阅读说明：本技术 一种无卤高阻燃耐油热缩标识管及其生产方法 (Halogen-free high-flame-retardant oil-resistant thermal shrinkage identification tube and production method thereof ) 是由 陈韩江 黄昭政 王宇源 冯雪雁 张增果 康树峰 于 2020-03-25 设计创作，主要内容包括：本发明公开一种无卤高阻燃耐油热缩标识管及其生产方法,其制备材料,按重量计,包括以下组份：聚乙烯80-100重量份；乙烯-辛烯嵌断共聚物10-20重量份；乙烯-丙烯酸酯-马来酸酐三元共聚物5-15重量份；六角片状氢氧化镁30-60重量份；无卤复合阻燃剂30-60重量份；润滑剂1-5重量份；敏化交联剂0.5-3重量份；抗氧剂1-3.5重量份；色母0-10重量份。本发明标识管极限氧指数大于35％,阻燃性能能够达到法国NF C32-070标准C2级；耐油效果满足法国NF F00-608标准,在70℃、168h耐柴油后体积和拉伸强度的变化率小于30％,标识字符的耐油牢固性能达到EN 50343的标准。(The invention discloses a halogen-free high-flame-retardant oil-resistant thermal shrinkage identification tube and a production method thereof, and the preparation material comprises the following components by weight: 80-100 parts of polyethylene; 10-20 parts by weight of an ethylene-octene block copolymer; 5-15 parts of ethylene-acrylate-maleic anhydride terpolymer; 30-60 parts of hexagonal flaky magnesium hydroxide; 30-60 parts of halogen-free composite flame retardant; 1-5 parts of a lubricant; 0.5-3 parts of sensitizing crosslinking agent; 1-3.5 parts of antioxidant; 0-10 parts of color master batch. The limiting oxygen index of the marking tube is more than 35 percent, and the flame retardant property can reach French NF C32-070 standard C2 level; the oil-resistant effect meets the French NF F00-608 standard, the change rate of the volume and the tensile strength is less than 30 percent after diesel oil resistance at 70 ℃ for 168h, and the oil-resistant firm performance of the identification characters reaches the EN 50343 standard.)

1. The utility model provides a there is not steamed high fire-retardant resistant oily pyrocondensation sign pipe which characterized in that: the preparation material of the halogen-free high-flame-retardant oil-resistant heat-shrinkable label tube comprises the following components in parts by weight:

80-100 parts by weight of polyethylene, wherein the polyethylene is one or a mixture of a plurality of low density polyethylene, linear low density polyethylene and high density polyethylene;

10 to 20 parts by weight of an ethylene-octene block copolymerThe ethylene-octene block copolymer has a melt index of 0.5-5 g/10min and a density of 0.870-0.890 g/cm³；

5-15 parts of ethylene-acrylate-maleic anhydride terpolymer, wherein the ethylene-acrylate-maleic anhydride terpolymer contains 8-12% of butyl acrylate, 1.0-3.0% of maleic anhydride and has a melt index of 3-7 g/10 min;

30-60 parts by weight of hexagonal flaky magnesium hydroxide, wherein the purity of the hexagonal flaky magnesium hydroxide is more than 99.5%, the average particle size is less than 1.2 mu m, and the bulk density is 0.25g/cm³；

30-60 parts of a halogen-free composite flame retardant, wherein the halogen-free composite flame retardant is prepared by compounding aluminum hydroxide, melamine cyanurate and aluminum hypophosphite in a weight ratio of (1-4) to (1-3);

1-5 parts by weight of a lubricant, wherein the lubricant is one or more of zinc stearate, silicone or ethylene bis stearamide;

0.5-3 parts by weight of sensitizing crosslinking agent, wherein the sensitizing crosslinking agent is one or two of trimethylolpropane tri (methyl) acrylate and triallyl isocyanurate;

1-3.5 parts of antioxidant, wherein the antioxidant is a composite agent prepared by blending a hindered phenol main antioxidant, a thioether auxiliary antioxidant, a hindered amine auxiliary antioxidant and a metal ion resistant agent in a weight ratio of (1-4) to (1-3) to (1-2) to (0.5-1);

0-10 parts of color master batch.

2. The halogen-free high-flame-retardant oil-resistant heat-shrinkable label tube as claimed in claim 1, wherein: the hexagonal flaky magnesium hydroxide and the halogen-free composite flame retardant account for 35-43% of the total weight.

3. The method for producing halogen-free high-flame-retardant oil-resistant heat-shrinkable label tube according to claims 1 to 2, characterized by comprising the steps of:

(1) and (3) processing the master batch: firstly, adding the preparation material of the halogen-free high-flame-retardant oil-resistant heat-shrinkable label tube in the claim 1 or 2 into an internal mixer, controlling the temperature of the material within 130 +/-10 ℃, mixing for 8-12 minutes, then forcibly feeding the mixture through a double-screw extruder, extruding, drawing strips and air-cooling and granulating at the temperature of 100-160 ℃ to obtain master batch particles;

(2) extruding into a tube: extruding the granulated master batch particles out of a semi-finished product of the identification tube at the temperature of 100-160 ℃ by a single-screw extruder;

(3) an irradiation step: irradiating the semi-finished product of the identification tube by an electron accelerator or a cobalt source or an ultraviolet light source;

(4) expanding and cooling: expanding the irradiated marking tube semi-finished product by 2-3 times by using expansion equipment at the temperature of 100-160 ℃; and then cooling and shaping are carried out, thus obtaining the halogen-free high-flame-retardant oil-resistant heat-shrinkable label tube.

Technical Field

The invention relates to a halogen-free high-flame-retardant oil-resistant heat-shrinkable label tube and a production method thereof.

Background

The heat-shrinkable label sleeve is generally applied to wires and cables to have a marking effect, has excellent comprehensive properties such as light weight, scratch resistance and the like, has high cost performance, can realize large-batch stable production, is permanently and reliably marked, and the like, and is widely applied to electric line marks of trains, airplanes, ships, aerospace and the like. With the development of science and technology, machine equipment is required to operate in a severe environment, higher requirements are put on a heat-shrinkable label sleeve, and the reliability and identifiability are required to be improved in more severe conditions. The marks used by part of equipment can be contacted with some fuel oil more or less, and meanwhile, when a fire disaster occurs, the halogen-containing flame-retardant material can generate toxic gas and smoke, so that the smooth operation of disaster relief work is influenced, secondary disasters are easily caused, and the used heat-shrinkable mark sleeve is required to have halogen-free high flame-retardant and fuel oil resistant performances.

Compared with halogen flame retardant and halogen-free flame retardant, the halogen-free flame retardant has lower efficiency, and can achieve the corresponding flame retardant effect by adding more flame retardants, but the oil resistance of the material is seriously reduced, and the requirements of volume and tensile strength change retention rate after oil resistance in French NF F00-608 standard cannot be met.

Disclosure of Invention

The invention aims to provide a halogen-free high-flame-retardant oil-resistant heat-shrinkable label tube with excellent oil resistance, chemical corrosion resistance, long-term heat resistance and scratch resistance.

In order to achieve the purpose, the halogen-free high-flame-retardant oil-resistant thermal shrinkage identification tube provided by the invention comprises the following preparation materials in parts by weight: 80-100 parts by weight of polyethylene, wherein the polyethylene is one or a mixture of a plurality of low density polyethylene, linear low density polyethylene and high density polyethylene; ethylene-octene10-20 parts of block copolymer (POE), wherein the melt index of the ethylene-octene block copolymer (POE) is 0.5-5 g/10min, and the density is 0.870-0.890 g/cm³(ii) a 5-15 parts of ethylene-acrylate-maleic anhydride terpolymer (EMH), wherein the ethylene-acrylate-maleic anhydride terpolymer (EMH) has the butyl acrylate content of 8-12%, the maleic anhydride content of 1.0-3.0% and the melt index of 3-7 g/10 min; 30-60 parts by weight of hexagonal flaky magnesium hydroxide, wherein the purity of the hexagonal flaky magnesium hydroxide is more than 99.5%, the average particle size is less than 1.2 mu m, and the bulk density is 0.25g/cm³(ii) a 30-60 parts of a halogen-free composite flame retardant, wherein the halogen-free composite flame retardant is prepared by compounding aluminum hydroxide, melamine cyanurate and aluminum hypophosphite in a weight ratio of (1-4) to (1-3); 1-5 parts by weight of a lubricant, wherein the lubricant is one or more of zinc stearate, silicone or ethylene bis stearamide; 0.5-3 parts by weight of sensitizing crosslinking agent, wherein the sensitizing crosslinking agent is one or two of trimethylolpropane tri (methyl) acrylate and triallyl isocyanurate; 1-3.5 parts of antioxidant, wherein the antioxidant is a composite agent prepared by blending a hindered phenol main antioxidant, a thioether auxiliary antioxidant, a hindered amine auxiliary antioxidant and a metal ion resistant agent in a weight ratio of (1-4) to (1-3) to (1-2) to (0.5-1); 0-10 parts of color master batch.

Preferably, the hexagonal flaky magnesium hydroxide and the halogen-free composite flame retardant account for 35-43% of the total parts.

The invention also provides a production method of the halogen-free high-flame-retardant oil-resistant heat-shrinkable label tube, which comprises the following steps:

(1) and (3) processing the master batch: firstly, adding the preparation material of the halogen-free high-flame-retardant oil-resistant heat-shrinkable label tube into an internal mixer, controlling the temperature of the material within 130 +/-10 ℃, mixing for 8-12 minutes, then forcibly feeding the mixture, extruding, bracing and air-cooling and granulating at the temperature of 100 plus or minus 10 ℃ through a double-screw extruder to obtain master batch particles;

(2) extruding into a tube: extruding the granulated master batch particles out of a semi-finished product of the identification tube at the temperature of 100-160 ℃ by a single-screw extruder;

(3) an irradiation step: irradiating the semi-finished product of the identification tube by an electron accelerator or a cobalt source or an ultraviolet light source;

(4) expanding and cooling: expanding the irradiated marking tube semi-finished product by 2-3 times by using expansion equipment at the temperature of 100-160 ℃; and then cooling and shaping are carried out, thus obtaining the halogen-free high-flame-retardant oil-resistant heat-shrinkable label tube.

Compared with the prior art, the invention has the following advantages and effects:

the excellent performance of the magnesium hydroxide flame retardant comes from the appearance, size and dispersity of crystals of the magnesium hydroxide flame retardant, and the hexagonal flaky magnesium hydroxide has the characteristics of high decomposition temperature, good thermal stability and high-efficiency flame retardance in thermoplastic polymers due to the special structure, mechanical property and dispersity, and can reduce the addition amount when being used together with aluminum hydroxide, hypophosphite and other flame retardants.

The halogen-free high-flame-retardant oil-resistant heat-shrinkable label tube has an excellent flame-retardant effect, the limiting oxygen index is more than 35%, and the flame-retardant grade can reach French NF C32-070 standard C2 grade.

The halogen-free high-flame-retardant oil-resistant heat-shrinkable label tube has a good oil-resistant effect, the oil-resistant effect can meet the standard requirement of NF F00-608 in France, and the change rate of volume and tensile strength is less than 30% after diesel oil resistance is carried out for 168 hours at 70 ℃; the oil-resistant firm performance of the identification characters reaches the standard requirement of EN 50343, and simultaneously meets the ROHS environmental protection requirement.

Detailed Description

In order to explain the technical contents, formulation ratios, and objects and effects of the present invention in detail, the following description will be given in conjunction with the embodiments.

The halogen-free high-flame-retardant oil-resistant thermal shrinkage identification tube comprises the following preparation materials in parts by weight: 80-100 parts of polyethylene, 10-20 parts of ethylene-octene block copolymer, 5-15 parts of ethylene-acrylate-maleic anhydride terpolymer, 30-60 parts of hexagonal sheet magnesium hydroxide, 30-60 parts of halogen-free composite flame retardant, 1-5 parts of lubricant, 0.5-3 parts of sensitizing crosslinking agent, 1-3.5 parts of antioxidant and 0-10 parts of color master batch.

In the embodiment of the invention, the polyethylene is one or a blend of several of low density polyethylene, linear low density polyethylene and high density polyethylene.

In the embodiment of the invention, the ethylene-octene block copolymer has a melt index of 0.5-5 g/10min and a density of 0.870-0.890 g/cm³。

In the embodiment of the invention, the ethylene-acrylate-maleic anhydride terpolymer has 8-12% of butyl acrylate, 1.0-3.0% of maleic anhydride and a melt index of 3-7 g/10 min.

In the embodiment of the invention, the purity of the hexagonal flaky magnesium hydroxide is more than 99.5 percent, the average particle size is less than 1.2 mu m, and the bulk density is 0.25g/cm³。

In the embodiment of the invention, the halogen-free composite flame retardant is prepared by compounding aluminum hydroxide, melamine cyanurate and aluminum hypophosphite in the weight ratio of (1-4) to (1-3).

In the embodiment of the invention, the lubricant is one or more of zinc stearate, silicone or ethylene bis stearamide.

In the embodiment of the invention, the sensitizing crosslinking agent is one or two of trimethylolpropane tri (meth) acrylate and triallyl isocyanurate.

In the embodiment of the invention, the antioxidant is a composite agent prepared by blending a hindered phenol main antioxidant, a thioether auxiliary antioxidant, a hindered amine auxiliary antioxidant and a metal ion resisting agent in the weight ratio of (1-4) to (1-3) to (1-2) to (0.5-1).

The invention relates to a production method of a halogen-free high-flame-retardant oil-resistant heat-shrinkable label tube, which comprises the following steps:

(1) and (3) processing the master batch: firstly, adding the preparation material of the halogen-free high-flame-retardant oil-resistant heat-shrinkable label tube into an internal mixer, controlling the temperature of the material within 130 +/-10 ℃, mixing for 8-12 minutes, then forcibly feeding the mixture, extruding, bracing and air-cooling and granulating at the temperature of 100 plus or minus 10 ℃ through a double-screw extruder to obtain master batch particles;

(2) extruding into a tube: extruding the granulated master batch particles out of a semi-finished product of the identification tube at the temperature of 100-160 ℃ by a single-screw extruder;

(3) an irradiation step: irradiating the semi-finished product of the identification tube by an electron accelerator or a cobalt source or an ultraviolet light source;

(4) expanding and cooling: expanding the irradiated marking tube semi-finished product by 2-3 times by using expansion equipment at the temperature of 100-160 ℃; and then cooling and shaping are carried out, thus obtaining the halogen-free high-flame-retardant oil-resistant heat-shrinkable label tube.

In order to study the formulation of the above materials, the following experiments were conducted (the number of experiments is large, and in many examples, the following examples and the reference to the examples are used to prove the feasibility and superiority of the formulation).

Several specific examples and comparative examples of this embodiment of the invention are set forth below, all parts being by weight unless otherwise indicated:

TABLE 1

TABLE 1 continuation

^＊Comparative example 1 formulation was made by adding 40 parts of ordinary random magnesium hydroxide

The components in examples 1 to 16 and comparative examples 1 to 4 in table 1 are respectively produced according to the above production method of the halogen-free high-flame-retardant oil-resistant heat-shrinkable label tube to obtain the halogen-free high-flame-retardant oil-resistant heat-shrinkable label tube.

The thermal shrinkage marking tubes were measured respectively, and the test results are shown in table 2.

TABLE 2

Test results for examples 1-16: the limit oxygen index is more than 35 percent, and the flame retardant property can reach French NF C32-070 standard C2 grade; has excellent oil-resistant effect, the performance meets the French NF F00-608 standard, the change rate of the volume and the tensile strength is less than 30 percent after diesel oil resistance is carried out for 168 hours at 70 ℃, the oil-resistant firm performance of the identification character meets the standard requirement of EN 50343, and simultaneously, the ROHS environmental protection requirement is met

In the comparative example 1, the common irregular magnesium hydroxide is used, in the comparative example 2, the amount of the hexagonal flaky magnesium hydroxide is reduced, in the comparative example 3, the proportion of the amount of the flame retardant is reduced, and the flame retardant effect can not meet the standard requirement; in comparative example 4, the proportion of the flame retardant is too large, and although the flame retardant performance is improved, the liquid resistance of the material cannot meet the standard requirement.

In conclusion, the halogen-free high-flame-retardant oil-resistant heat-shrinkable label tube is prepared by optimizing the flame-retardant system, and the application range and the field of the product are favorably expanded.

The present invention is not limited to the above-described embodiments, and various changes may be made by those skilled in the art, which changes are equivalent or similar to the present invention and are intended to be included within the scope of the appended claims.