TWI762175B - Self-healing resin composition and use thereof - Google Patents

Abstract

A self-healing resin composition is disclosed, which comprises: 100 parts of polyurethane resin; and 0.1 to 10 parts of additives, wherein the additives comprises an UV absorber, a light stabilizer and an antioxidant. The UV absorber comprises 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylp henyl)-1,3,5- triazine and 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylp henyl)-1,3,5- triazine, the light stabilizer is N-(1-Acetyl-2,2,6,6-tetramethyl-4-piperidinyl)-2-dodecylsuccinimide, and the antioxidant is benzenepropanoic acid, 3,5-bis (1,1-dimethyl-ethyl)-4-hydroxy-C7-C9 branched alkyl esters. A weight ratio of the UV absorber, the light stabilizer and the antioxidant is 2~3 : 1 : 1. In addition, a use of the aforesaid self-healing resin composition is also disclosed.

Description

Self-healing resin composition and use thereof

The present disclosure relates to a self-healing resin composition and use thereof, in particular to a self-healing resin composition with good heat resistance and/or weather resistance and use thereof.

In recent years, the development of self-healing resin can make the coating formed by the self-healing resin have the function of scratch repair, so as to reduce the problem of re-spraying and repair after the coating is scratched, thereby prolonging the service life of the coating and greatly reducing the Maintenance costs for users.

However, when the coating formed by the self-healing resin is exposed to UV light for a long time or exposed to a high temperature environment, the coating will have the problem of fading, or the problem of poor self-healing recovery rate after scratching.

In view of this, there is an urgent need to develop a self-healing resin, which can improve the problem of fading or poor self-healing recovery rate caused by long-term UV light irradiation or exposure to high temperature environments, thereby improving the formation of self-healing resins. The service life of the coating is to save the user's maintenance cost.

The present disclosure provides a self-healing resin composition, comprising: 100 parts by weight of a polyurethane resin; and 0.1 to 10 parts by weight of additives, wherein the additives include an ultraviolet light absorber, a light Stabilizers and an antioxidant, UV absorbers including 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis( 2,4-Dimethylphenyl)-1,3,5-triazine(2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2 ,4-dimethylphenyl)-1,3,5-triazine) and 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6 -Bis(2,4-dimethylphenyl)-1,3,5-triazine(2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6- bis(2,4-dimethylphenyl)-1,3,5-triazine), the photostabilizer is N-(1-acetyl-2,2,6,6-tetramethyl-4-piperidinyl)- 2-Dodecylsuccinimide (N-(1-Acetyl-2,2,6,6-tetramethyl-4-piperidinyl)-2-dodecylsuccinimide), and the antioxidants are phenylpropionic acid, 3,5-bis (1,1-Dimethyl-ethyl)-4-hydroxy-C7-C9 branched alkyl ester (Benzenepropanoic acid, 3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-C7- C9 branched alkyl esters), and the weight ratio of UV absorber, light stabilizer and antioxidant is 2~3:1:1.

In the self-healing resin composition of the present disclosure, by adding additives containing a specific ratio and specific components of an ultraviolet light absorber, a light stabilizer and an antioxidant to the polyurethane resin, the formed polyurethane resin coating can have good properties. Heat and/or weather resistance. In particular, for the coating formed by the self-healing resin composition provided by the present disclosure, after the heat resistance and weather resistance test, the color difference of the coating before and after the test is not large, and at the same time, the formed coating can still exhibit good scratches Restorative. Therefore, the coating formed by the self-healing resin composition of the present disclosure has an improved service life.

In the present disclosure, ultraviolet light absorbers include 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2, 4-Dimethylphenyl)-1,3,5-triazine and 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]- 4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine. In more detail, in the present disclosure, the UV absorber is 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxybenzene yl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-[(2-hydroxy-3-dodecyloxypropyl) Oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine mixture.

In the present disclosure, based on 100 parts by weight of the polyurethane resin, the content of the additive may be 0.1 to 10 parts by weight, for example, 0.5 to 2 parts by weight or 1 to 2 parts by weight.

In the present disclosure, the antioxidant can be phenylpropionic acid, 3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-C7-C9 branched alkyl ester, for example, can be phenylpropionic acid acid, 3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-branched octyl ester.

In the present disclosure, the polyurethane resin can be a polymer obtained by reacting a polyol and a polyisocyanate. Wherein, the weight ratio of polyol to polyisocyanate may be between 3:1 and 5:1, for example, between 3.2:1 and 4.8:1 or 3.5:1 and 4.5:1. In an embodiment of the present disclosure, the weight ratio of polyol to polyisocyanate may be about 4:1.

In the present disclosure, the polyol may be a polyester polyol. Among them, polyester polyols can be obtained by dehydration condensation of polyols and carboxylic acids. Specific examples of polyols include, but are not limited to, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 2,3-butanediol, 1,4-butanediol, 2-methyl-1 ,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1, 9-nonanediol, methyl-1,8-octanediol, cyclohexane 1,4-diol, cyclohexane 1,4-dimethanol, ethylene glycol, dipropylene glycol, or combinations thereof; the foregoing polyols Can be used alone or in combination of two or more. Further, specific examples of the carboxylic acid include, but are not limited to, succinic acid, maleic acid, adipic acid, glutaric acid, pimelic acid, arginic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, Phthalic acid, isophthalic acid, terephthalic acid or a combination thereof; the aforementioned carboxylic acids may be used alone or in combination of two or more. However, the present disclosure is not limited to this.

In the present disclosure, the polyisocyanate can be selected from the group consisting of aliphatic polyisocyanates, aromatic polyisocyanates, and mixtures thereof. In one embodiment of the present disclosure, the polyisocyanate can be Aliphatic polyisocyanates. Specific examples of polyisocyanates include, but are not limited to, isophorone diisocyanate (IPDI), hydrogenated diphenylmethane diisocyanate (4,4'-dicyclohexylmethane diisocyanate; HMDI), hexamethylene diisocyanate ( Hexamethylene diisocyanate (HDI), xylylene diisocyanate (1,3-Bis(isocyanatomethyl)benzene; XDI), Tetramethyl xylylene diisocyanate (TMXDI), hexamethylene Diisocyanate trimer (Hexamethylene diisocyanate trimer; HDI TRIMER), hexamethylene diisocyanate biuret (Hexamethylene diisocyanate biuret; HDB) or mixtures thereof; The aforementioned polyisocyanates can be used alone or in combination of two or more. However, the present disclosure is not limited to this. In an embodiment of the present disclosure, the polyisocyanate is hexamethylene diisocyanate.

In the present disclosure, the self-healing resin composition may further include a solvent. Among them, the type of solvent is not particularly limited, and it depends on the demand. Here, examples of the solvent may include, but are not limited to, ethyl acetate (Ethyl Acetate), butyl acetate (Butyl Acetate), Propylene Glycol Monomethyl ether (Propylene Glycol Monomethyl ether) or a combination thereof; the foregoing solvents may be used alone or in combination of two The above are used in combination. However, the present disclosure is not limited to this.

In addition, the present disclosure further provides the use of the aforementioned self-healing resin composition for forming a coating on a substrate. More specifically, the present disclosure is to coat the aforementioned self-healing resin composition on a substrate to form a coating. Here, the substrate may be a metal substrate, on which a pigment layer (eg, baking paint) is selectively disposed; but the present disclosure is not limited thereto.

The following describes the implementation of the present disclosure with specific examples, and those skilled in the art can easily understand other advantages and effects of the present disclosure from the contents disclosed in this specification. The present disclosure can also be implemented or applied through other different specific embodiments, and various details in this specification can also be modified and changed for different viewpoints and applications without departing from the spirit of the present creation.

As used in the specification and the appended claims, the singular forms "a" and "the" include one or plural referents unless the context dictates otherwise.

As used in the specification and the appended claims, the term "or" generally includes "and/or" unless the context dictates otherwise.

Also, as used herein, the term "about" generally means within 20%, or within 10%, or within 5%, or within 3%, or within 2%, or within 1% of a given value or range within 0.5%. The quantity given here is an approximate quantity, that is, the meaning of "about" can still be implied without the specific description of "about".

The present disclosure will be more specifically described by way of embodiments, but these embodiments are not intended to limit the scope of the present disclosure. Unless otherwise specified, in the following Preparation Examples, Examples and Comparative Examples, the temperature is in degrees Celsius, and the parts and percentages are by weight. The relationship between parts by weight and parts by volume is like the relationship between kilograms and liters.

Polyurethane resin

The polyurethane resin used in the following examples and comparative examples is provided by Taier Adhesive (Guangdong) Co., Ltd., the polyester polyol model is Z-922-4A (main agent), and the polyisocyanate model Z-922 -4B (which is hexamethylene diisocyanate) (curing agent).

UV Absorber (A)

The ultraviolet light absorbers used in the following examples and comparative examples include: (A1) 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl] -4,6-Bis(2,4-dimethylphenyl)-1,3,5-triazine(2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]- 4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine) and 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxy Phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine(2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2- hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine) (Eversorb® 40; CAS No.: 153519-44-9); and (A2)α-[3-[ 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl]-ω-[3-[3 -(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]poly(oxy-1, 2-Ethylenediyl)(α-[3-[3-(2H-Benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl]-ω-[3- A mixture of [3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]poly(oxy-1,2-ethanediyl)) (Eversorb® 80; CAS No.: 104810-48-2+104810-47-1). The structures of Eversorb® 40 and Eversorb® 80 are shown below.

(A1) Eversorb® 40

(A2) Eversorb® 80

Photostabilizer (B)

The light stabilizers used in the following examples and comparative examples include: (B1) N-(1-acetyl-2,2,6,6-tetramethyl-4-guaidinyl)-2-dodecyl Acetylsuccinimide (N-(1-Acetyl-2,2,6,6-tetramethyl-4-piperidinyl)-2-dodecylsuccinimide) (Eversorb® 97; CAS No.: 106917-31-1); (B2 ) Bis-(N-methyl-2,2,6,6-tetramethyl-4-pyridinyl)decanediester (Bis-(N-methyl,2,2,6,6-tetramethyl-4- piperidinyl)sebacate) and methyl-(N-methyl,2,2,6,6-tetramethyl-4-pyridinyl)sebacate (Methyl-(N-methyl,2,2,6,6) -tetramethyl-4-piperidinyl)sebacate) mixture (Eversorb® 93; CAS No.: 41556-26-7+82919-37-7); and (B3) sebacic acid, bis(2,2,6,6 -Product of the reaction of tetramethyl-1-(octyloxy)-4-piperidinyl) ester with 1,1-dimethylethyl hydroperoxide and octane (Decanedioic acid, bis(2,2, 6,6-tetramethyl-1-(octyloxy)-4-piperidinyl)ester, reaction products with 1,1-dimethylethylhydroperoxide and octane) (Eversorb® 95; CAS No.: 129757-67-1). The structures of Eversorb® 97, Eversorb® 93 and Eversorb® 95 are shown below.

(B1) Eversorb® 97

(B2) Eversorb® 93

(B3) Eversorb® 95

Antioxidant (C)

The antioxidants used in the following examples and comparative examples are phenylpropanoic acid, 3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-C7-C9 branched alkyl ester (Benzenepropanoic acid) ,3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-C7-C9 branched alkyl esters)(Everaox® 101; CAS No.: 125643-61-0), whose principal component structure is shown below .

(C) Everaox® 101

Preparation of self-healing resin composition

Weigh 10 g of the main agent (Z-922-4A), and then pour 0.2 g of the additive into the main agent according to the types and proportions of additives shown in Table 1 below, and stir slightly. Next, 2.5 g of a curing agent (Z-922-4B) was added, and finally 3 g of a solvent (ethyl acetate:butyl acetate:propylene glycol methyl ether=10:17:7) was added. After the main agent, curing agent, additives and solvent are fully and uniformly stirred, the resin compositions of the examples and comparative examples can be obtained. As for the resin composition of the blank group, except that no additives were added, the types and amounts of the main agent, curing agent and solvent were the same as the above, and the preparation method was also the same as the above.

Table 1

Preparation of self-healing coatings

The base material is white tinplate, the size of tinplate is 77mm long, 47mm wide, 0.3mm thick, and the upper layer is coated with white paint. The speed of the coating machine was set to 7, and the self-healing resin compositions of the above-prepared examples, control examples and blank groups were coated on white tinplate using RDS#35 wire rod, and left to level for 1 minute. Finally, put the leveled test piece into a hot air oven at 120°C for 3 to 5 minutes for quick-drying and curing, and then take it out and place it at room temperature for 24 hours to obtain a test piece with a self-healing coating formed on the substrate. .

Weathering test

A weathering tester (brand: Q LAB, model: QUV/se) was used, and the weathering condition was set to ASTM G154-2. The wavelength of the lamp source is 310nm, and the illuminance is 0.71W/m2/nm. Cycle conditions are: 4 hours Irradiated with UV light, the temperature of the blackboard was 60(±3)°C; after 4 hours of cooling, the temperature of the blackboard was 50(±3)°C. The above-prepared examples, control examples and blank test pieces were placed under this weather-resistant condition, and the irradiation time was 700 hours.

Heat resistance test

Use a hot air oven (brand: DENG YNG, model DO45), and the heat-resistant conditions are in accordance with GB/T1735. Set the hot air oven temperature to 125°C ± 2°C. The test pieces of the above-prepared examples, control examples and blank groups were placed under this heat-resistant condition, and the heat-aging time was 600 hours.

Wear resistance test

Use an abrasion resistance tester (brand: Jinliang Industrial, model: A20-339) for testing. Turn on the power and set the count to 10 times. Replace steel wool under the dynamometer rod. Place the test piece in the test position, clamp the upper and lower chucks, add a 500g weight on the top, and lower the measuring rod. The measuring rod goes back and forth 10 times and it stops automatically. Finally, loosen the upper and lower chucks and take out the test piece.

Chromatic aberration

Use a colorimeter (brand: KONICA MINOLTA, model: CM-5) and AATCC gray scale for measurement. Among them, the relationship between the number of stages and the color difference (ΔE) is shown in Table 2 below.

Table 2

Gloss

The measurement was performed using a gloss machine (brand: BYK, model: micro-TRI-gloss).

The results of abrasion resistance, color difference and gloss recovery before the weather resistance test, after the weather resistance test and after the heat resistance test of the examples, the control example and the blank group are shown in Table 3 below.

table 3

a: The time required for the test piece that has not undergone the weather resistance and heat aging test to recover to 100% gloss retention rate after the abrasion resistance test.

)，試片起始光澤度保留率為100%。 b: The initial gloss of the test piece, how much gloss is maintained after the weather resistance or heat aging test, which is called the gloss retention rate (

), the initial gloss retention rate of the test piece was 100%.

c: The test piece after the weather resistance or heat aging test, and then the ratio of the gloss after the wear resistance test to the before test.

d: The time required for the test piece to recover to 80% of the gloss retention rate after the weather resistance or heat aging test.

e: For the test piece having the coating layer formed with the composition of Comparative Example 4, the part that could not be subjected to subsequent heat and weather resistance tests due to oil slick on the surface is indicated by "-".

The above-mentioned so-called "initial gloss" refers to the gloss of the indicator sheet before the weather resistance, heat resistance and abrasion resistance test.

As shown in the results in Table 3, for the self-healing resin composition of the example, the gloss recovery rate after weathering and abrasion resistance is about 8 times higher than that of the blank group, and it is also significantly improved compared with the control example. In addition, it can be found from various observation indicators that the examples are better than the blank examples and the control examples, and the time required for the recovery of weathering scratches (recovery to 80% gloss retention rate) in the examples can be achieved within 5 minutes. However, the time required for the recovery of heat-resistant scratches (recovery to 80% gloss retention rate) can be achieved within 10 minutes or even 5 minutes in the examples, but the blank examples cannot be achieved. To achieve, the control also takes 10 minutes or more.

To sum up, when the self-healing resin composition of the present disclosure is used to form a coating, the formed coating still retains good self-healing ability after weathering and heat resistance tests. In addition, the coating after weather resistance and heat resistance test also maintains good scratch repair ability after wear resistance test. Therefore, the self-healing composition of the present disclosure can indeed improve the problems of fading or poor self-healing recovery rate caused by long-time UV light irradiation or exposure in a high-temperature environment, thereby increasing the service life of the coating.

Claims (9)

A self-healing resin composition, comprising: 100 parts by weight of a polyurethane resin; and 0.1 to 10 parts by weight of the additive, wherein the additive comprises an ultraviolet light absorber, a light stabilizer and an antioxidant, the ultraviolet light absorber comprises 2-[4-[(2-hydroxy-3-tridecane oxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine(2-[4-[(2 -hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine) and 2-[4-[(2-hydroxy-3- Dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine(2-[4- [(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine), the light stabilizer is N-(1- Acetyl-2,2,6,6-tetramethyl-4-piperidinyl)-2-dodecylsuccinimide (N-(1-Acetyl-2,2,6,6-tetramethyl- 4-piperidinyl)-2-dodecylsuccinimide), and the antioxidant is phenylpropionic acid, 3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-C7-C9 branched alkyl ester ( Benzenepropanoic acid,3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-C7-C9 branched alkyl esters), and the weight ratio of the UV absorber, the light stabilizer and the antioxidant is 2 ~3:1:1. The self-healing resin composition according to claim 1, wherein the polyurethane resin is a polymer obtained by reacting a polyol and a polyisocyanate. The self-healing resin composition of claim 2, wherein the weight ratio of the polyol to the polyisocyanate is between 3:1 and 5:1. The self-healing resin composition according to claim 3, wherein the weight ratio of the polyol to the polyisocyanate is 4:1. The self-healing resin composition according to claim 2, wherein the polyol is a polyester polyol. The self-healing resin composition of claim 2, wherein the polyisocyanate is selected from the group consisting of aliphatic polyisocyanates, aromatic polyisocyanates and mixtures thereof. The self-healing resin composition according to claim 6, wherein the polyisocyanate is an aliphatic polyisocyanate. The self-healing resin composition according to claim 1, wherein the content of the additive is 0.5 to 2 parts by weight. A use of the self-healing resin composition according to any one of claims 1 to 8, for forming a coating on a substrate.