阅读说明：本技术 水性乳液抗紫外线整理剂及其制备方法 (Water-based emulsion ultraviolet-resistant finishing agent and preparation method thereof ) 是由 徐栋良 徐达峰 蒋莲芳 于 2020-05-21 设计创作，主要内容包括：本发明涉及一种水性乳液抗紫外整理剂及其制备方法,涉及纺织品功能整理剂及其制备技术领域。本发明的水性乳液抗紫外整理剂由按重量份计的单羟基二苯甲酮类紫外线吸收剂50-70份、苯并三唑类紫外线吸收剂10-30份、非离子乳化剂10-20份、阳离子乳化剂3-7份和软水80-120份制成,其制备方法包括备料、混料和乳化步骤,制得的水性乳液抗紫外整理剂具有极佳的紫外线吸收效果、应用方便、抗迁移性好且能最大程度降低对服装面料服用性能的负面影响。(The invention relates to an aqueous emulsion ultraviolet-resistant finishing agent and a preparation method thereof, and relates to the technical field of textile functional finishing agents and preparation thereof. The water-based emulsion ultraviolet-resistant finishing agent is prepared from 50-70 parts of monohydroxybenzophenone ultraviolet absorbent, 10-30 parts of benzotriazole ultraviolet absorbent, 10-20 parts of nonionic emulsifier, 3-7 parts of cationic emulsifier and 80-120 parts of soft water in parts by weight, and the preparation method comprises the steps of material preparation, material mixing and emulsification.)

1. An aqueous emulsion ultraviolet-resistant finishing agent is characterized in that: is prepared from the following components in parts by weight,

50-70 parts of monohydroxybenzophenone ultraviolet absorbent

10-30 parts of benzotriazole ultraviolet absorber

10-20 parts of nonionic emulsifier

3-7 parts of cationic emulsifier

80-120 parts of soft water.

2. The aqueous emulsion uv-resistant finish according to claim 1, characterized in that: the monohydroxybenzophenone ultraviolet absorbent is one or a mixture of more of the substances shown in the chemical formula I,

formula I:

wherein R represents C₂~C₈Straight chain alkyl or branched alkyl.

3. The aqueous emulsion uv-resistant finish according to claim 2, characterized in that: the monohydroxybenzophenone ultraviolet absorbent is one or a mixture of more of the substances shown in the chemical formula I,

formula I:

wherein R represents C₂~C₈A branched alkyl group.

4. The aqueous emulsion uv-resistant finish according to claim 2, characterized in that: the monohydroxy benzophenone ultraviolet finishing agent is liquid under the environment of 1 standard atmospheric pressure and 25 ℃.

5. The aqueous emulsion uv-resistant finish according to claim 2, characterized in that: the monohydroxy benzophenone ultraviolet finishing agent is 2-hydroxy-4-isooctyl benzophenone.

6. The aqueous emulsion UV-resistant finish according to any one of claims 1 to 5, characterized in that: the benzotriazole ultraviolet absorbent is 2- (2-hydroxy-5-methylphenyl) benzotriazole.

7. The aqueous emulsion UV-resistant finish according to any one of claims 1 to 5, characterized in that: is prepared from the following components in parts by weight,

60 parts of monohydroxybenzophenone ultraviolet absorber

20 parts of benzotriazole ultraviolet absorber

15 portions of non-ionic emulsifier

5 portions of cationic emulsifier

100 parts of soft water.

8. The aqueous emulsion UV-resistant finish according to any one of claims 1 to 5, characterized in that: the nonionic emulsifier is castor oil polyoxyethylene ether EL-40, and the cationic emulsifier is octadecyl trimethyl ammonium chloride.

9. A preparation method of an aqueous emulsion anti-ultraviolet finishing agent is characterized by comprising the following steps: comprises the following steps of (a) carrying out,

preparing materials: weighing 50-70 parts of monohydroxybenzophenone ultraviolet absorbent, 10-30 parts of benzotriazole ultraviolet absorbent, 10-20 parts of nonionic emulsifier, 3-7 parts of cationic emulsifier and 80-120 parts of soft water according to the weight part ratio;

mixing materials: mixing the weighed monohydroxybenzophenone ultraviolet absorbent, benzotriazole ultraviolet absorbent, nonionic emulsifier and cationic emulsifier, heating to 50-60 ℃ under stirring, preserving heat, and continuously stirring until the mixed material is melted to obtain a melted mixed material;

emulsification: and under the stirring condition, dropwise adding the weighed soft water into the melted mixture, and emulsifying to obtain the aqueous emulsion ultraviolet-resistant finishing agent.

10. The method for preparing the aqueous emulsion ultraviolet-resistant finishing agent according to claim 9, characterized in that: the stirring speed in the emulsification step is 5000-15000 rpm.

Technical Field

The invention relates to the technical field of textile functional finishing agents and preparation thereof, in particular to an aqueous emulsion ultraviolet-resistant finishing agent and a preparation method thereof.

Background

The research on the anti-ultraviolet finishing agent has attracted attention for a long time, and the anti-ultraviolet finishing agent can be divided into the following parts according to an anti-ultraviolet mechanism: reflective uvioresistant finishing agent, absorptive uvioresistant finishing agent and nano uvioresistant finishing agent. The reflective ultraviolet finishing agent is mostly used for sunshades, tents and the like, but rarely used for garment materials because the air permeability, hand feeling and washability of the finished fabric are poor, the color, fastness and whiteness of the fabric are reduced to some extent, and some of the fabric even cause anaphylactic reaction of human bodies; however, in the application of nano ultraviolet-resistant finishing, there are many problems to be solved, such as: how to prevent agglomeration of the nanomaterial, how to reduce the loss of strength of the fabric during the finishing process, etc. Therefore, the mainstream anti-ultraviolet finishing agent for the garment fabric in the market still mainly adopts the absorption type ultraviolet finishing agent.

The absorption type ultraviolet-resistant finishing agent is also called an ultraviolet absorbent, can strongly and selectively absorb high-energy ultraviolet rays and release the high-energy ultraviolet rays in other forms with lower energy (such as light or heat with longer wavelength), so that the damage of the ultraviolet rays to the skin of a human body is avoided, and the absorbent is not damaged by the ultraviolet rays. Common uv absorbers are:

benzophenone compounds:

the carbonyl group and the hydroxyl group in the molecule of the compound form an intramolecular hydrogen bond to form a chelate ring structure. After absorbing ultraviolet rays, internal hydrogen bonds oscillate, stable chelate rings are opened, absorbed energy is released in the form of heat energy, and carbonyl groups in molecules are excited by absorbed ultraviolet light energy to generate tautomerism of an enol structure, so that a part of energy is consumed. The common compounds are 2, 4-dihydroxy benzophenone and the like, the compounds have a plurality of hydroxyl groups, have better adsorption capacity on fibers, can absorb ultraviolet rays with the wavelength of 280-400 nm, and are mainly used for fibers such as polypropylene, polyester, cellulose and the like. However, such benzophenone-based ultraviolet absorbers containing two hydroxyl groups absorb ultraviolet rays of 300 to 400nm in a biased manner, hardly absorb ultraviolet rays of 280nm or less, absorb a part of visible light, capture color, and have a tendency to yellow.

② salicylic acid esters:

salicylic acid ester ultraviolet absorbers also have intrinsic hydrogen bonds in the molecule, have low ultraviolet absorption capacity at the beginning, and have a narrow absorption range (less than 340nm), but the absorption gradually increases after a certain period of irradiation. The reason is that molecular rearrangement occurs under the irradiation of ultraviolet rays to form a benzophenone structure with strong ultraviolet absorption capability, thereby strengthening the ultraviolet absorption capability of the benzophenone structure. The dihydroxy benzophenone and the derivatives thereof generated after rearrangement can absorb part of visible light to present yellow. Resulting in yellowing of the finished fabric.

③ benzotriazoles:

the action principle of the benzotriazole ultraviolet absorbers is similar to that of benzophenones: the benzotriazole has better ultraviolet absorption effect than benzophenone ultraviolet absorbent, can absorb light of 300-400nm, does not absorb light with wavelength of more than 400nm, and has the advantages of difficult yellowing, volatility resistance, oil resistance and the like. However, the benzotriazole absorbent has a very close structure to that of a disperse dye, so that the application range of the benzotriazole absorbent is limited, the benzotriazole absorbent needs to be treated by a high-temperature and high-pressure method when being used for terylene, and if the benzotriazole absorbent is applied to chinlon, wool, silk and cotton fabrics, a proper amount of sulfonic acid groups are required to be grafted in the molecules of the benzotriazole absorbent for modification. Further, such an ultraviolet absorber is a solid powder, and it is necessary to grind the powder for a long time, and is used in the form of a powder or a suspension. The grinding time is long, the nano-scale is difficult to achieve in the conventional grinding, the durability of the finished ultraviolet absorbent attached to the surface of the fabric is poor, and the color light change of the fabric is easily caused by the attachment of the powdery ultraviolet absorbent.

(iv) triazines:

the triazine and triazole ultraviolet absorbers both contain N, effectively absorb ultraviolet rays by means of intramolecular hydrogen bonds formed by N, H and conversion of enol-type and ketone-type structures, and have high absorption capacity on ultraviolet rays of 280-380 nm. The absorption effect of the triazine absorbent is in direct proportion to the number of hydroxyl groups, so that the triazine absorbent has poor compatibility with high polymers, and the finished fabric is easy to color.

Organic nickel:

the organic nickel polymer has low absorption capacity, when the organic nickel polymer molecule receives the energy of ultraviolet irradiation and is excited into an excited state, and when the ultraviolet light is lost, the excited state returns to the ground state, so that the ultraviolet energy is converted into a spectrum with low energy for emission. Thereby reducing the transmittance of ultraviolet rays. The organic nickel absorbent can form a chelate complex with part of the fiber fabric under certain conditions, but the organic nickel absorbent is often colored and has limited use.

Although the garment fabric anti-ultraviolet finishing agent taking the ultraviolet absorbent as the main component has a certain anti-ultraviolet effect, the garment fabric anti-ultraviolet finishing agent also has the defects of narrow absorption range, yellowing of finished fabrics, limited application range and the like. In order to improve the performance of the uv absorbers, researchers have modified the existing absorbers to improve the application performance. For example, zhuhuang [ study of ultraviolet-resistant finishing of fabric [ J ]. proceedings of Shanghai engineering and technology university, 2001,15 (3): 227-231 ] and the like, the anti-ultraviolet finishing agents UV-5 and UV-6 are obtained by compounding a self-made absorbent, a scattering agent, an adhesive and a softening agent, a set of finishing process is explored through experiments, a good anti-ultraviolet effect is obtained, and meanwhile, the whiteness and the air permeability of the finished fabric are reduced to a certain degree due to the use of the scattering agent, the adhesive and the softening agent, and the use comfort is influenced.

Therefore, how to develop an anti-ultraviolet finishing agent for garment materials, which can improve the anti-ultraviolet performance of the fabric while keeping the original wind of the fabric, remains a problem to be solved by those skilled in the art.

Disclosure of Invention

In view of the defects in the prior art, one of the purposes of the invention is to provide an aqueous emulsion ultraviolet-resistant finishing agent which has the advantages of good ultraviolet-resistant effect, convenient use and small negative influence on the wearability of clothing.

The above object of the present invention is achieved by the following technical solutions:

an aqueous emulsion uvioresistant finishing agent is prepared from the following components in parts by weight,

the monohydroxybenzophenone ultraviolet absorber in the invention refers to an organic compound with ultraviolet absorption property, wherein benzophenone contains only one hydroxyl in the molecule. The anti-ultraviolet finishing agent in an aqueous emulsion state is prepared by taking monohydroxybenzophenone ultraviolet absorbent and benzotriazole ultraviolet absorbent as main raw materials and matching with nonionic emulsifier and cationic emulsifier according to a specific ratio, has good storage stability, can be directly used for finishing clothing fabrics or used after dilution, and is convenient to use. After the garment fabric is finished by the uvioresistant finishing agent, the uvioresistant finishing agent has excellent blocking effect on ultraviolet rays in the range of 240 plus one 400nm, and the uvioresistant performance is obviously improved. Meanwhile, the negative influence on the wearability (color light, hygroscopicity, hand feeling and light fastness) of the garment material is reduced to the maximum extent. Compared with the solid powdery anti-ultraviolet finishing agent prepared by conventional grinding, the fabric after finishing has better durability of anti-ultraviolet effect, and simultaneously, the whitening problem easily caused by the powdery anti-ultraviolet finishing agent is not easy to occur.

Further, the monohydroxybenzophenone ultraviolet absorbent is one or a mixture of more of the substances shown in the chemical formula I,

formula I:

wherein R represents C₂～C₈Straight chain alkyl or branched alkyl.

By adopting the technical scheme, the ultraviolet absorption effect of the prepared water-based emulsion ultraviolet-resistant finishing agent is excellent.

Further, the monohydroxybenzophenone ultraviolet absorbent is one or a mixture of more of the substances shown in the chemical formula I,

formula I:

wherein R represents C₂～C₈A branched alkyl group.

Due to the existence of the branched chain, the branched chain alkyl increases the steric hindrance of the alkyl, so that R in the molecule of the monohydroxybenzophenone ultraviolet absorbent is more difficult to fold, the melting point of the branched chain alkyl is correspondingly reduced, and the branched chain alkyl is more easily fused with the benzotriazole ultraviolet absorbent to prepare the anti-ultraviolet finishing agent in an emulsion state. Meanwhile, the anti-ultraviolet finishing agent has good anti-migration performance.

Further, the monohydroxybenzophenone ultraviolet finishing agent is liquid under the environment of 1 standard atmospheric pressure and 25 ℃.

The liquid monohydroxy benzophenone ultraviolet finishing agent is better beneficial to the mixing and dissolving of all components, and the prepared ultraviolet-resistant finishing agent has better stability and ultraviolet-resistant finishing effect.

Further, the monohydroxybenzophenone ultraviolet finishing agent is 2-hydroxy-4-isooctyl benzophenone.

By adopting the technical scheme, the prepared ultraviolet-resistant finishing agent has excellent ultraviolet absorption effect and migration resistance.

Further, the benzotriazole ultraviolet absorbent is 2- (2-hydroxy-5-methylphenyl) benzotriazole.

By adopting the technical scheme, the 2- (2-hydroxy-5-methylphenyl) benzotriazole and the monohydroxybenzophenone ultraviolet absorbent are mixed to achieve the effect of synergistically improving the ultraviolet resistance effect of the garment material.

Further, the adhesive is prepared from the following components in parts by weight,

the applicant finds out through repeated experiments that the effect of the aqueous emulsion uvioresistant finishing agent with the proportion is optimal by considering three factors of uvioresistant effect, emulsion stability and influence on the wearability of the garment fabric.

Further, the nonionic emulsifier is castor oil polyoxyethylene ether EL-40, and the cationic emulsifier is octadecyl trimethyl ammonium chloride.

The invention also aims to provide a preparation method of the water-based emulsion ultraviolet-resistant finishing agent, and the water-based emulsion ultraviolet-resistant finishing agent prepared by the method has the advantages of good ultraviolet-resistant effect, convenience in use and small negative influence on the wearability of clothing.

The above object of the present invention is achieved by the following technical solutions:

a preparation method of an aqueous emulsion anti-ultraviolet finishing agent comprises the following steps,

preparing materials: weighing 50-70 parts of monohydroxybenzophenone ultraviolet absorbent, 10-30 parts of benzotriazole ultraviolet absorbent, 10-20 parts of nonionic emulsifier, 3-7 parts of cationic emulsifier and 80-120 parts of soft water according to the weight part ratio;

mixing materials: mixing the weighed monohydroxybenzophenone ultraviolet absorbent, benzotriazole ultraviolet absorbent, nonionic emulsifier and cationic emulsifier, heating to 50-60 ℃ under stirring, preserving heat, and continuously stirring until the mixed material is melted to obtain a melted mixed material;

emulsification: and under the stirring condition, dropwise adding the weighed soft water into the melted mixture, and emulsifying to obtain the aqueous emulsion ultraviolet-resistant finishing agent.

The preparation method has simple process steps, and the prepared water-based emulsion ultraviolet-resistant finishing agent has excellent ultraviolet absorption effect, convenient application and good migration resistance, and can reduce the negative influence on the wearability of the garment material to the maximum extent.

Further, the stirring speed in the emulsification step is 5000-15000 rpm. .

By adopting the technical scheme, the prepared water-based emulsion ultraviolet-resistant finishing agent has better stability and finishing effect.

In summary, the invention includes at least one of the following beneficial technical effects:

1. the anti-ultraviolet finishing agent in the state of aqueous emulsion is prepared by taking monohydroxybenzophenone ultraviolet absorbent and benzotriazole ultraviolet absorbent as main raw materials and matching with nonionic emulsifier and cationic emulsifier according to a specific ratio, has good storage stability, can be directly used for finishing clothing fabric or used for finishing clothing fabric after being diluted, and is convenient to use; after the garment fabric is finished by the uvioresistant finishing agent, the uvioresistant finishing agent has excellent blocking effect on ultraviolet rays in the range of 240-400nm, and the uvioresistant performance is obviously improved; meanwhile, the negative influence on the wearability (color light, hygroscopicity, hand feeling and light fastness) of the garment material is reduced to the maximum extent. Compared with the solid powdery anti-ultraviolet finishing agent prepared by conventional grinding, the fabric after finishing has better durability of anti-ultraviolet effect, and simultaneously the whitening problem easily caused by the powdery anti-ultraviolet finishing agent is not easy to occur;

2. in the preferred scheme, the monohydroxybenzophenone ultraviolet absorbent with the R group being branched chain alkyl is selected, and can be easily fused with the benzotriazole ultraviolet absorbent to prepare the anti-ultraviolet finishing agent in an emulsion state, so that the synergistic anti-ultraviolet effect is good, and the anti-ultraviolet finishing agent has good anti-migration performance;

3. in the preferred scheme, the anti-ultraviolet finishing effect of the aqueous emulsion anti-ultraviolet finishing agent prepared by taking 2-hydroxy-4-isooctyl benzophenone and 2- (2-hydroxy-5-methylphenyl) benzotriazole as ultraviolet absorbing components is excellent;

4. the invention correspondingly discloses a preparation method of the water-based emulsion ultraviolet-resistant finishing agent, which has the advantages of simple process steps, excellent ultraviolet absorption effect of the prepared water-based emulsion ultraviolet-resistant finishing agent, convenience in application, good migration resistance and capability of reducing the negative influence on the wearability of clothing fabrics to the greatest extent.

Detailed Description

The present invention will be described in further detail with reference to examples.

The UV absorbers selected in the following examples or comparative examples may be purchased commercially, custom synthesized or self-made, and specifically the sources of the materials are shown in Table 1:

TABLE 1 table of sources of substances

Wherein, the 2-hydroxy-4-ethoxy benzophenone, the 2-hydroxy-4- (2-methylpropoxy) benzophenone, the 2-hydroxy-4- (2-ethylbutoxy) benzophenone and the 2-hydroxy-4-isobutoxy benzophenone are respectively prepared according to the following methods:

(A) preparation of 2-hydroxy-4-ethoxy benzophenone

214g of 2, 4-dihydroxy benzophenone, 78g of chloroethane, 115g of soda ash, 20g of PEG-40020 g and 10g of potassium bromide are put into a 500ml four-neck flask provided with a thermometer and a stirring device, the temperature is raised to 100 ℃ after the putting, and stirring is started; and continuously heating to 150 ℃, refluxing and water dividing, cooling after water dividing is finished (about 8 hours), adding water for washing, standing for layering, and distilling out a product of the oil layer by high vacuum rectification, wherein the product is the preparation of the 2-hydroxy-4-ethoxy benzophenone.

(B) Preparation of 2-hydroxy-4- (2-methylpropoxy) benzophenone

214g of 2, 4-dihydroxy benzophenone, 112g of 1-chloro-2-methylpropane, 115g of soda ash, 20g of PEG-40020 g and 10g of potassium bromide are put into a 500ml four-neck flask provided with a thermometer and a stirring device, the temperature is raised to 100 ℃ after the putting, and stirring is started; and continuously heating to 150 ℃, refluxing and water dividing, cooling after water dividing is finished (about 8 hours), adding water for washing, standing for layering, and distilling out a product, namely the 2-hydroxy-4- (2-methylpropoxy) benzophenone, from an oil layer by high vacuum rectification.

(C) Preparation of 2-hydroxy-4- (2-ethylbutoxy) benzophenone

214g of 2, 4-dihydroxy benzophenone, 145g of 1-chloro-2-ethylbutane, 115g of soda ash, 20g of PEG-40020 g and 10g of potassium bromide are put into a 500ml four-neck flask provided with a thermometer and a stirring device, the temperature is raised to 100 ℃ after the putting, and stirring is started; and continuously heating to 150 ℃, refluxing and water dividing, cooling after water dividing is finished (about 8 hours), adding water for washing, standing for layering, and distilling out a product, namely the 2-hydroxy-4- (2-ethylbutoxy) benzophenone, from an oil layer by high vacuum rectification.

(D) Preparation of 2-hydroxy-4-isobutoxy benzophenone

214g of 2, 4-dihydroxy benzophenone, 112g of 1-chlorobutane, 115g of soda ash, 20g of PEG-40020 g and 10g of potassium bromide are put into a 500ml four-neck flask provided with a thermometer and a stirring device, the temperature is raised to 100 ℃ after the putting, and stirring is started; and continuously heating to 150 ℃, refluxing and water dividing, cooling after water dividing is finished (about 8 hours), adding water for washing, standing for layering, and distilling out a product, namely the 2-hydroxy-4-butoxy benzophenone, from an oil layer by high vacuum rectification.

The chloroethane, 1-chloro-2-methylpropane, 1-chloro-2-ethylbutane and 1-chlorobutane are all industrial grade and are obtained by commercial purchase.