CN113527936A

CN113527936A - Water-dispersible light stabilizer

Info

Publication number: CN113527936A
Application number: CN202010283307.2A
Authority: CN
Inventors: 韩玉凤; 林龙; 杨威; 安平; 孙春光; 李海平
Original assignee: Rianlon Corp
Current assignee: Rianlon Corp
Priority date: 2020-04-13
Filing date: 2020-04-13
Publication date: 2021-10-22

Abstract

The invention relates to a water-dispersible light stabilizer which comprises 75-95 parts by weight of light stabilizer; 5-25 parts of an emulsifier; the emulsifier is selected from at least one of an anionic surfactant or a nonionic surfactant. According to the invention, the hydrophobic light stabilizer is better dispersed in a water system through the emulsifier, the stability of the system is not influenced, a better weather-resistant effect is achieved, and the weather-resistant problem of the water-based polymer material industry is solved.

Description

Water-dispersible light stabilizer

Technical Field

The invention relates to a water-dispersible light stabilizer and application thereof in a water-based polymer material, in particular to a water-based paint.

Background

With the increasing importance of people on safety and environmental protection in recent years, the solvent-based coatings and other materials formed by solvent systems have a large amount of Volatile Organic Compounds (VOC) and can affect the health of human bodies, so that various solutions are developed by the coating industry for the problem of the solvent-based coatings, including: water-based paint, photo-curing paint, powder paint, etc. Among them, the water-soluble paint is widely accepted and applied because the coating system can follow the equipment of solvent-based paint.

Because most coatings require weathering, light stabilizers, including in particular uv absorbers and hindered amine light stabilizers, are added during the coating preparation. However, most ultraviolet absorbers and hindered amine light stabilizers are hydrophobic organic compounds, and are generally dispersed in water, so that the ultraviolet absorbers and hindered amine light stabilizers can be unevenly dispersed when added into a water-based coating system, and the application of the ultraviolet absorbers and hindered amine light stabilizers in the water-based coating system is limited.

At present, the light stabilizer for the water-based paint is mainly prepared or added by three methods, firstly, the light stabilizer is dissolved in a cosolvent in the form of the cosolvent, and then the light stabilizer dissolved in the cosolvent is added into the paint, and the method still has the problem of solvent volatilization and does not fundamentally solve the problem; the second is a water-based light stabilizer disclosed in the patent with the publication number of CN106987078A, and the specific preparation method is as follows: uniformly mixing the monomer, the solvent, the catalyst and the auxiliary agent, heating and stirring for 2-8 h, cooling to room temperature, adding a neutralizing agent, uniformly stirring to obtain a water-based resin prepolymer, and uniformly mixing the water-based resin prepolymer with the light stabilizer, the auxiliary agent and water to obtain the water-dispersible light stabilizer. In the whole preparation process of the technical scheme, various substances such as a catalyst, a solvent, an auxiliary agent, a neutralizing agent and the like need to be added, the process is relatively complicated, the cost is higher, in addition, the preparation time of the intermediate product, namely the aqueous resin prepolymer, needs at least 2 hours, and the whole preparation period is longer; thirdly, a hydrophobic light stabilizer is made into water-soluble by an emulsifier, for example, in a patent with the publication number of CN109135395A, a water-soluble light stabilizer and a preparation method thereof are disclosed, the water-soluble light stabilizer is added with water with the temperature of 30-50 ℃, and delamination and precipitation are easily caused in the process of storage and transportation; the emulsifier used in the patent is mainly surfactant of SDS, SLS, SDBS, AOT, Tween series, PEG series and AEO series, and the emulsifier is selective and small.

The method of using the light stabilizer for the aqueous polymer material by adding the emulsifier is important for forming a stable emulsion system, and the structure and the property of the emulsifier determine the stability and the dispersion effect of the water-dispersible light stabilizer. For industrial applications, it is necessary to provide more emulsifier choices and to establish more stable, more dispersing, water-dispersible light stabilizers.

Disclosure of Invention

Aiming at the defects in the prior art, the invention provides a water-dispersible light stabilizer and application thereof. The oil-soluble light stabilizer has excellent water dispersibility through a corresponding emulsifier, and is superior to the existing water-dispersible light stabilizer in stability and water-dispersible effect, thereby expanding the application range of the light stabilizer.

The first purpose of the invention is to provide a water-dispersible light stabilizer which comprises 75-95 parts by weight of light stabilizer; 5-25 parts of an emulsifier; the emulsifier is selected from at least one of an anionic surfactant or a nonionic surfactant.

The anionic surfactant is selected from sulfonate type anionic surfactants or sulfate type anionic surfactants; the nonionic surfactant is selected from ether nonionic surfactants or ester nonionic surfactants.

The second purpose of the invention is to provide the application of the water-dispersible light stabilizer in the aqueous high polymer material. Especially in aqueous resins; preferably, the water-based acrylic resin, the water-based polyurethane resin, the water-based epoxy resin, the water-based polyester resin, the water-based phenolic resin, the water-based alkyd resin and the water-based amino resin are applied; further, the aqueous polyurethane composition can be applied to the fields of downstream water-based paints, water-based inks, water-based adhesives, water-based sealants, water-based leathers, water-based shoe sole pastes and the like, and is more preferably applied to water-based paints.

The third purpose of the invention is to provide a method for preparing the water-dispersible light stabilizer, wherein 75-95 parts of the light stabilizer and 5-25 parts of the surfactant are uniformly mixed to obtain the water-dispersible light stabilizer.

The invention achieves the following positive effects:

(1) the invention avoids the use of cosolvent, and the product has no volatile organic solvent; the effective content of the water-dispersible light stabilizer is 75-95%, the appearance of the light stabilizer is not changed, and the performance test proves that the original light aging resistance is not reduced.

(2) The hydrophobic ultraviolet absorbent and hindered amine light stabilizer are better dispersed in the aqueous high polymer material through the selection of the emulsifier, and meanwhile, the stability and self-stability of the system are not influenced, layering and agglomeration are avoided, and the transportation is convenient; no layering occurs after the mixture is placed at room temperature for 9 months, no layering occurs after the mixture is frozen and thawed at the temperature of-20 ℃ for 96 hours, and no layering occurs after the mixture is stored at the temperature of 50-70 ℃ for 3 months at an accelerated speed.

(3) The water-dispersible light stabilizer has good water solubility and even self-emulsification process in water (as in example 4) to form a uniform stable microemulsion. The microemulsion has the characteristics of small particle size, good stability, difficult demulsification and the like.

(4) The product has good compatibility and homogeneity in the water-based paint, can be uniformly distributed in a water-based paint system, does not react with other additives in the water-based paint, does not generate particles, does not generate oil stains, shrinkage cavities and other defects due to precipitation, can play the same protection role for the water-based paint, and solves the weather resistance problem of the water-based paint industry and other water-based high polymer materials with weather resistance requirements.

(5) The water-dispersible light stabilizer is simple to prepare, and the water-dispersible light stabilizer with good stability can be prepared by simple mixing.

Drawings

FIG. 1 is an infrared spectrum of a liquid light stabilizer and a water dispersible light stabilizer of example 4;

FIG. 2 is a UV absorption chromatogram of the liquid light stabilizer and the water dispersible light stabilizer of example 4;

figure 3 is a TGA plot of the liquid light stabilizer and the water dispersible light stabilizer of example 4.

Detailed Description

The present invention will be described in detail with reference to the following embodiments, but it should be understood that the scope of the present invention is not limited by these embodiments and the principle of the present invention, but is defined by the claims.

In the present invention, any matter or thing which is not mentioned is directly applicable to the art known in the art without any change except for what is explicitly described. Moreover, any embodiment described herein may be freely combined with one or more other embodiments described herein, and the technical solutions or ideas thus formed are considered part of the original disclosure or original description of the present invention, and should not be considered as new matters not disclosed or contemplated herein, unless a person skilled in the art would consider such combination to be clearly unreasonable.

All features disclosed in this invention may be combined in any combination and such combinations are understood to be disclosed or described herein unless a person skilled in the art would consider such combinations to be clearly unreasonable.

The numerical points disclosed in the present specification include not only the numerical points specifically disclosed in the examples but also the endpoints of each numerical range in the specification, and ranges in which any combination of the numerical points is disclosed or recited should be considered as ranges of the present invention.

In the present invention, "optionally" means including or not including, such as "optionally a" means including a or not including a.

Technical and scientific terms used herein are to be defined only in accordance with their definitions, and are to be understood as having ordinary meanings in the art without any definitions.

The invention provides a water-dispersible light stabilizer which comprises 75-95 parts by weight of a light stabilizer; 5-25 parts of an emulsifier; the emulsifier is selected from at least one of an anionic surfactant or a nonionic surfactant.

As a preferred embodiment of the invention, it is better to control the dosage of the emulsifier to be 5-25% of the total weight of the water-dispersible light stabilizer, and when the dosage of the emulsifier is less than 5%, the emulsification effect is not good; at emulsifier levels above 25%, the emulsifying effect is beneficial, but results in a reduction in the effective level of light stabilizer.

Preferably, the amount of the light stabilizer is 80-95 parts, 85-95 parts or 90-95 parts; the dosage of the emulsifier is 5-20 parts, 5-15 parts or 5-10 parts.

The screening of a proper emulsifier is the key for determining the water dispersion effect of the light stabilizer, the emulsifier consists of lipophilic groups and hydrophilic groups, has excellent surface activity, can be adsorbed on a two-phase interface to form an oriented adsorption film, reduces the surface tension of the interface, can endow dispersed phase droplets with certain aggregation obstacle, reduces the collision probability between the droplets and improves the storage stability of a two-immiscible liquid phase dispersion system. The hydrophilic/lipophilic balance value (HLB value), molecular structure and content of the emulsifier can influence the emulsifying effect, and the structure of the hydrophilic group and the chemical structure of the lipophilic group (carbon chain length, branched chain, benzene ring and the like) are main factors influencing the hydrophilic/lipophilic balance value (HLB value) of the emulsifier, so that the type of the aqueous dispersion is determined. The chargeability of the emulsifier and the polarity of the emulsified oil phase affect the steric, electrical or mechanical barriers between the dispersed phase droplets, further affecting the droplet size and the stability of the aqueous dispersion.

In addition, the combination of two or more emulsifiers, such as nonionic emulsifiers and anionic emulsifiers, is more favorable for forming a closely-arranged adsorption film on a two-phase interface and is favorable for maintaining the stability of the aqueous dispersion.

In a preferred embodiment of the present invention, among the anionic surfactants, a sulfonate type anionic surfactant is selected from a higher fatty acid amide sulfonate, or a higher fatty acid ester sulfonate (MES), or an a-olefin sulfonate (AOS); the sulfate surfactant is fatty alcohol polyoxyethylene ether sulfate. Preferably, the anionic surfactant is fatty alcohol polyoxyethylene ether sulfate sodium salt (AES).

In a preferred embodiment of the present invention, the nonionic surfactant is an ether nonionic surfactant selected from the group consisting of: surfactants of octyl phenol polyoxyethylene ether (OP) series, nonyl phenol polyoxyethylene ether (NP) series, castor oil polyoxyethylene Ether (EL) series, hydrogenated castor oil polyoxyethylene ether (HEL) series, fatty alcohol polyoxyethylene ether (MOA) series, and isomeric alcohol polyoxyethylene ether (E13) series; the ester nonionic surfactant is a surfactant of fatty acid polyoxyethylene ester (A) series.

Preferably, the surfactant of the octylphenol polyoxyethylene ether (OP) series is selected from at least one of OP-4, OP-5, OP-6, OP-7 and OP-10;

preferably, the surfactant of the nonylphenol polyoxyethylene ether (NP) series is selected from: at least one of NP-4, NP-5, NP-6, NP-7, and NP-10;

preferably, the surfactant of castor oil polyoxyethylene Ether (EL) series is selected from: at least one of EL-10, EL-12, EL-20, EL-40, EL-60;

preferably, the surfactant of the hydrogenated castor oil polyoxyethylene ether (HEL) series is selected from: at least one of HEL-20 and HEL-40;

preferably, the surfactant of the isomeric alcohol polyoxyethylene ether (E13) series is selected from at least one of E1305, E1306, E1307, E1308 and E1310.

Preferably, the fatty alcohol-polyoxyethylene ether (MOA) series surfactant is selected from at least one of MOA3 and MOA 5.

Preferably, the surfactant of the fatty acid polyoxyethylene ester (A) series is selected from at least one of A110 and A115.

The chemical structure of the lipophilic group is a main factor influencing the affinity of the emulsifier to the oil phase, and the emulsifier with good affinity to the oil phase and moderate HLB can be more uniformly adsorbed between two phase interfaces. It has been found that emulsifiers having an HLB value of less than 6 are less hydrophilic with respect to light stabilizers, and tend to form water-in-oil emulsions, making it difficult to form stable aqueous dispersions in water. Emulsifiers with HLB values greater than 18 are highly hydrophilic, readily soluble in water, poorly compatible with active ingredients, poorly emulsifying, and not conducive to the formation of a uniformly distributed, tightly arranged adsorption film between the two phase interfaces. Meanwhile, the strong polar group enables the emulsifier to be easy to aggregate and separate out, and the long-term storage stability of the aqueous dispersion is poor. In a preferred embodiment of the present invention, the HLB value of the nonionic surfactant is preferably controlled to 6-18, and the effect of the HLB value is more preferably controlled to 6-15, for example, a nonionic surfactant having an HLB value of 8-14 or 10-14 can be selected.

In one water-dispersible light stabilizer of the present invention, the light stabilizer is at least one of an ultraviolet absorber or a hindered amine light stabilizer, preferably an ultraviolet absorber or a hindered amine light stabilizer having a melting point of less than 80 ℃ at normal pressure, more preferably an ultraviolet absorber and/or a hindered amine light stabilizer that is liquid at normal temperature at normal pressure.

In a specific embodiment of the present invention, the uv absorber is selected from the group consisting of benzamidine uv absorbers, benzotriazole uv absorbers, hydroxyphenyl triazine uv absorbers, and benzophenone uv absorbers. More preferably, the uv absorber may be selected from: n- (ethoxycarbonylphenyl) -N '-methyl-N' -phenylformamidine (UV-1), octyl 3- (2H-benzotriazole) -5-tert-butyl-4-hydroxy-phenylpropionate (UV-384), 3- (2H-benzotriazole) -5-tert-butyl-4-hydroxy-phenylpropionate and C₇-C₉Alcohol reaction product and propylene glycol methyl ether acetate mixture (UV-384-2), 3- [3- (2-H-benzotriazole-2-yl) -4-hydroxy-5-tert-butylphenyl]-propionic acid-polyethylene glycol 300 ester with bis {3- [3- (2H-benzotriazol-2-yl) -4-hydroxy-5-tert-butylphenyl]-propionic acid } -polyethylene glycol 300 ester mixture (UV-1130), 2-hydroxy-4-n-octoxybenzophenone (UV-531), 2- [4- [ 2-hydroxy-3-tridecyloxypropyl]Oxy radical]-2-hydroxyphenyl]-4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine and 2- [4- [ 2-hydroxy-3-dodecyloxypropyl]Oxy radical]-2-hydroxyphenyl]-one or more of a mixture of 4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazines (UV-400).

The structural formula of the ultraviolet absorbent is as follows:

the above ultraviolet absorbers are known compounds, and are commercially available or prepared by means of techniques known in the art.

In a specific embodiment of the present invention, the hindered amine light stabilizer is selected from non-polymeric hindered amine light stabilizers, preferably, the molecular weight of the hindered amine light stabilizer is controlled to 200-1200; more preferably, the hindered amine light stabilizer is selected from one or more of bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidinyl) sebacate (UV-123), bis (1,2,2,6, 6-pentamethyl-4-piperidinyl) sebacate in combination with methyl-1, 2,2,6, 6-pentamethyl-4-piperidine-sebacate (UV-292), ethyl 2- [2,2,6, 6-tetramethyl-4- (3,5, 5-trimethyl-hexanoyloxy) -piperidinyl ] -3,5, 5-trimethylhexanoate (e.g. Tinuvin 249).

The structural formula of the hindered amine light stabilizer is as follows:

2- [2,2,6, 6-tetramethyl-4- (3,5, 5-trimethyl-hexanoyloxy) -piperidinyl ] -3,5, 5-trimethylhexanoic acid ethyl ester.

The hindered amine light stabilizer is a known compound, and can be obtained commercially or prepared by adopting a technical means known in the field.

In a preferred embodiment of the present invention, the water-dispersible light stabilizer further comprises a co-emulsifier, which has better hydrophilicity or lipophilicity, and can rapidly disperse the water-dispersible light stabilizer in water or effectively combine the emulsifier with an oil phase, and has a synergistic effect with an anionic surfactant/nonionic surfactant, so that the emulsification effect is better. The coemulsifier is oleic acid, polyethylene glycol PEG series, fatty alcohol series surfactant. In the present invention, the aliphatic alcohol is an aliphatic alcohol having a chain of 8 to 22 carbon atoms.

Preferably, the surfactant of the polyethylene glycol PEG series is selected from at least one of PEG200, PEG300, PEG400, PEG600, PEG800, PEG1000 and PEG 1500;

preferably, the surfactant of the fatty alcohol series is selected from C₈-C₁₃At least one alcohol, e.g. n-octanol, n-nonanolN-decanol, undecanol, dodecanol, tridecanol. The amount of the co-emulsifier added is 2% to 20% by weight of the total weight of the water-dispersible light stabilizer, and may be, for example, 5%, 8%, 10%, 12%, 15%, or 18%.

As a preferred embodiment of the invention, the water-dispersible light stabilizer comprises 75-95 parts by weight of a light stabilizer containing UV-1130 and 5-25 parts by weight of AES emulsifier. Preferably, the UV-1130-containing light stabilizer comprises 85-95 parts of UV-1130-containing light stabilizer and 5-15 parts of AES emulsifier.

The light stabilizer containing UV-1130 refers to a mixture of UV-1130, UV-1130 and UV-292, UV-1130 and UV-123, or UV-1130 and UV-384. The mass ratio of the light stabilizer UV-1130 to UV-292 (or UV-123 or UV-384-2) is (0.5-4):1, for example the mass ratio of the two is 1:1, or 1.5:1, or 2:1, or 2.5:1, or 3: 1. Researches show that the ethylene oxide addition chain segment contained in the molecular structure of UV-1130 enables the ethylene oxide addition chain segment to have hydrophilicity, the chain segment and the hydrophilic group of an emulsifier have good synergistic effect, when the UV-1130 is compounded with the UV-292 (or the UV-123 or the UV-384-2), a small amount of emulsifier AES can be added to achieve good emulsification effect, when water is added for emulsification, the surface tension of two-phase interfaces is favorably reduced, and due to the combined action of the hydrophilic groups in the UV-1130 and the AES, a compound product with the UV-292 (or the UV-123 or the UV-384-2) has excellent self-emulsification characteristics, and a microemulsion with smaller particle size, more stability and transparent appearance is spontaneously formed in water. The effect is prominent when the content of the AES as the emulsifier is controlled to be 5-10 percent.

The water-dispersible light stabilizer system can also be added with a co-emulsifier PEG, wherein the PEG can be PEG300, PEG400, PEG600 or PEG800, the PEG has a solubilizing effect of enabling the light stabilizer UV-1130 to be rapidly dispersed in water, and the AES with an anionic property is helpful for the stability of the emulsion. The mass ratio of the co-emulsifier PEG to the emulsifier AES is 1: 0.5-2.0, and preferably 1: 1.0-1.5.

As a preferred embodiment of the invention, the water dispersible light stabilizer comprises, by weight, UV-29275-95 parts of light stabilizer and 5-25 parts of E13 series emulsifier. Preferably, the hindered amine light stabilizer UV 29285-95 parts, and the E13 series surfactant 5-15 parts. Researches show that the lipophilic group of the E13 series emulsifier has good affinity with UV-292 and good emulsification effect, and particularly, the E13 series emulsifier with the HLB value of 10-14 has better emulsification effect. The E13 series emulsifier is selected from at least one of E1305, E1306, E1307, E1308 and E1310, and is more preferably the compound of two E13 emulsifiers. In particular, the water dispersible light stabilizer UV-292 can be added with an auxiliary emulsifier oleic acid, and the oleic acid is helpful for the effective combination of the emulsifier and the oil phase. The mass ratio of the emulsifier E13 to the co-emulsifier oleic acid is preferably (1-6): 1, more preferably (2-5): 1.

in a preferred embodiment of the invention, the water-dispersible light stabilizer comprises, by weight, 5-25 parts of OP series or NP series emulsifier and 384-2 or 38475-95 parts of UV-2 or 38475-95 parts of light stabilizer. Particularly, the OP series or NP series emulsifier with HLB value of 8-14 has better effect. The OP series emulsifier is preferably OP-4, or OP-5, or OP-6, or OP-7, or OP-10. The NP series emulsifier is preferably at least one of NP-4, NP-5, NP-6, NP-7 and NP-10; optimally, for UV384 or UV384-2, the emulsifier OP-7 or NP-7 or OP-10 or NP-10 works best.

In a preferred embodiment of the invention, the water-dispersible light stabilizer comprises, by weight, 78-95 parts of a light stabilizer UV-12375 and 5-25 parts of an EL series and/or HEL series and/or MOA series emulsifier. Researches show that the EL/HEL and the MOA series emulsifiers have good synergistic effect when being compounded, and the mass ratio of the EL/HEL to the MOA series emulsifiers is 1:0.2-2, preferably 1: 0.5-1.5. The emulsifier EL-10 and the emulsifier MOA-3 with similar HLB are compounded and have better synergistic effect.

In another preferred embodiment of the invention, the water-dispersible light stabilizer comprises 75-95 parts by weight of light stabilizer UV-400and 5-25 parts by weight of EL series and/or HEL series emulsifier. The emulsifier is preferably EL-10, or EL12, or EL-20, or EL-40, or EL-60; or at least one of HEL-20 or HEL-40. In particular, the water dispersible light stabilizer can be added with auxiliary emulsifier fatty alcohol, and the fatty alcohol can effectively combine the emulsifier with the oil phase. The mass ratio of the emulsifier EL and/or HEL to the co-emulsifier fatty alcohol is preferably (0.5-1.5): 1, more preferably 1:1. Optimally, for the UV-400 system, the emulsifier EL-10 is better combined with the auxiliary emulsifier dodecanol.

On the basis of the common knowledge in the field, the above preferred conditions can be combined with each other to obtain the preferred embodiments of the invention.

The present invention relates to emulsifying agents and co-emulsifying agents which are known and commercially available or may be prepared by techniques known in the art.

The second purpose of the invention is to provide the application of the water-dispersible light stabilizer in high molecular materials, in particular in aqueous resins; the epoxy resin is preferably applied to waterborne acrylic resin, waterborne polyurethane resin, waterborne epoxy resin, waterborne polyester resin, waterborne phenolic resin, waterborne alkyd resin and waterborne amino resin; further, the aqueous polyurethane composition can be applied to the application fields of downstream water-based coatings, water-based inks, water-based adhesives, water-based sealants, water-based leathers, water-based shoe sole pastes and the like, and is more preferably applied to water-based coatings.

The water-dispersible light stabilizer can be applied to downstream underwater coatings, such as water-based automobile coatings, water-based industrial coatings, water-based wood coatings, water-based protective coatings and other water-based coatings.

The water-dispersible light stabilizer of the present invention may also include additives known in the art as anti-aging aids, processing aids, and the like.

The anti-aging auxiliary agent comprises an antioxidant, a metal deactivator, a carbon radical trapping agent and the like, such as a hindered phenol antioxidant, an amine antioxidant, a phosphite antioxidant, a thioester antioxidant, a metal deactivator and a carbon radical trapping agent.

According to different application requirements, the aqueous polymer material may further include a processing aid or an additive, including at least one of a preservative, a dispersant, a cosolvent, a defoamer, a wetting agent, a pigment, a filler, an antistatic agent, an accelerator, a tackifier, a rheology control agent, a stabilizer, and the like.

The aqueous resin, the stabilizer, the processing aid and the additive are all known substances and can be obtained commercially or prepared by adopting technical means known in the field.

The water-dispersible light stabilizer can be directly added into the aqueous polymer material for use or diluted by adding water before use. Under the condition of good stirring condition, the water-dispersible light stabilizer can be directly added into the aqueous high polymer material for use, otherwise, bubbles are easily generated, and the use effect is poor; the water-dispersible light stabilizer is generally used after dilution, and depending on the characteristics of the aqueous polymer material, the water-dispersible light stabilizer is diluted with water in a ratio of 1:2 to 1:200, preferably 1:5 to 1:100, so that the foaming problem can be effectively avoided.

Preferably, when the water-dispersible light stabilizer is used in an aqueous polymer material, the amount of the water-dispersible light stabilizer is 0.1% to 3%, such as 0.3%, 0.5%, 1% and 2% of the polymer material.

The third purpose of the invention is to provide a method for preparing the water-dispersible light stabilizer, wherein 75-95 parts of the light stabilizer and 5-25 parts of the surfactant are uniformly mixed according to parts by weight to obtain the water-dispersible light stabilizer.

Preferably, in the above preparation method, the mixture is heated to 20-80 deg.C and stirred, preferably 30-60 deg.C, and stirred until the mixture is uniform.

The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. The operations referred to in the examples are all those of ordinary skill in the art unless otherwise specified;

the water-dispersible light stabilizer in the embodiment of the invention is prepared by mixing and stirring, and is heated to 20-80 ℃ during mixing according to the actual process requirements.

Example 1

A water-dispersible light stabilizer, which consists of the following components: 88g of UV-1130 as an ultraviolet absorber, 6.8g of AES as an emulsifier and 5.2g of PEG-600 as a co-emulsifier.

Example 2

A water-dispersible light stabilizer, which consists of the following components: 88g of hindered amine light stabilizer UV-292, 12g of emulsifier E1310.

Example 3

A water-dispersible light stabilizer, which consists of the following components: 75g of UV absorber UV-384-2, 12.5g of emulsifier OP-7 and 12.5g of emulsifier OP-10.

Example 4

A water-dispersible light stabilizer, which consists of the following components: 45g of an ultraviolet absorber UV-1130 and 45g of a light stabilizer UV-292 of a hindered amine, 10g of an AES emulsifier.

Example 5

A water-dispersible light stabilizer, which consists of the following components: 95g of hindered amine light stabilizer UV-123, 2.5g of emulsifier EL-10 and 2.5g of emulsifier MOA-3.

Example 6

A water-dispersible light stabilizer, which consists of the following components: 75g of hindered amine light stabilizer UV-123, 25g of emulsifier EL-12.

Example 7

A water-dispersible light stabilizer, which consists of the following components: 85g of ultraviolet absorber UV-400, 10g of emulsifier EL-10 and 5g of coemulsifier dodecanol.

Comparative example 1

A water-dispersible light stabilizer, which consists of the following components: 90g of ultraviolet absorbent UV-1130, 7g of emulsifier Tween 80 and 3g of emulsifier SDS.

Comparative example 2

A water-dispersible light stabilizer, which consists of the following components: 88g of hindered amine light stabilizer UV-292, 12g of emulsifier Tween 80.

Comparative example 3

A water-dispersible light stabilizer, which consists of the following components: 90g of hindered amine light stabilizer UV-292, 7.5g of emulsifier Tween 80 and 2.5g of emulsifier SPAN-80.

Comparative example 4

A water-dispersible light stabilizer, which consists of the following components: 75g of an ultraviolet absorber UV-384-2 and 25g of an emulsifier OP-15.

Comparative example 5

A water-dispersible light stabilizer, which consists of the following components: 75g of UV absorber UV-384-2, 25g of emulsifier E1312.

Comparative example 6

A water-dispersible light stabilizer, which consists of the following components: 45g of UV absorber UV-1130 and 45g of hindered amine light stabilizer UV-292, 10g of emulsifier SDS.

Comparative example 7

A water-dispersible light stabilizer, which consists of the following components: 75g of hindered amine light stabilizer UV-123 and 25g of emulsifier OP-15.

Comparative example 8

The water-dispersible light stabilizer comprises the following components in parts by weight: 75g of hindered amine light stabilizer UV-400 and 25g of emulsifier OP-13.

Stability, water dispersibility and application Effect detection of light stabilizer

1. Stability test of light stabilizer

1.1 detection of photostable Properties:

the water-dispersible light stabilizer obtained in example 4 and the emulsifier-free liquid light stabilizer (UV-1130: UV 292: 1 blend) were compared and analyzed and detected by an infrared spectrometer, an ultraviolet spectrophotometer and a thermogravimetric analyzer, and the results are shown in fig. 1, fig. 2 and fig. 3, respectively. As can be seen from fig. 1-3: the infrared absorption peak positions of the liquid light stabilizer and the water dispersible light stabilizer are similar, the ultraviolet absorption positions are consistent, the thermal weight loss conditions are similar and have no obvious change, and the fact that the water dispersible light stabilizer does not change the properties of the liquid light stabilizer is proved.

1.2 detection of the stability of the light stabilizer: the light stabilizer samples obtained in the above examples and comparative examples were examined by visual inspection and static stability experiments.

Appearance: visually observing the appearance and recording;

standing storage experiment: the water-dispersible light stabilizer is sealed and respectively placed at room temperature, 20 ℃ and 50-70 ℃ for storage, and the phenomena of delamination, sedimentation, turbidity and the like are observed every day and recorded.

TABLE 1 stability test results for light stabilizers

As can be seen from table 1: the appearance of the water dispersible light stabilizer in examples 1-7 is consistent with the appearance of the liquid light stabilizer; the water-dispersible light stabilizer in examples 1-7 has good stability after room temperature placement, freeze-thaw test at-20 ℃ and accelerated storage test at 50-70 ℃.

2. Water dispersing effect and stability test of light stabilizer

The light stabilizer samples obtained in the above examples and comparative examples were diluted 20 times with water, and the water dispersion effect and the centrifugal stability were observed and examined.

Water dispersion effect: the water dispersion effect is judged by visual observation of the color and uniformity of the appearance of the light stabilizer after water is added, and uniform emulsion without precipitation or precipitation has good water dispersion effect, otherwise, the water dispersion effect is poor. The appearance of the microemulsion is white transparent emulsion, and the appearance of the aqueous dispersion is milky uniform emulsion.

Centrifugal stability: the water-dispersible light stabilizer is centrifuged for 30min in a GT10-1 low-speed centrifuge at a set rotating speed of 3000rpm, and the layering condition is observed.

The results of the above stability experiments are recorded in table 2.

TABLE 2 Water Dispersion Effect and stability test results of light stabilizer

As can be seen from table 2: water-dispersible light stabilizer examples 1-3, 5-7 were milky homogeneous emulsions in appearance and example 4 was a microemulsion self-emulsifying in the presence of water, which was a white transparent emulsion in appearance. Centrifugal stability experiments at 3000r/30min show that the water-dispersible light stabilizer of examples 1-7 has good water dispersion effect and good stability after being added with water. Through tests, the experimental results are also applicable to the emulsion formed by diluting the water-dispersible light stabilizer by 10-100 times with water.

3. Application examples

3.1 application in Water-based 1K Wood lacquer varnish Material

The water dispersible light stabilizer of example 4 was used in an aqueous 1K wood lacquer varnish material, and wood lacquer varnishes containing no water dispersible light stabilizer, 0.3% of the light stabilizer of example 4 and 0.5% of the light stabilizer of example 4 were prepared according to the formulation of table 3.

TABLE 3 aqueous 1K Wood lacquer varnish formulation

Application of 1K wood lacquer varnish: selecting a density board from blank control, 1# and 2# varnish coating substrates, wherein the density board is subjected to the following treatment temperature: 25 +/-2 ℃; treating humidity: 65% +/-2; drying for 7 days for later use, and then respectively polishing and flattening the density boards by No. 240 sand paper; spraying white primer, wherein the wet film thickness is 100-120 microns, and drying for 16 hours; polishing and flattening 320 sand paper; finally, spraying water-based 1K wood lacquer varnish on the surface of the density board coated with the white bottom, wherein the wet film thickness is 100-120 microns, and drying for 7 days.

Testing the light aging resistance of the water-based 1K wood lacquer varnish: carrying out ultraviolet exposure test on the density board prepared by the process, wherein the test instrument is a Q-Lab QUV/Spray ultraviolet fluorescence aging test box, the light source is a UVA340 lamp tube, the temperature of a blackboard is set to be 60 ℃, and continuous illumination is carried out; and measuring the color of the aged density board surface composite coating, wherein a tester is a Konica Minolta CM-5 spectrocolorimeter, recording the absolute value of the color and calculating the color difference. The results are shown in Table 4.

TABLE 4 color difference of density boards after spraying of aqueous 1K wood lacquer varnish

Sample (I)	24h	48h	72h	96h	120h	144h	168h
								Blank control	0.65	1.41	1.67	1.92	2.07	2.32	2.28
1#	0.54	0.84	1.07	0.9	0.47	0.95	0.91
								2#	0.22	0.54	0.53	0.28	0.35	0.5	0.49

As can be seen from table 4: the water-dispersible light stabilizer can play a role in resisting light aging in 1K waterborne wood paint and slow down the color change of the paint, and the varnish with 0.5 percent of addition amount has better light aging resistance than the varnish with 0.3 percent of addition amount.

3.2 application in Water-based 2K Wood lacquer varnish Material

The water dispersible light stabilizer of example 4 was used in an aqueous 2K wood lacquer varnish material, and the wood lacquer varnish containing no water dispersible light stabilizer, 0.3% of the light stabilizer of example 4 and 0.5% of the light stabilizer of example 4 was prepared according to the formulation of table 5.

TABLE 5 aqueous 2K Wood lacquer varnish formulation

Note: the main material in the formula also contains a curing agent, wherein the curing agent is Bayhydur XP 2655/PMA, the mass ratio is 80:20, and the main resin/curing agent is 5: 1.

application of 2K wood lacquer varnish: selecting a density board from blank control, 1# and 2# varnish coating substrates, wherein the density board is subjected to the following treatment temperature: 25 +/-2 ℃; treating humidity: 65% +/-2; drying for 7 days for later use, and then respectively polishing and flattening the density boards by No. 240 sand paper; spraying white primer, wherein the wet film thickness is 100-120 microns, and drying for 16 hours; polishing and flattening 320 sand paper; finally, spraying water-based 2K wood lacquer varnish on the surface of the density board coated with the white bottom, wherein the wet film thickness is 100-120 microns, and drying for 7 days.

Testing the light aging resistance of the water-based 2K wood lacquer varnish: carrying out ultraviolet exposure test on the density board prepared by the process, wherein the test instrument is a Q-Lab QUV/Spray ultraviolet fluorescence aging test box, the test light source is a UVA340 lamp tube, the temperature of a blackboard is set to be 60 ℃, and continuous illumination is carried out; and measuring the color of the aged density board surface composite coating, wherein a tester is a Konica Minolta CM-5 spectrocolorimeter, recording the absolute value of the color and calculating the color difference. The results are shown in Table 6.

TABLE 6 color difference of density boards after spraying of aqueous 2K wood lacquer varnish

Sample (I)	24h	48h	72h	96h	120h	144h	168h
								Blank control	0.71	1.21	1.88	2.48	2.96	3	3.06
1#	0.46	1.01	1.6	1.51	2.06	2.34	2.25
								2#	0.23	0.66	1.17	1.26	1.43	1.59	1.72

As can be seen from table 6: the water-dispersible light stabilizer can play a role in resisting light aging in 2K waterborne wood paint and slow down the color change of the paint, and the varnish with 0.5 percent of addition amount has better effect of resisting light aging than the varnish with 0.3 percent of addition amount.

Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims

1. The water-dispersible light stabilizer is characterized by comprising 75-95 parts by weight of light stabilizer; 5-25 parts of an emulsifier; the emulsifier is selected from at least one of an anionic surfactant or a nonionic surfactant;

2. The water-dispersible light stabilizer according to claim 1, wherein the anionic surfactant is a sulfonate anionic surfactant selected from a higher fatty acid amide sulfonate, a higher fatty acid ester sulfonate (MES), or an alpha-olefin sulfonate (AOS); the sulfate salt type surfactant is selected from fatty alcohol polyoxyethylene ether sulfate; preferably fatty alcohol polyoxyethylene ether sulphate sodium salt (AES);

in the nonionic surfactant, the ether nonionic surfactant is selected from surfactants of octyl phenol polyoxyethylene ether (OP) series, nonyl phenol polyoxyethylene ether (NP) series, castor oil polyoxyethylene Ether (EL) series, hydrogenated castor oil polyoxyethylene ether (HEL) series, fatty alcohol polyoxyethylene ether (MOA) series and isomeric alcohol polyoxyethylene ether (E13) series; the ester nonionic surfactant is a surfactant of fatty acid polyoxyethylene ester (A) series; preferably, the HLB value of the nonionic surfactant is 6-18.

3. The water dispersible light stabilizer of claim 2, wherein the surfactant of the OP series is selected from at least one of OP-4, OP-5, OP-6, OP-7, OP-10;

the surfactant of the NP series is at least one of NP-4, NP-5, NP-6, NP-7 and NP-10;

the EL series surfactant is at least one selected from EL-10, EL-12, EL-20, EL-40 and EL-60;

the surfactant of the HEL series is selected from at least one of HEL-20 and HEL-40;

the surfactant of the A series is selected from at least one of A110 and A115;

the surfactant of the E13 series is selected from at least one of E1305, E1306, E1307, E1308 and E1310;

the surfactant of the MOA series is selected from at least one of MOA3 and MOA 5.

4. The water dispersible light stabilizer of claim 1, wherein the light stabilizer is an ultraviolet absorber or hindered amine light stabilizer having a melting point of less than 80 ℃ at ambient pressure;

the ultraviolet absorbent is selected from benzamidine ultraviolet absorbent, benzotriazole ultraviolet absorbent, hydroxyphenyl triazine ultraviolet absorbent and benzophenone ultraviolet absorbent; preferably, the uv absorber may be selected from: n- (ethoxycarbonylphenyl) -N '-methyl-N' -phenylformamidine (UV-1), octyl 3- (2H-benzotriazole) -5-tert-butyl-4-hydroxy-phenylpropionate (UV-384), 3- (2H-benzotriazole) -5-tert-butyl-4-hydroxy-phenylpropionate and C₇-C₉Alcohol reaction product and propylene glycol methyl ether acetate mixture (UV-384-2), 3- [3- (2-H-benzotriazole-2-yl) -4-hydroxy-5-tert-butylphenyl]-propionic acid-polyethylene glycol 300 ester with bis {3- [3- (2H-benzotriazol-2-yl) -4-hydroxy-5-tert-butylphenyl]-propionic acid } -polyethylene glycol 300 ester mixture (UV-1130), 2-hydroxy-4-n-octoxybenzophenone (UV-531), 2- [4- [ 2-hydroxy-3-tridecyloxypropyl]Oxy radical]-2-hydroxyphenyl]-4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine and 2- [4- [ 2-hydroxy-3-dodecyloxypropyl]Oxy radical]-2-hydroxyphenyl]-one or more of a mixture of 4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazines (UV-400);

the hindered amine light stabilizer is selected from non-polymeric hindered amine light stabilizers, preferably the hindered amine light stabilizer is selected from one or more of bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidinyl) sebacate (UV-123), bis (1,2,2,6, 6-pentamethyl-4-piperidinyl) sebacate in combination with methyl-1, 2,2,6, 6-pentamethyl-4-piperidine-sebacate (UV-292), ethyl 2- [2,2,6, 6-tetramethyl-4- (3,5, 5-trimethyl-hexanoyloxy) -piperidinyl ] -3,5, 5-trimethylhexanoate.

5. The water dispersible light stabilizer according to any one of claims 1 to 4, which comprises 75 to 95 parts by weight of a light stabilizer containing UV-1130, 5 to 25 parts by weight of AES emulsifier; the light stabilizer containing the UV-1130 is UV-1130, or a mixture of the UV-1130 and the UV-292, or a mixture of the UV-1130 and the UV-123, or a mixture of the UV-1130 and the UV-384 or the UV-384-2.

6. The water-dispersible light stabilizer according to claim 5, wherein the AES emulsifier is present in an amount of from 5% to 10% by weight based on the total weight of the water-dispersible light stabilizer.

7. The water dispersible light stabilizer according to any one of claims 1 to 4, which comprises, in parts by weight, light stabilizer UV-29275-95 parts, E13 series emulsifier 5-25 parts; preferably, the HLB of the E13 series emulsifier is 10-14; alternatively, the first and second electrodes may be,

the light stabilizer comprises, by weight, UV-384-2 or UV-38475-95 parts of a light stabilizer and 5-25 parts of an OP series and/or NP series emulsifier; preferably, the HLB value of the OP series or NP series emulsifier is 8-14; alternatively, the first and second electrodes may be,

the light stabilizer comprises, by weight, UV-12375-95 parts of a light stabilizer, and 5-25 parts of an EL series and/or HEL series and/or MOA series emulsifier; alternatively, the first and second electrodes may be,

the light stabilizer comprises, by weight, 75-95 parts of UV-400and 5-25 parts of EL series and/or HEL series emulsifiers.

8. The water-dispersible light stabilizer according to any one of claims 1 to 7, characterized in that the water-dispersible light stabilizer further comprises a co-emulsifier which is oleic acid, polyethylene glycol PEG series, or fatty alcohol series surface active agents;

preferably, the polyethylene glycol PEG series surfactant is selected from at least one of PEG200, PEG300, PEG400, PEG600, PEG800, PEG1000 and PEG 1500; the fatty alcohol series surfactant is selected from C₈-C₁₃At least one of alcohols.

9. The water-dispersible light stabilizer according to claim 8, wherein the co-emulsifier is added in an amount of 2-20% by weight based on the total weight of the water-dispersible light stabilizer.

10. Use of a water-dispersible light stabilizer according to any one of claims 1 to 9 in an aqueous polymeric material; particularly in aqueous resins, preferably in aqueous acrylic resins, aqueous polyurethane resins, aqueous epoxy resins, aqueous polyester resins, aqueous phenolic resins, aqueous alkyd resins, aqueous amino resins; further can be applied to the fields of downstream water-based paint, water-based ink, water-based adhesive, water-based sealant, water-based leather and water-based sole sizing agent.