阅读说明：本技术 一种阻燃胶乳及其制备方法和应用 (Flame-retardant latex and preparation method and application thereof ) 是由 戴国达 李兵 于 2020-12-29 设计创作，主要内容包括：本发明提供一种阻燃胶乳及其制备方法和应用,所述阻燃胶乳按照重量份包括如下组分：氯丁胶乳70～90重量份、硫化剂1～6重量份、促进剂1～3重量份和卤素类阻燃剂10～40重量份；所述阻燃胶乳通过选择氯丁胶乳,并且搭配添加特定份数的卤素类阻燃剂,使得得到的阻燃胶乳具有优异的阻燃和耐高温性能；将其与手套芯共同制备成的阻燃乳胶手套具有优异的耐高温阻燃性能,可以满足对劳动防护用品的耐高温、阻燃性的高要求。(The invention provides flame-retardant latex and a preparation method and application thereof, wherein the flame-retardant latex comprises the following components in parts by weight: 70-90 parts of neoprene latex, 1-6 parts of vulcanizing agent, 1-3 parts of accelerant and 10-40 parts of halogen flame retardant; the chloroprene latex is selected as the flame-retardant latex, and halogen flame retardants in specific parts are added, so that the flame-retardant latex has excellent flame retardance and high temperature resistance; the flame-retardant latex gloves prepared by the flame-retardant latex and the glove cores have excellent high-temperature resistance and flame retardance, and can meet the high requirements on high-temperature resistance and flame retardance of labor protection products.)

1. The flame-retardant latex is characterized by comprising the following components in parts by weight: 70-90 parts of neoprene latex, 1-6 parts of vulcanizing agent, 1-3 parts of accelerant and 10-40 parts of halogen flame retardant.

2. The flame-retardant latex according to claim 1, wherein the viscosity of the flame-retardant latex is 500 to 2000 mPa-s.

3. Flame retardant latex according to claim 1 or 2, characterized in that the vulcanising agent comprises sulphur and/or zinc oxide.

4. The flame retardant latex according to any one of claims 1 to 3, wherein said accelerator comprises any one or a combination of at least two of zinc diethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc dibutyldithiocarbamate, tetramethylthiuram disulfide or diphenylguanidine.

5. The flame retardant latex according to any one of claims 1 to 4, wherein the halogen flame retardant comprises any one or a combination of at least two of an antimony-bromine composite flame retardant, an antimony-based flame retardant, a bromine-based flame retardant, and a phosphorus-based flame retardant.

6. The flame retardant latex according to any one of claims 1 to 5, further comprising any one or a combination of at least two of a pH regulator, a surfactant, an antioxidant, a thickener or a toner;

preferably, the content of the pH regulator in the flame-retardant latex is 0.5-1.5 parts by weight;

preferably, the pH adjuster comprises potassium hydroxide and/or ammonia;

preferably, the content of the surfactant in the flame-retardant latex is 1-2 parts by weight;

preferably, the surfactant comprises sodium dodecylbenzene sulfonate;

preferably, the content of the antioxidant in the flame-retardant latex is 1-2 parts by weight;

preferably, the content of the thickening agent in the flame-retardant latex is 7-9 parts by weight;

preferably, the content of the color enhancer in the flame-retardant latex is 2-3 parts by weight.

7. A process for the preparation of a flame retardant latex according to any one of claims 1 to 6, characterized in that it comprises: the neoprene latex, a vulcanizing agent, an accelerator, a halogen flame retardant, an optional pH regulator, an optional surfactant, an optional antioxidant and an optional toner are mixed to obtain the flame retardant latex.

8. The method according to claim 7, wherein the mixing time is 60 to 120 min;

preferably, the step of adding a thickening agent and standing is further included after the mixing;

preferably, the standing time is more than 12 h.

9. A flame retardant latex glove, wherein the flame retardant latex glove comprises the flame retardant latex of any one of claims 1 to 6 and a glove core;

preferably, the material of the glove core comprises polyimide fibers.

10. A method of making the flame retardant latex glove of claim 9, wherein the method of making comprises: dipping, coating anti-slip treatment, soaking and washing and co-vulcanizing a glove core by using the flame-retardant latex of any one of claims 1 to 6 to obtain the flame-retardant latex glove.

Technical Field

The invention belongs to the technical field of labor protection products, and particularly relates to flame-retardant latex as well as a preparation method and application thereof.

Background

With the continuous development of economy, the requirements of various industries on labor protection products are gradually improved, and some glove products with high strength and flame resistance are needed to meet the requirements of different users, but at present, domestic industrialized products are mainly used for producing common latex for butyronitrile labor protection gloves and disposable medical examination gloves, so that the development of some glove products with special brands and performance requirements is necessary, the application field and the application of the glove products are widened, and the market requirements are met.

The high temperature resistant and flame retardant gloves are special high temperature resistant gloves used in high temperature environment, different high temperature resistant gloves can be selected according to the temperature of hand contact, and the design of the palm and the forefinger wear-resistant skin layer of the extremely high temperature mixed chemical fiber five-finger gloves is the most popular direction for the research of the flame retardant gloves at present. There are many reports on gloves having flame retardant properties. CN209660511U discloses fire-retardant gloves of protectiveness, which comprises a glove, the lower extreme of gloves is connected with the cuff, and the inside of cuff is provided with the elastic cord, and one side of elastic cord is connected with the fixed band, the fixed band runs through one side of cuff, the lower extreme surface of fixed band is provided with below the nylon hasp glutinous face, and the front surface of cuff is provided with on the nylon hasp glutinous face, and the fixed band is through the nylon hasp on glutinous face and the nylon hasp under glutinous face connect this fire-retardant gloves of protectiveness set up at the gloves lower extreme, be provided with the elastic cord in the inside of cuff, can stretch out and draw back the size of cuff through the elasticity area, and fix through the fixed band in one side of elastic cord, can come to adjust the size of cuff according to user's arm size like this, can mention the safety protection performance of gloves. CN211431162U discloses fire-retardant formula labor protection gloves in high temperature workshop, including fire-retardant gloves, the fixedly connected with non-slip raised on fire-retardant gloves surface, the bottom fixedly connected with wrist band of fire-retardant gloves, the fixed glove mouth of having seted up in wrist band bottom, the fixed surface of wrist band is connected with the lantern ring, and the wrist band is close to the insulating fire-retardant layer of outside fixedly connected with, and the inboard fixedly connected with in insulating fire-retardant layer has soft cotton layer, and soft cotton layer inside fixed mounting has temperature monitor. The utility model discloses a through setting up temperature monitoring device, real time monitoring is carried out to gloves temperature, when the temperature reached and caused the injury to the human body, triggered alarm equipment had guaranteed the personal safety of the person of wearing, had guaranteed the normal work of the person of wearing, through setting up at the inside miniature vibrations massage device of wrist band, alleviated the person of wearing and wear increase wrist pressure for a long time, caused muscle ache scheduling problem, improved the work efficiency of the person of wearing. CN111364138A discloses a composite yarn for manufacturing high-temperature operation protective articles, which comprises the following components in percentage by mass: modified polyphenylene sulfide fiber: 20-98%; aromatic polyamide fiber: 1-40%; flame retardant cellulose fiber: 1-40%; the modified polyphenylene sulfide fiber is an oxidized and modified polyphenylene sulfide fiber, sulfur atoms in a polyphenylene sulfide structure are partially or completely oxidized into sulfone groups or sulfoxide groups through oxidation modification, and the modified polyphenylene sulfide fiber has the characteristics of no melting, no shrinkage and extinguishing after leaving fire at high temperature. The protective gloves/work clothes and the like prepared from the yarn are not easy to have the potential safety hazard of hand damage caused by fiber fusion and adhesion to skin under the high-temperature condition, and a brand-new yarn material is provided for labor protection under special working conditions.

However, researches and practices find that the excellent high-temperature-resistant flame-retardant effect of the high-temperature-resistant gloves is not ideal only by selecting the fibers of the glove cores and designing the skin layers, and the flame-retardant effect at extremely high temperature (more than 300 ℃) is greatly reduced, so that the market demand cannot be met.

Therefore, the development of the flame-retardant latex with high temperature resistance and excellent flame-retardant performance and the flame-retardant latex gloves prepared by the flame-retardant latex have important research significance.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide flame-retardant latex and a preparation method and application thereof, wherein the flame-retardant latex comprises the combination of neoprene latex, a vulcanizing agent, an accelerator and a halogen flame retardant, and the flame-retardant latex has excellent flame retardance and high-temperature resistance by selecting the neoprene latex and adding a specific part of the halogen flame retardant; the flame-retardant latex gloves prepared from the flame-retardant latex and the glove cores have excellent high-temperature resistance and flame retardance, and can meet the high requirements on high-temperature resistance and flame retardance of labor protection products.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the present invention provides a flame retardant latex, comprising the following components in parts by weight: 70-90 parts of neoprene latex, 1-6 parts of vulcanizing agent, 1-3 parts of accelerant and 10-40 parts of halogen flame retardant.

The neoprene latex may be 72 parts by weight, 74 parts by weight, 76 parts by weight, 78 parts by weight, 80 parts by weight, 82 parts by weight, 84 parts by weight, 86 parts by weight, 88 parts by weight, and specific points therebetween, which are not exhaustive of the invention for reasons of brevity and clarity.

The vulcanizing agent may be 12.3 parts by weight, 1.6 parts by weight, 1.9 parts by weight, 2.3 parts by weight, 2.6 parts by weight, 2.9 parts by weight, 3.2 parts by weight, 3.5 parts by weight, 3.9 parts by weight, 4.2 parts by weight, 4.6 parts by weight, 5 parts by weight, 5.3 parts by weight, 5.6 parts by weight, or 5.9 parts by weight, and specific point values therebetween are limited in space and for the sake of brevity, and the invention is not exhaustive of the specific point values included in the ranges.

The accelerator may be 1.2 parts by weight, 1.4 parts by weight, 1.6 parts by weight, 1.8 parts by weight, 2 parts by weight, 2.2 parts by weight, 2.4 parts by weight, 2.6 parts by weight, or 2.8 parts by weight, and specific values therebetween, not to be limited by the space and for the sake of brevity, the invention is not exhaustive of the specific values included in the ranges.

The halogen-based flame retardant includes 13 parts by weight, 16 parts by weight, 19 parts by weight, 23 parts by weight, 26 parts by weight, 29 parts by weight, 33 parts by weight, 36 parts by weight, or 39 parts by weight, and specific points therebetween, which are not exhaustive of the invention for the sake of brevity and clarity.

The flame-retardant latex provided by the invention comprises the combination of neoprene latex, a vulcanizing agent, an accelerator and a halogen flame retardant; the flame-retardant latex is prepared by selecting neoprene latex as a matrix, wherein the neoprene latex has good ozone resistance and flame-retardant adhesive property; the halogen flame retardant is added into the latex, is a good additive flame retardant and is added into the neoprene latex, so that the flame-retardant latex with excellent high-temperature resistance and flame retardance is obtained.

Preferably, the viscosity of the flame-retardant latex is 500 to 2000 mPas, such as 700 mPas, 900 mPas, 1100 mPas, 1300 mPas, 1500 mPas, 1700 mPas or 1900 mPas, and the specific values therebetween are not exhaustive for the sake of brevity and are not intended to limit the scope of the invention to the specific values included therein.

Preferably, the vulcanizing agent comprises sulphur and/or zinc oxide.

Preferably, the accelerator comprises any one of or a combination of at least two of zinc diethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc dibutyldithiocarbamate, tetramethylthiuram disulphide or diphenylguanidine.

Preferably, the halogen flame retardant comprises any one of or a combination of at least two of an antimony-bromine composite flame retardant, an antimony-based flame retardant, a bromine-based flame retardant or a phosphorus-based flame retardant.

Preferably, the flame retardant latex further comprises any one or a combination of at least two of a pH regulator, a surfactant, an antioxidant, a thickener and a color enhancer.

Preferably, the content of the pH regulator in the flame-retardant latex is 0.5 to 1.5 parts by weight, such as 0.6 part by weight, 0.7 part by weight, 0.8 part by weight, 0.9 part by weight, 1 part by weight, 1.1 part by weight, 1.2 parts by weight, 1.3 parts by weight or 1.4 parts by weight, and specific points therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive list of specific points included in the range.

Preferably, the pH adjuster comprises potassium hydroxide and/or ammonia.

Preferably, the surfactant is contained in the flame retardant latex in an amount of 1 to 2 parts by weight, for example, 1.1 parts by weight, 1.2 parts by weight, 1.3 parts by weight, 1.4 parts by weight, 1.5 parts by weight, 1.6 parts by weight, 1.7 parts by weight, 1.8 parts by weight or 1.9 parts by weight, and specific points therebetween are not exhaustive, and for brevity and brevity, the specific points included in the range are not limited to the space and are not exhaustive.

Preferably, the surfactant comprises sodium dodecylbenzene sulfonate.

Preferably, the antioxidant is present in the flame retardant latex in an amount of 1 to 2 parts by weight, such as 1.1 parts by weight, 1.2 parts by weight, 1.3 parts by weight, 1.4 parts by weight, 1.5 parts by weight, 1.6 parts by weight, 1.7 parts by weight, 1.8 parts by weight, or 1.9 parts by weight, and specific values therebetween, are not exhaustive and for the sake of brevity.

Preferably, the thickener is contained in the flame retardant latex in an amount of 7 to 9 parts by weight, for example, 7.2 parts by weight, 7.4 parts by weight, 7.6 parts by weight, 7.8 parts by weight, 8 parts by weight, 8.2 parts by weight, 8.4 parts by weight, 8.6 parts by weight or 8.8 parts by weight, and specific points therebetween are not exhaustive, and the invention is not limited to the specific points included in the range for brevity and conciseness.

Preferably, the thickener may be selected from carboxylic acid-based thickeners and/or cellulose-based thickeners.

Preferably, the content of the color enhancer in the flame-retardant latex is 2 to 3 parts by weight, such as 2.1 parts by weight, 2.2 parts by weight, 2.3 parts by weight, 2.4 parts by weight, 2.5 parts by weight, 2.6 parts by weight, 2.7 parts by weight, 2.8 parts by weight or 2.9 parts by weight, and specific points therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific points included in the range.

In a second aspect, the present invention provides a process for the preparation of a flame retardant latex according to the first aspect, said process comprising: the neoprene latex, a vulcanizing agent, an accelerator, a halogen flame retardant, an optional pH regulator, an optional surfactant, an optional antioxidant and an optional toner are mixed to obtain the flame retardant latex.

Preferably, the mixing time is 60-120 min, such as 65min, 70min, 75min, 80min, 85min, 90min, 95min, 100min, 105min, 110min or 115min, and the specific points between the above points are limited by space and for brevity, the invention is not exhaustive of the specific points included in the range.

Preferably, the method further comprises the steps of adding a thickening agent and standing after mixing.

Preferably, the time of standing is more than 12h, such as 13h, 14h, 15h, 16h, 17h, 18h, 19h or 20h, and the specific values therebetween are limited for space and simplicity, and the invention is not exhaustive.

In a third aspect, the present invention provides a flame retardant latex glove comprising the flame retardant latex of the first aspect and a glove core.

Preferably, the material of the glove core comprises polyimide fibers.

In a fourth aspect, the present invention provides a method of making a flame retardant latex glove as defined in the third aspect, said method comprising: dipping, coating anti-slip treatment, soaking and washing, and co-vulcanizing the glove core by using the flame-retardant latex of the first aspect to obtain the flame-retardant latex glove.

Compared with the prior art, the invention has the following beneficial effects:

according to the flame-retardant latex provided by the invention, chloroprene latex is selected as a matrix, and a halogen flame retardant in a specific part is added to prepare the flame-retardant latex with excellent high-temperature resistance and flame retardance; the flame-retardant latex gloves prepared by the flame-retardant latex and the glove cores together can achieve the effect of self-extinguishing in case of naked fire and can be used at the high temperature of 300 ℃, and particularly, the self-extinguishing time of the flame-retardant latex gloves is 0-4 s, the number of wear-resistant turns is 1500-2200, and the requirements on flame retardance and wear resistance of the flame-retardant latex gloves can be completely met.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

Examples 1 to 3

A flame-retardant latex was prepared as described in Table 1, wherein the conductive latexes of examples 1 to 3 had viscosities of 500 mPas, 1000 mPas and 2000 mPas, respectively, and the amounts of the respective components were expressed in "parts by weight".

TABLE 1

	Example 1	Example 2	Example 3
				Neoprene latex	80	70	90
Antimony-bromine composite flame retardant	25	10	40
				Sulfur	1	0.5	1.5
Zinc oxide	3	1.5	4.5
				Accelerator ZDC	1.5	1	3
Antioxidant 2246	1.8	1	2
				Sodium dodecyl benzene sulfonate	1.5	1	2
Thickening agent	8	7	9
				Toner	2.5	2	3

The preparation method of the flame-retardant latex provided in the embodiment 1 to 3 includes: chloroprene latex (Nippon Tosoh Co., Ltd., LA502), sulfur, zinc oxide, accelerator ZDC, antimony and bromine composite flame retardant (Namo plastic commercial Co., Ltd., FR-22, Shijiazhuang), potassium hydroxide, sodium dodecylbenzenesulfonate, antioxidant 2246 and toner (black pigment, (Jiangxi Sanyue New Material Co., Ltd., PH-960)) were mixed for 100min, and thickener (Jiangnan Xufa Kai chemical raw materials Co., Ltd., Japan, CMC) was added and allowed to stand for 720min to obtain the flame retardant latex.

Example 4

A flame-retardant latex which is different from the latex in the embodiment 1 in that the addition amount of the antimony-bromine composite flame retardant is 15 parts by weight, the addition amount of the chloroprene latex is 90 parts by weight, and other components, the use amounts and the preparation method are the same as those in the embodiment 1.

Example 5

A flame-retardant latex, which is different from the latex in example 1 in that the addition amount of the antimony-bromine composite flame retardant is 35 parts by weight, the addition amount of the chloroprene latex is 70 parts by weight, and other components, the use amounts and the preparation method are the same as those in example 1.

Example 6

A flame retardant latex, which is different from the latex of example 1 in that a brominated flame retardant (kaiki koku kokai ltd., KBE-2012) is used to replace the antimony-bromine composite flame retardant of example 1, and other components, use amounts and preparation methods are the same as those of example 1.

Comparative example 1

A flame-retardant latex, which is different from the latex in the embodiment 1 in that the addition amount of the antimony-bromine composite flame retardant is 5 parts by weight, the addition amount of the chloroprene latex is 100 parts by weight, and other components, the use amounts and the preparation method are the same as those in the embodiment 1.

Comparative example 2

A flame-retardant latex, which is different from the latex in the embodiment 1 in that the addition amount of the antimony-bromine composite flame retardant is 45 parts by weight, the addition amount of the chloroprene latex is 60 parts by weight, and other components, the use amounts and the preparation method are the same as those in the embodiment 1.

Comparative example 3

A flame retardant latex which differs from example 1 in that a natural rubber latex is used instead of the polychloroprene latex of example 1, and the other components, amounts and preparation methods are the same as those of example 1.

Application examples 1 to 6

A flame-retardant latex glove comprises the flame-retardant latex obtained in examples 1-6 and a glove core (Dongtai Weizhu knitwear factory, polyimide fiber);

the preparation method comprises the following steps: and (3) dipping the glove core by using the flame-retardant latex for 8s, performing coating slip-resistant treatment, soaking and washing for 40min, and jointly vulcanizing for 90min at 100 ℃ to obtain the flame-retardant latex glove.

Comparative application examples 1 to 3

A conductive latex glove comprises the flame-retardant latex obtained in comparative examples 1-3 and a glove core (Dongtai Weishu knitwear factory, polyimide fiber);

the preparation method is the same as the application example 1, and the flame-retardant latex glove is obtained. And (3) performance testing:

(1) self-extinguishing time: cutting a sample of 4cm multiplied by 6cm, clamping the sample by using a pair of tweezers, moving the sample to the position above the flame to burn, moving the sample which is burning out of the flame, and recording the self-extinguishing time of the sample after the sample is moved out of the flame;

(2) wear resistance: the test was carried out according to the abrasion resistance test in EN388:2016 protective gloves for protection against mechanical hazards.

The flame-retardant latex gloves obtained in application examples 1 to 6 and comparative application examples 1 to 3 were tested according to the test method, and the test results are shown in table 2:

TABLE 2

	Self-extinguishing time (seconds)	Abrasion resistance (number of turns)
			Application example 1	0.5	2000
Application example 2	4	2200
			Application example 3	0	1600
Application example 4	2	2100
			Application example 5	0	1500
Application example 6	1	2000
			Comparative application example 1	5	2300
Comparative application example 2	0	500
			Comparative application example 3	15	1000

As can be seen from the data in table 2:

the flame-retardant latex gloves provided by the invention have shorter self-extinguishing time, which shows that the gloves have better flame retardance; and has excellent wear resistance.

Specifically, the self-extinguishing time of the flame-retardant latex gloves obtained in the application examples 1-6 is 0-4 s, and the number of wear-resistant circles is 1500-2200; compared with the flame-retardant latex gloves obtained in the comparative application example 1, the self-extinguishing time is reduced, the wear resistance is greatly improved compared with the flame-retardant latex gloves obtained in the comparative application example 2, and the wear resistance and the self-extinguishing time of the flame-retardant latex gloves obtained in the comparative application example 3 are improved; the flame-retardant latex gloves prepared by the invention adopt the specific flame-retardant latex, the addition parts of the flame retardant and the chloroprene latex in the flame-retardant latex are controlled, the flame-retardant latex with both flame retardance and wear resistance meeting the requirements is prepared, and the flame-retardant latex gloves meeting the requirements are further obtained.

The applicant states that the present invention is illustrated by the above examples of a flame retardant latex and the preparation and application thereof, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must be implemented by relying on the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.