was continued for 3 hours. Next, the temperature was raised to 140 ° C to carry out the reaction. The acid value of the reactants was then measured with potassium hydroxide. When the acid value of the reactant is equal to 10, the reaction is terminated. Thereafter, the reactant is cooled to 50 ° C, and neutralized with potassium carbonate in an acid-base until the pH of the reactant is 4.0 to 6.0, thereby preparing an ultraviolet light absorber (S-1; the following formula (VIII) Show that where e is 7). The light transmittance of the obtained ultraviolet light absorbing agent was evaluated by the evaluation method of the following evaluation method, and the result is as described in the first table, and the method for detecting the light transmittance is described later.

Synthesis Examples S-2 to S-4 and Comparative Synthesis Examples AS-1 and AS-2

Synthesis Examples S-2 to S-4 and Comparative Synthesis Examples AS-1 and AS-2 were reacted using the same apparatus and method as in Synthesis Example S-1. The difference is that Synthetic Examples S-2 to S-4 and Comparative Synthesis Examples AS-1 and AS-2 use different kinds and different ratios of reactants, and the formulation and detection results are shown in Table 1, here. Unless otherwise stated, the ultraviolet light absorbers prepared in Synthesis Examples S-2 to S-4 are represented by the following formulas (X) to (XII) (S-2; as shown in the following formula (X), wherein f is 6 S-3; represented by the following formula (XI), wherein f is 7. S-4; as shown in the following formula (XII), wherein f is 6.).

Preparation of UV resistant resin materials

The ultraviolet-resistant resin materials of Examples 1 and 2 and Comparative Examples 1 to 3 were prepared according to Table 2 below.

Example 1

1 wt% of the ultraviolet light absorber prepared in Synthesis Example S-1 was added to 99 wt% of the resin material, and mixed, and Example 1 was obtained. The obtained ultraviolet-resistant resin material was evaluated in the following evaluation manners, and the results are as described in Table 2, wherein the compatibility of the ultraviolet-resistant resin material and the detection method of yellowing resistance are described later. The above-mentioned resin material is a copolymer of styrene and butyl acrylate manufactured by Changxing Chemical Co., Ltd., and its model number is 6512-1.

Examples 2 to 4 and Comparative Examples 1 and 2

Examples 2 to 4 and Comparative Examples 1 and 2 were prepared in the same manner as in Example 1. The difference is that Examples 2 to 4 and Comparative Examples 1 and 2 Different types and different proportions of ultraviolet light absorbers are used respectively, and the formulation and test results are shown in Table 2, and are not described here.

Comparative example 3

In Comparative Example 3, the ultraviolet light absorbing agent was not added, and the yellowing resistance of the ultraviolet resistant resin material of the following evaluation method was carried out only by the above-mentioned resin material, and the detection results are shown in Table 2.

Evaluation method

Light transmission

The light transmittance of the ultraviolet light absorber is visually observed for the transmittance of the ultraviolet light absorber. The results are shown in Table 1, wherein "○" represents that the ultraviolet light absorber is transparent, and "△" represents a heterogeneous phase containing the solid of the ultraviolet light absorber.

2. Translucency of UV resistant resin materials

The light transmissive property of the ultraviolet resistant resin material is applied to a polyethylene terephthalate (PET) substrate by the above examples and comparative examples, and dried to form a film to be tested. The length and width dimensions of the PET substrate were 10 cm and 5 cm, respectively, and the thickness of the resin coating was 200 μm.

Next, the transparency of the resin coating was observed visually. The results are shown in Table 2, wherein "○" indicates that the resin coating layer was transparent, and "△" indicates that the resin coating layer was cloudy.

3. Resistance to yellowing of UV resistant resin materials

The yellowing resistance of the ultraviolet resistant resin material is observed by visually observing the color of the aforementioned test piece, and the Y ₁ value of the test piece is judged according to the color rendering of the Y primary color portion of M=0 in FIG. ₁ . Figure 1 shows the MY color map in the CMYK color chart, where C represents cyan, M represents magenta, Y stands for yellow and K stands for black.

Next, the above-mentioned test piece was irradiated with an ultraviolet lamp having a power of 120 W/cm. After 8 hours of irradiation, the color of the sheet to be tested was visually observed, and the Y ₂ value of the sheet to be tested was judged against the first graph by the aforementioned method. Then, the ΔY value of the sheet to be tested is calculated by the following formula (XXIV). The results are shown by the yellowing resistance of the ultraviolet resistant resin material of Table 2, wherein "○" represents ΔY≦10, and "△" represents ΔY>10.

△Y=Y ₂ -Y ₁ (XXIV)

Please refer to Table 1, which shows the composition and composition ratio of the ultraviolet light absorber and the evaluation results of the above-mentioned light transmittance.

According to the results of the first table, the synthesis examples S-1, S-2, S-3, and S-4 were compared with the comparative synthesis examples AS-1 and AS-2, and the synthesis examples S-1, S-2, and S were compared. -3 and S-4 ultraviolet light absorbers are transparent.

According to the results of the second table, in Examples 1 to 4, the ultraviolet light absorber has good compatibility with the resin material and does not affect the appearance of the substrate. Furthermore, the ultraviolet light absorbing agent of the present invention can effectively absorb ultraviolet light, and can improve the yellowing resistance of the ultraviolet resistant resin material, thereby achieving the effect of protecting the resin material.

According to the above embodiments of the present invention, the ultraviolet light absorber of the present invention The advantage is that it can effectively absorb ultraviolet light to protect the resin material, and can avoid yellowing of the resin material. Furthermore, the ultraviolet light absorbing agent of the present invention has good compatibility with the resin material, and has good light transmittance when mixed with the resin material.

Further, in the case where maleic anhydride (C) is added, the ultraviolet light absorber synthesized in accordance with the foregoing method can be polymerized with a resin material to form a chemical bond, and react to form a resin material having an ultraviolet light absorbing group. In the case where maleic anhydride (C) is not added, if the polymer (B) used is APEG, VPEG or TPEG, the ultraviolet light absorber formed may be polymerized with the resin material to form a chemical bond. It can react to form a resin material having an ultraviolet light absorbing group.

The present invention has been disclosed in the above embodiments, and is not intended to limit the present invention. Any one of ordinary skill in the art to which the present invention pertains can make various changes without departing from the spirit and scope of the invention. The scope of protection of the present invention is therefore defined by the scope of the appended claims.

The above and other objects, features, advantages and embodiments of the present invention will become more <RTIgt; <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt;

Claims (22)

An ultraviolet light absorber having a structure represented by the following formula (I): In the formula (I), the X ₁ represents a structure represented by the following formula (II) or formula (III), and the X ₂ represents a hydrogen group, an alkyl group, a phenyl group, a halogen or an alkanocarboxylic acid group, and the X ₃ Is selected from the group consisting of the structures of formula (IV) to formula (VI), the X ₄ represents a methyl group, a propenyl group, a methacryl group or a methylbutenyl group, and the a is 2 to 50 An integer, wherein when X ₃ represents the formula (IV) or the formula (V), the Z ₁ represents a structure represented by the following formula (VII), and when the X ₃ represents the formula (VI), Z ₁ represents a single bond, and the X ₄ does not represent the methyl group; In the formula (II), R ₁ and R ₂ each represent a hydrogen group, an alkyl group, a phenyl group, a halogen, a hydroxyl group or an alkanocarboxylic acid group, and the R ₁ and the R ₂ are each equal or unequal; In the formula (III), the R ₃ represents a hydrogen group, an alkyl group, a phenyl group, a halogen, a hydroxyl group or an alkanocarboxylic acid group; in the formula (IV), the Z ₂ series has a carbon number of 2 to 4 a chain or a branched alkyl group, and the oxygen atom is bonded to the aromatic ring of the formula (I); in the formula (V), the Z ₃ is a single bond or a linear chain having a carbon number of 1 to 9 or a branched alkyl group; and in the formula (VI), the Z ₄ is a linear or branched alkyl group having 1 to 3 carbon atoms, and the alkyl group and the aromatic ring bond of the formula (I) Knot. The ultraviolet light absorber according to claim 1, wherein when X ₄ represents the methyl group, the a is an integer of 4 to 10. The ultraviolet light absorber according to claim 1, wherein when X ₄ represents the propenyl group, the methacryl group or the methylbutenyl group, the a is an integer of 5 to 9. An ultraviolet light absorber having a structure represented by the following formula (VIII): Wherein e is an integer from 4 to 10. An ultraviolet light absorber having a structure represented by the following formula (IX): Wherein e represents an integer from 4 to 10. An ultraviolet light absorber having a structure represented by the following formula (X): Wherein f represents an integer from 5 to 9. An ultraviolet light absorber having a structure represented by the following formula (XI): Wherein f represents an integer from 5 to 9. An ultraviolet light absorber having a structure represented by the following formula (XII): Wherein f represents an integer from 5 to 9. A method for producing an ultraviolet light absorber, comprising: providing a reactant, wherein the reactant is polymerized from 28.5 mol% to 57 mole% of one aromatic compound, and 28.5 mole% to 57 mole%. And a composition of 14.25 mole% to 42.75 mole% of maleic anhydride, wherein the aromatic compound comprises a structure represented by the following formula (XIII): In the formula (XIII) in which X ₅ representatives of the following structural formula (XIV) or Formula (XV) as shown, the X ₆ represents hydrogen, alkyl, phenyl, halogen or a carboxylic acid group, the X ₇ Represents a structure represented by the following formula (XVI) or formula (XVII): In the formula (XIV), R ₄ and R ₅ represent a hydrogen group, an alkyl group, a phenyl group, a halogen, a hydroxyl group or an alkanocarboxylic acid group, and the R ₄ and the R ₅ are each equal or unequal; In the formula (XV), R ₆ represents a hydrogen group, an alkyl group, a phenyl group, a halogen group, a hydroxyl group or an alkanocarboxylic acid group; in the formula (XVI), the Z ₅ group has a linear chain of 2 to 4 carbon atoms. Or a branched alkyl group; and in the formula (XVII), the Z ₆ single bond or a linear or branched alkyl group having a carbon number of 1 to 9; and the high molecular polymer is polyethylene glycol Methyl ether, polyethylene glycol propylene ether, polyethylene glycol methyl propylene ether or polyethylene glycol methyl butyl ether, the molecular weight of the polyethylene glycol methyl ether is 120 to 2232, the polyethylene glycol propylene ether The molecular weight is 146 to 2258, the molecular weight of the polyethylene glycol methyl propylene ether is 158 to 2270, and the molecular weight of the polyethylene glycol methyl butylene ether is 174 to 2286; and the total weight based on the reactant is 100 To the parts by weight, 0.1 part by weight to 1 part by weight of one catalyst is added to the reactant, and the reaction is carried out in the presence of an inert gas until the acid value of the reactant is less than or equal to 10 to form an intermediate product. , the catalyst An acid catalyst or a base catalyst; and adding a neutralizing agent to the intermediate product, and performing a neutralization reaction to obtain the ultraviolet light absorber, wherein the ultraviolet light absorber has the requirements of claims 1 to 5 The structure described in any one of the above. The method for producing an ultraviolet light absorber according to claim 9, wherein the aromatic compound is used in an amount of 32.2 mole% to 35.5 mole%, and the polymer polymer is used in an amount of 32.2 mole% to 35.5 mole%. The amount of maleic anhydride used is from 32.2 mole% to 35.5 mole%. The method for producing an ultraviolet light absorber according to claim 9, wherein the catalyst is used in an amount of from 0.5 part by weight to 0.7 parts by weight based on 100% by weight based on the total mass of the reactant. The method for producing an ultraviolet light absorber according to claim 9, wherein the polyethylene glycol methyl ether has a molecular weight of 208 to 472, and the polyethylene glycol propylene ether has a molecular weight of 278 to 454. The molecular weight of the methacrylic ether is 292 to 468, and the molecular weight of the polyethylene glycol methyl butylene ether is 306 to 482. The method of producing an ultraviolet light absorber according to claim 9, wherein the acid catalyst is selected from the group consisting of sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, and any combination thereof. The method for producing an ultraviolet light absorber according to claim 9, wherein the base catalyst is selected from the group consisting of an alkali metal group metal catalyst, an alkaline earth metal catalyst, and any combination thereof. The method for producing an ultraviolet light absorber according to claim 9, wherein the neutralizing agent is an acid agent, an alkali agent or an adsorbent. A method for producing an ultraviolet light absorber, comprising: providing a reactant, wherein the reactant is composed of 33.3 mole% to 66.6 mole% of one aromatic compound and 33.3 mole% to 66.6 mole% of one high molecular polymer. Wherein the aromatic compound comprises a structure represented by the following formula (XVIII): In the formula (XVIII) in which X ₈ represent the following formula (XIX) or formula (XX) of the configuration shown, the group X ₉ represents hydrogen, alkyl, phenyl, halogen or carboxylic acid group, the X ₁₀ Represents the structure shown by the following formula (XXI): In the formula (XIX), R ₇ and R ₈ represent a hydrogen group, an alkyl group, a phenyl group, a halogen, a hydroxyl group or an alkanocarboxylic acid group, and the R ₇ and the R ₈ are each equal or unequal; In the formula (XX), the R ₉ represents a hydrogen group, an alkyl group, a phenyl group, a halogen, a hydroxyl group or an alkanocarboxylic acid group; and in the formula (XXI), the Z ₇ series has a carbon number of 1 to 3 a chain or a branched alkyl group; and the polymer is polyethylene glycol propylene ether, polyethylene glycol methyl propylene ether or polyethylene glycol methyl butyl ether, the molecular weight of the polyethylene glycol propylene ether The molecular weight of the polyethylene glycol methyl propylene ether is 158 to 2270, and the molecular weight of the polyethylene glycol methyl butylene ether is 174 to 2286; and the total weight of the reactant is 100 parts by weight. Adding 0.1 parts by weight to 1 part by weight of one of the catalyst to the reactant, and carrying out the reaction in the presence of an inert gas until the acid value of the reactant is less than or equal to 10 to form an intermediate product, wherein The catalyst is an acid catalyst or a base catalyst; and a neutralizing agent is added to the intermediate product, and a neutralization reaction is carried out to obtain the ultraviolet light absorber, wherein the ultraviolet light The absorber has a structure according to any one of items 1 to 3 as a request or request entries 6-8. The method for producing an ultraviolet light absorber according to claim 16, wherein the aromatic compound is used in an amount of 47.6 mole% to 52.4 mole% and the polymer is used in an amount of 47.6 mole% to 52.4 mole%. The method for producing an ultraviolet light absorber according to claim 16, wherein the catalyst is used in an amount of from 0.5 part by weight to 0.7 part by weight based on 100% by weight based on the total mass of the reactant. A method of producing an ultraviolet light absorber according to claim 16, which The polyethylene glycol propylene ether has a molecular weight of 278 to 454, the polyethylene glycol methyl propylene ether has a molecular weight of 292 to 468, and the polyethylene glycol methyl butylene ether has a molecular weight of 306 to 482. The method of producing an ultraviolet light absorber according to claim 16, wherein the acid catalyst is selected from the group consisting of sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, and any combination thereof. The method for producing an ultraviolet light absorber according to claim 16, wherein the base catalyst is selected from the group consisting of an alkali gold metal catalyst, an alkaline earth metal catalyst, and any combination thereof. The method for producing an ultraviolet light absorber according to claim 16, wherein the neutralizing agent is an acid agent, an alkali agent or an adsorbent.