Polyurethane-based UV absorber

Abstract

A polyurethane-based UV absorber, obtained by reacting a UV absorber having a reactive hydrogen with a polyisocyanate and a diol or polyol; wherein the weight average molecular weight of the polyurethane-based UV absorber is in a range of 10,000 to 200,000.

Claims

1. A polyurethane-based UV absorber, obtained by reacting a UV absorber having a reactive hydrogen with a polyisocyanate and a diol or polyol; wherein the weight average molecular weight of the polyurethane-based UV absorber is in a range of 10,000 to 200,000.

2. The polyurethane-based UV absorber as claimed in claim 1, wherein the reactive hydrogen as functional group comprised in the UV absorber is selected from the group consisting of: —OH, —NH.sub.2, and —NH—.

3. The polyurethane-based UV absorber as claimed in claim 1, wherein the UV absorber is selected from the group consisting of benzotriazole UV absorber, benzophenone UV absorber, triazine UV absorber, oxanilide UV absorber, and cyanoacrylate UV absorber.

4. The polyurethane-based UV absorber as claimed in claim 1, wherein the polyisocyanate is selected from the group consisting of isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate (HMDI), hexamethylene diisocyanate (HDI), 1,3-Bis(isocyanatomethyl)benzene (XDI), tetramethyl xylylene diisocyanate (TMXDI), 2,2,4-trimethylhexamethylene diisocyanate (HDI TRIMER), hexamethylene diisocyanate biuret (HDB), and a mixture thereof.

5. The polyurethane-based UV absorber as claimed in claim 1, wherein the diol or polyol is selected from the group consisting of anionic diol or polyol, cationic diol or polyol, nonionic diol or polyol, and a mixture thereof.

6. The polyurethane-based UV absorber as claimed in claim 5, wherein the anionic diol or polyol is selected from the group consisting of 2,2-Bis(hydroxymethyl)butyric acid (DMBA), 2,2-Bis(hydroxymethyl)propionic acid (DMPA), 1,4-butanediol-2-Sodium, and a mixture thereof.

7. The polyurethane-based UV absorber as claimed in claim 5, wherein the cationic diol or polyol is selected from the group of N-methyldiethanolamine (MDEA), methyldiethanolamine (MPEDEA), Triethanolamine, and a mixture thereof.

8. The polyurethane-based UV absorber as claimed in claim 5, wherein the nonionic diol or polyol is selected from the group consisting of ethylene glycol (EG), diethylene glycol (DEG), 1,4-butanediol (BDO), polytetramethylene ether glycol (PTMG), polyethylene glycol (PEG), polypropylene glycol (PPG), polyethylene adipate (PEA), polypropylene adipate (PBA), and a mixture thereof.

9. The polyurethane-based UV absorber as claimed in claim 1, wherein a chain extender is further reacted with the polyisocyanate and the diol or polyol.

10. The polyurethane-based UV absorber as claimed in claim 9, wherein the chain extender is selected from the group consisting of polyamines, which comprises two or more reactive hydrogen as functional group selected from the group consisting of —OH, —NH.sub.2, and —NH—, and a mixture thereof.

11. A composition for enhancing light fastness, comprising the polyurethane-based UV absorber as claimed in claim 1.

12. The composition as claimed in claim 12, further comprising an additive which is selected from the group consisting of a neutralizing agent, a carrier, a diluent, an excipient, and a stabilizer.

13. The composition as claimed in claim 12, which is applied on coatings, adhesives, sealants, or elastomers.

Description

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

[0018] The following specific examples are used to illustrate the present invention. Any person who is skilled in the art can easily conceive other advantages and effects of the present invention. Although the present invention has been explained in relation to its preferred embodiment, many other possible modifications and variations can be made without departing from the spirit and scope of the present invention as hereinafter claimed.

[0019] Unless specified otherwise, singular words “a” and “the” used in the invention specification and claims include plural subjects.

[0020] Unless specified otherwise, term “or” used in the invention specification and claims include meaning of and/or.

[0021] The term “weight average molecular weight” here is Mw value of polystyrene measured by using gel permeation chromatography (GPC) solvent: tetrahydrofuran (THF).

[0022] The methods of preparation are described by the following embodiments in details, and the similar methods of embodiments can be used to prepare said polyurethane-based UV absorber. The methods of preparing polyurethane-based UV absorber (such as synthetical method, reaction condition, and sequences) and material are not limited to the present invention.

[0023] The polyurethane-based UV absorber has excellent water dispersibility, permeability, and storage stability. Furthermore, it can be widely applied. The polyurethane-based UV absorber can be applied on various materials including, but not limited to, fiber materials, leather materials (such as a natural leather and synthetic leather), foam, and wood. Particularly, the applied fiber materials includes nature fibers (such as plant fibers, animal fibers (for example, wool) and mineral fibers), and artificial fibers (such as regenerated fibers, semi-synthetic fibers, and synthetic fibers (such as polyester fiber and nylon fibers). Preferably, the fiber material is a natural cellulose fiber (such as cotton, linen, flax, hemp, and ramie), an animal fiber (for example, wool), a regenerated fiber (for example, viscose rayon), and a synthetic fiber (such as polyester fibers and nylon fibers). More preferably, the fiber material is cotton. The polyurethane-based UV absorber can be also applied on mixed fibers, blended fabrics or mixed fabrics containing aforementioned fiber materials.

[0024] The light fastness enhancer can optionally include other auxiliaries such as, but not limited to, UV absorber, light stabilizer, antioxidant, surfactant, leveling agent, thickener, defoamer and a mixture thereof.

[0025] The present invention will be illustrated by preferred embodiment. However, the following examples should not be constructed in any way to limit the scope of the present invention. Unless specified otherwise, percentage referring content and mass used in examples and comparative examples are calculated by weight.

Example 1—Preparation of Compound 1

[0026] 68.2 g of α-[3-[3-(2H-Benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl]-ω-hydroxypoly(oxo-1,2-ethanediyl) (Everlight Chemical Industrial Corporation) was provided in a flask, and then added with 50.5 g of HDI TRIMER. The mixture was then heated to 65-75° C. When the NCO group was titrated till the end point of the reaction (Free NCO %/=7%), 5.4 g of DMBA was added. The mixture is titrated till NCO group was titrated to the end point of the reaction (Free NCO %/=3.99%). Then 16.0 g of acetone and 5.4 g of N,N-Dimethylethylamine were added. Consequently, the prepolymer 1 was obtained.

[0027] Prepolymer 1 was added with 300.0 g of deionized water, and then stirred at a high speed. The mixture was added with 2.8 g of EDA and 1.6 g of AEEA as chain extender, and then stirred till dispersed completely. Consequently, the compound 1 (Mw=43,800, measured by GPC) was obtained.

Example 2—Preparation of Compound 2

[0028] 70.0 g of α-[3-[3-(2H-Benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl]-ω-hydroxypoly(oxo-1,2-ethanediyl) (Everlight Chemical Industrial Corporation) was provided in a flask, and then added with 50.5 g HDI TRIMER. The mixture was heated to 65-75° C. When the NCO group was titrated till the end point of the reaction (Free NCO %=6.6%), 2.2 g of DMBA and 10.5 g of PEG300 (polyethylene glycol, Mw=300) were added. Then the NCO group was titrated till the end point of the reaction (Free NCO %=2.8%), and then 16.0 g of acetone and 2.6 g of N,N-Dimethylethylamine were added. Consequently, the prepolymer 2 was obtained.

[0029] Prepolymer 2 was added with 300.0 g of deionized water, and then stirred at a high speed. The mixture was added with 2.4 g of EDA and 1.4 g of AEEA as chain extender, and then stirred till dispersed completely. Consequently, the compound 2 (Mw=13,200, measured by GPC) was obtained.

Example 3—Preparation of Compound 3

[0030] 70.0 g of α-[3-[3-(2H-Benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl]-ω-hydroxypoly(oxo-1,2-ethanediyl) (Everlight Chemical Industrial Corporation) was provided in a flask, and then added with 50.5 g HDI TRIMER. The mixture was heated to 65-75° C. When the NCO group was titrated till the end point of the reaction (Free NCO %=7.1%), 1.79 g of MDEA and 10.5 g of PEG300 were added. Then the NCO group was titrated till the end point of the reaction (Free NCO %=3.67%), and then 16.0 g of acetone and 1.8 g of acetic acid were added. Consequently, the prepolymer 3 was obtained.

[0031] Prepolymer 3 was added with 300.0 g of deionized water, and then stirred at a high speed till dispersed completely. Consequently, compound 3 (Mw=131,700, measured by GPC) was obtained.

Example 4—Preparation of Compound 4

[0032] 70.0 g of α-[3-[3-(2H-Benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl]-ω-hydroxypoly(oxo-1,2-ethanediyl) (Everlight Chemical Industrial Corporation) was provided in a flask, and then added with 50.5 g HDI TRIMER. The mixture was heated to 65-75° C. When the NCO group was titrated till the end point of the reaction (Free NCO %=6.67%), 3.57 g of MDEA was added. Then the NCO group was titrated till the end point of the reaction (Free NCO %=3.7%), and then 16.0 g of acetone and 4.32 g of acetic acid were added. Consequently, the prepolymer 4 was obtained.

[0033] Prepolymer 4 was added with 300.0 g of deionized water, and then stirred at a high speed till dispersed completely. Consequently, the compound 4 (Mw=74,400 measured by GPC) was obtained.

Example 5—Preparation of Compound 5

[0034] 70.0 g of α-[3-[3-(2H-Benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl]-ω-hydroxypoly(oxo-1,2-ethanediyl) (Everlight Chemical Industrial Corporation) was provided in a flask, and then added with 47.8 g HDB. The mixture was heated to 65-75° C. When the NCO group was titrated till the end point of the reaction (Free NCO %=7.2%), 2.2 g of DMBA and 10.5 g of PEG300 were added. Then the NCO group was titrated till the end point of the reaction (Free NCO %=3.5%), 16.0 g of acetone and 2.6 g of N,N-Dimethylethylamine were added. Consequently, the prepolymer 5 was obtained.

[0035] Prepolymer 5 was added with 300.0 g of deionized water, and then stirred at a high speed till dispersed completely. Consequently, the compound 5 (Mw=91,900 measured by GPC) was obtained.

[0036] The aforementioned monomer structure of compound 1 and compound 2 can be represented by formula (II), and compound 3 to 5 can be represented by formula (I):

##STR00003##

[0037] wherein the average weight molecular weight (Mw) of A, B, C, D, and other compounds are shown in Table 1.

TABLE-US-00001 TABLE 1 Com- Compound 1 Compound 2 Compound 3 Compound 4 pound 5 A UVA UVA UVA UVA UVA B HDI HDI HDI HDI HDB TRIMER TRIMER TRIMER TRIMER C DMBA DMBA/ MDEA/ MDEA DMBA/ PEG300 PEG300 PEG300 D EDA/AEEA EDA/AEEA — — — Mw 43,800 13,200 131,700 74,400 91,900 UVA is UV absorber, which is α-[3-[3-(2H-Benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl]-ω-hydroxypoly(oxo-1,2-ethanediyl).

Comparative Example 1

[0038] 55.67 g of α-[3-[3-(2H-Benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl]-ω-hydroxypoly(oxo-1,2-ethanediyl) (Everlight Chemical Industrial Corporation) was provided in a 250 ml flask, and then stirred. Then heated to 50° C., and then added with 22.20 g of HDI TRIMER and 19.50 g of DMAc (N,N-Dimethylacetamide). The mixture was heated to 90° C., and the reaction was performed for 2-3 hours (the NCO group was titrated till the end point of the reaction). Then, the mixture was cooled down to 70° C., and then added with 2.59 g of MDEA (N-methyldiethanolamine), which is neutralized by 1.30 g of AcOH (acetic acid) in advance, and 7.20 g of DMAc. The mixture was heated to 90° C., and the reaction was performed for 2-3 hours (the NCO group was titrated till the end point of the reaction). The mixture was cooled down to 50° C., and then the comparative example 1 was obtained.

[0039] The aforementioned monomer structure of comparative example 1 can be represented by formula (I):

##STR00004##

[0040] wherein A is α-[3-[3-(2H-Benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl]-ω-hydroxypoly(oxo-1,2-ethanediyl), B is HDI TRIMER, and C is MDEA. The average weight molecular weight of comparative example 1 is about 3608.4.

Test Example 1—Light Fastness Test

[0041] The solution (80 g/l-120 g/l) of aforementioned examples and comparative examples were poured over the roller of a padding machine to proceed padding treatment for dyed sample fabrics (13 cm×5 cm) under less than 80% of wet pickup condition, and then dyed sample fabrics were put in an oven at 60° C. for 15 minutes. After drying, dyed sample fabrics were divided into two groups which are non-washed group and washed-five-times group. Non-washed group was conducted light fastness testing according to AATCC 16-2010 method 3 (20 light units), and measured the degree of fading by a spectrophotometer after exposure to artificial daylight. The results were graded by the instrument. Furthermore, the washed five-times-group was conducted a light fastness testing after washing testing as follows.

Test Example 2—Washing Test

[0042] The washed five-times-group was provided, and added with the accompanying fabric, which is 50/50 poly-cotton blend (92 cm×92 cm), to 1.8 kg in total. Then added with 66 g of washing powder (1933 AATCC washing powder) to wash, and the water temperature was set as 49° C.±3° C. The washing procedure was set as standard setting: water level is 18±0.5 gal; agitation speed is 179±.sup.2 spm; washing time is 12 minutes; spin speed is 645±15 rpm; final spin time is 6 minutes. The dyed sample fabrics were added with 66 g of washing powder to proceed next washing cycle without drying until 5 washing cycles were finished. The washing procedure is conducted according to AATCC 135-2004′ method.

[0043] The results of non-washed group and washed five-times-group are shown in table 2 and table 3 respectively. The Blank is dyed sample fabrics without adding any solution.

TABLE-US-00002 TABLE 2 Comparative example 1 Compound 1 Compound 2 Compound 3 Compound 4 Compound 5 Blank Grade: 3 Grade: 3.5 Grade: 3 Grade: 2.5 Grade: 2.5 Grade: 2.5 Non- Grade: 4 Grade: 4.5 Grade: 4 Grade: 3.5 Grade: 3.5 Grade: 3.5 washed Enhanced 1 1 1 1 1 1 grade of light fastness

TABLE-US-00003 TABLE 3 Comparative example 1 Compound 1 Compound 2 Compound 3 Compound 4 Compound 5 Blank Grade: 3 Grade: 3.5 Grade: 3 Grade: 2.5 Grade: 2.5 Grade: 2.5 Washed Grade: 3 Grade: 4 Grade: 4 Grade: 3 Grade: 3.5 Grade: 3.5 five times Enhanced 0 0.5 1 0.5 1 1 grade of light fastness

[0044] It can be seen that light fastness of dyed sample fabrics was enhanced by 1 grade after added with solution of compounds according to table 2. In accordance with table 3, the light fastness of dyed sample fabrics added with comparative example 1 solution decreased after washing five times. By contrast, the light fastness of dyed sample fabrics added with solution of examples 1-5 were still enhanced by 0.5-1 degree. Further, examples 1 and 2 comprise chain extender respectively and examples 3-5 do not comprise chain extender; by comparison, both of them provide dyed sample fabrics with excellent light fastness and washing fastness.

[0045] Although the present invention has been explained in relation to its preferred embodiment, it is to be understood that many other possible modifications and variations can be made without departing from the spirit and scope of the invention as hereinafter claimed.