阅读说明：本技术 一种外被料及其制备方法和应用 (External coating material and preparation method and application thereof ) 是由 肖崇 田建军 詹敏 郑东升 何强 于 2020-12-30 设计创作，主要内容包括：本发明涉及一种外被料及其制备方法和应用,所述外被料按照重量份数包括如下组分：氢化苯乙烯-异戊二烯-乙烯支化异戊二烯-苯乙烯树脂30-50重量份；聚对苯二甲酸丁二醇酯5-10重量份；聚丙烯5-20重量份；助剂20-70重量份。本发明在外被料配方中同时引入氢化苯乙烯-异戊二烯-乙烯支化异戊二烯-苯乙烯树脂和聚对苯二甲酸丁二醇酯,且与配方中其他组分按照特定的比例搭配,能够使得到的外被料具有超柔软、耐刮、手感细腻、干爽和耐化学品的特点。并且,本发明采用的原料为环保无毒原料,可回收再利用率高,生产方式清洁高效,对环境无污染。(The invention relates to an external coating material and a preparation method and application thereof, wherein the external coating material comprises the following components in parts by weight: 30-50 parts by weight of hydrogenated styrene-isoprene-ethylene branched isoprene-styrene resin; 5-10 parts of polybutylene terephthalate; 5-20 parts of polypropylene; 20-70 parts of an auxiliary agent. According to the invention, the hydrogenated styrene-isoprene-ethylene branched isoprene-styrene resin and the polybutylene terephthalate are simultaneously introduced into the formula of the outer covering material and are matched with other components in the formula according to a specific proportion, so that the obtained outer covering material has the characteristics of super softness, scratch resistance, fine hand feeling, dryness and chemical resistance. In addition, the raw materials adopted by the invention are environment-friendly and nontoxic, the recycling rate is high, the production mode is clean and efficient, and the environment is not polluted.)

1. The outer coating material is characterized by comprising the following components in parts by weight:

2. the coating according to claim 1, wherein the hydrogenated styrene-isoprene-ethylene branched isoprene-styrene resin has a weight average molecular weight of 150000-250000.

3. The precoat according to claim 1, wherein the polybutylene terephthalate has a viscosity of 1.0 to 1.3 dl/g.

4. The outercover of claim 1, wherein the polypropylene comprises a co-polypropylene having a melt index of 3 to 15g/10min at a temperature of 230 ℃ and a weight of 2.16 kilograms.

5. The topcoat material of claim 1, wherein the adjuvant comprises any one or a combination of at least two of a plasticizer, a filler, an antioxidant, or a lubricant.

6. The overmold of claim 5, wherein said plasticizer comprises white oil;

and/or, the filler comprises calcium carbonate;

and/or the antioxidant comprises n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate;

and/or, the lubricant comprises a silicone masterbatch.

7. The overcoating material according to claim 6, characterized in that said calcium carbonate has a particle size of 2500 mesh to 5000 mesh.

8. The coating according to any one of claims 1 to 7, comprising the following components in parts by weight:

9. a method of preparing a coating according to any one of claims 1 to 8, comprising the steps of:

taking the raw material components according to the corresponding weight parts;

and mixing the raw material components, extruding and plasticizing to obtain the coating material.

10. Use of a coating according to any one of claims 1 to 8 in the manufacture of an earphone cord or a cable cord.

Technical Field

The invention relates to the technical field of high polymer materials, in particular to an outer coating material and a preparation method and application thereof.

Background

With the increasing demands of people on life, the quality requirements of products contacting with human bodies are higher and higher, for example, earphones frequently contacting with human bodies are expected to resist cosmetics when being required to have performances such as smoothness, fineness and the like, and are very soft and easy to store, but the earphone outer covering material in the prior art is difficult to combine the performances such as smoothness, fineness, softness, scratch resistance, chemical resistance and the like.

Therefore, the development of an outer coating material with the characteristics of super softness, scratch resistance, fine hand feeling, dryness, chemical corrosion resistance and the like is urgently needed in the field.

Disclosure of Invention

The invention aims to provide an outer covering material, in particular to an earphone wire outer covering material, and particularly provides an ultra-soft cosmetic earphone wire outer covering material which has the characteristics of ultra-softness, scratch resistance, fine hand feeling, dryness and chemical corrosion resistance.

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

the invention provides an outer quilt material which comprises the following components in parts by weight:

in the present invention, the hydrogenated styrene-isoprene-ethylene branched isoprene-styrene resin is added in an amount of 30 to 50 parts by weight, for example, 32 parts by weight, 34 parts by weight, 36 parts by weight, 38 parts by weight, 40 parts by weight, 42 parts by weight, 44 parts by weight, 46 parts by weight, 48 parts by weight, etc.; the polybutylene terephthalate is added in an amount of 5 to 10 parts by weight, for example, 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, 7 parts by weight, 7.5 parts by weight, 8 parts by weight, 8.5 parts by weight, 9 parts by weight, 9.5 parts by weight, or the like; the polypropylene is added in an amount of 5 to 20 parts by weight, for example, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, or the like; the addition amount of the auxiliary is 20 to 70 parts by weight, for example, 22 parts by weight, 24 parts by weight, 26 parts by weight, 28 parts by weight, 30 parts by weight, 32 parts by weight, 34 parts by weight, 36 parts by weight, 38 parts by weight, 40 parts by weight, 42 parts by weight, 44 parts by weight, 46 parts by weight, 48 parts by weight, 50 parts by weight, 52 parts by weight, 54 parts by weight, 56 parts by weight, 58 parts by weight, 60 parts by weight, 62 parts by weight, 64 parts by weight, 66 parts by weight, 68 parts by weight, and the like.

In consideration of the defects of the earphone line outer coating in the prior art, the invention uses hydrogenated styrene-isoprene-ethylene branched isoprene-styrene resin for modification to replace the traditional hydrogenated styrene-butadiene-styrene resin (SEBS), has good compatibility with polybutylene terephthalate, has blocked displacement between molecular branches due to the special structure of the hydrogenated styrene-isoprene-ethylene branched isoprene-styrene resin, is difficult to rebound in macroscopic representation, endows the product with low elasticity, has good softness due to good oil absorption, introduces polybutylene terephthalate for modification, endows the product with good cosmetic corrosion resistance, scratch resistance and dry performance, and develops the ultra-soft cosmetic-resistant earphone line outer coating, the product has the characteristics of super softness, scratch resistance, fine hand feeling, dryness and chemical corrosion resistance. In addition, the raw materials adopted by the invention are environment-friendly and nontoxic, the recycling rate is high, the production mode is clean and efficient, and the environment is not polluted.

The contents of the components in the outer covering material provided by the invention can be controlled within the above ranges, so that the outer covering material can be matched with each other to realize the effects of super softness, scratch resistance, fine hand feeling, dryness and chemical corrosion resistance. Wherein, if the addition amount of the hydrogenated styrene-isoprene-ethylene branched isoprene-styrene resin is too large, the processing is difficult, and the surface of the formed coating material is rough; if the amount of polybutylene terephthalate added is too large, the overall hardness of the coating material will be too high, and the effect of ultra-softness will be lost.

Preferably, the coating does not contain a hydrogenated styrene-butadiene-styrene resin.

Preferably, the hydrogenated styrene-isoprene-ethylene branched isoprene-styrene resin has a weight average molecular weight of 150000-250000, such as 160000, 170000, 180000, 190000, 200000, 210000, 220000, 230000, 240000 and the like. According to the invention, the weight average molecular weight of the hydrogenated styrene-isoprene-ethylene branched isoprene-styrene resin is preferably in the range, so that the hydrogenated styrene-isoprene-ethylene branched isoprene-styrene resin can be better compatible with polybutylene terephthalate and polypropylene, and the softness, scratch resistance, fineness, dryness and chemical corrosion resistance of the outer covering material are further improved.

The hydrogenated styrene-isoprene-ethylene branched isoprene-styrene resin of the present invention is a substance existing in the art, and can be prepared by a method conventional in the art, or can be commercially obtained.

Preferably, the polybutylene terephthalate has a viscosity of 1.0 to 1.3dl/g, such as 1.05dl/g, 1.1dl/g, 1.15dl/g, 1.2dl/g, 1.25dl/g, 1.28dl/g, and the like. According to the invention, the viscosity of the polybutylene terephthalate is preferably in the range, so that the polybutylene terephthalate can be better compatible with the hydrogenated styrene-isoprene-ethylene branched isoprene-styrene resin and polypropylene, and the softness, scratch resistance, fineness, dryness and chemical corrosion resistance of the coating are further improved.

Preferably, the polypropylene comprises a copolymer polypropylene having a melt index of 3 to 15g/10min (e.g., 4g/10min, 5g/10min, 6g/10min, 7g/10min, 8g/10min, 9g/10min, etc.) at a temperature of 230 ℃ and a weight of 2.16 kg.

Preferably, the auxiliary agent comprises any one or a combination of at least two of a plasticizer, a filler, an antioxidant or a lubricant.

Preferably, the plasticizer comprises white oil.

Preferably, the plasticizer has a kinematic viscosity of 150-500mm at 25 ℃²S, e.g. 160mm²/s、180mm²/s、200mm²/s、220mm²/s、240mm²/s、260mm²/s、280mm²/s、300mm²/s、320mm²/s、340mm²/s、360mm²/s、380mm²/s、400mm²/s、420mm²/s、440mm²/s、460mm²/s、480mm²And/s, etc.

Preferably, the filler comprises calcium carbonate, preferably ground calcium carbonate.

Preferably, the calcium carbonate has a particle size of 2500 mesh to 5000 mesh, for example 2600 mesh, 2800 mesh, 3000 mesh, 3200 mesh, 3400 mesh, 3600 mesh, 3800 mesh, 4000 mesh, 4200 mesh, 4400 mesh, 4600 mesh, 4800 mesh, and the like.

Preferably, the antioxidant comprises n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.

Preferably, the lubricant comprises a silicone masterbatch.

Preferably, the silicone master batch contains silicone 60% to 80% by mass, for example, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, and the like.

Preferably, the silicone base particle has a silica content of 20% to 40% by mass, for example, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, etc.

Preferably, the coating material comprises the following components in parts by weight:

according to the invention, the components in the outer covering material are preferably compounded according to the proportion, so that the softness, the scratch resistance, the fineness, the dryness and the chemical corrosion resistance of the outer covering material are further improved.

In the above formulation, the plasticizer is added in an amount of 20 to 50 parts by weight, for example, 22 parts by weight, 24 parts by weight, 26 parts by weight, 28 parts by weight, 30 parts by weight, 32 parts by weight, 34 parts by weight, 36 parts by weight, 38 parts by weight, 40 parts by weight, 42 parts by weight, 44 parts by weight, 46 parts by weight, 48 parts by weight, and the like.

The second purpose of the invention is to provide a preparation method of the coating material, which comprises the following steps:

taking the raw material components according to the corresponding weight parts;

and mixing the raw material components, extruding and plasticizing to obtain the coating material.

Preferably, the mixing is for a time of 15 to 30min, such as 16min, 17min, 18min, 19min, 20min, 21min, 22min, 23min, 24min, 25min, 26min, 27min, 28min, 29min, etc., at a rate of 20 rpm to 40 rpm, such as 22 rpm, 24 rpm, 26 rpm, 28 rpm, 30 rpm, 32 rpm, 34 rpm, 36 rpm, 38 rpm, etc.

Preferably, the extrusion plasticization is performed in a twin-screw extruder.

Preferably, the feed diameter of the twin-screw extruder is 65 mm.

Preferably, the temperature for extrusion plasticizing is 180-210 ℃, such as 182 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃, 208 ℃ and the like.

Preferably, the preparation method further comprises: and after the extrusion plasticizing, carrying out bracing water cooling, air cooling, grain cutting and packaging.

Preferably, the preparation method specifically comprises the following steps:

mixing hydrogenated styrene-isoprene-ethylene branched isoprene-styrene resin, polybutylene terephthalate, polypropylene and an auxiliary agent according to the formula ratio for 15-30min, extruding and plasticizing at the temperature of 180-210 ℃ in a double-screw extruder with the feeding diameter of 65mm, and performing bracing water cooling, air cooling, grain cutting and packaging to obtain the coating material.

The invention also aims to provide the application of the coating material in preparing earphone wires or cable wires.

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

according to the invention, the hydrogenated styrene-isoprene-ethylene branched isoprene-styrene resin and the polybutylene terephthalate are simultaneously introduced into the formula of the outer covering material and are matched with other components in the formula according to a specific proportion, so that the obtained outer covering material has the characteristics of super softness, scratch resistance, fine hand feeling, dryness and chemical corrosion resistance. In addition, the raw materials adopted by the invention are environment-friendly and nontoxic, the recycling rate is high, the production mode is clean and efficient, and the environment is not polluted.

The outer covering material provided by the invention has the advantages of tensile strength of 6.3-7.2Mpa, elongation at break of 493-568%, Shore hardness of 65-67A, no surface abnormality after chemical corrosion resistance test, and stiffness of 62-76 TSU.

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.

The following examples and comparative examples use the following raw materials with the following detailed information:

examples 1 to 6 and comparative examples 1 to 6

The above examples and comparative examples each provide an outer coating material, and the specific formulation is detailed in table 1.

The preparation methods of the overcoats provided in the above examples and comparative examples are as follows:

(1) adding the substances in the formula shown in Table 1 into a 300L stirring pot, and mixing at low speed for 20min in the stirring pot;

(2) discharging the mixed raw materials obtained in the step (1) to a twin-screw machine with the diameter of 65mm, and extruding and plasticizing at the temperature of 200 ℃;

(3) and (3) carrying out bracing water cooling, air cooling, grain cutting and packaging on the extruded and plasticized rubber material through a double-screw eye die to obtain the outer quilt material.

Performance testing

The following performance tests were performed on the overcoats provided in the above examples and comparative examples:

(1) tensile strength and elongation at break properties were tested according to ASTM D412;

(2) hardness testing was according to ASTM D2240;

(3) chemical corrosion resistance test, test conditions: forming colloidal particles into a color plate with the specification of 100mm multiplied by 60mm multiplied by 2mm, wiping the surface of the color plate clean by cotton cloth, uniformly coating vaseline hand cream on the surface of the color plate, placing the color plate in a constant-temperature constant-humidity box (the temperature is 65 ℃ and the humidity is 95%), taking out the color plate after placing for 24 hours, wiping the surface of the color plate clean by the cotton cloth, and observing whether abnormal phenomena such as discoloration, bubbles, spots, peeling, corrosion, serious yellowing and the like exist;

(4) softness test, test conditions: extruding the processed rubber material to form an earphone cord quilt with the diameter of 1.8mm, and then testing the softness of the rubber material by a TABER stiffness tester, wherein the lower the testing value is, the better the softness is.

The results of the above performance tests are shown in table 1.

TABLE 1

As can be seen from Table 1, the external coating material provided by the invention can show the characteristics of super softness, scratch resistance, fine hand feeling, dryness and chemical corrosion resistance by adding a specific amount of hydrogenated styrene-isoprene-ethylene branched isoprene-styrene resin and polybutylene terephthalate, and has better mechanical properties. Wherein the tensile strength is 6.3-7.2Mpa, the elongation at break is 493-568%, the Shore hardness is 65-67A, the surface is free from abnormality after chemical corrosion resistance test, and the stiffness is 62-76 TSU.

In comparative example 3, the addition amount of the hydrogenated styrene-isoprene-ethylene branched isoprene-styrene resin is less than 30 parts, oil is difficult to lock, the wire is easy to produce oil, the hand feeling is sticky and not smooth, and the tensile strength and the elongation at break are obviously poorer than those of the example; in comparative example 4, the amount of the hydrogenated styrene-isoprene-ethylene branched isoprene-styrene resin added was more than 50 parts, and the resulting composition was difficult to process, poor in plasticization, rough in wire appearance, non-slippery, and significantly deteriorated in tensile strength and elongation at break as compared with those of examples.

In comparative example 5, the addition amount of polybutylene terephthalate is less than 5 parts, the chemical resistance is poor, and the surface yellowing phenomenon appears in the test; comparative example 6, in which the amount of polybutylene terephthalate added was more than 10 parts, was not well dispersed, was easily delaminated, and the tensile strength and elongation at break of the wire were low, and the wire was easily cracked.

It is understood from comparison of examples 3 and 6 that the addition of SEBS to the coating material (example 6) significantly reduces the tensile strength and elongation at break, and also causes difficulties in processing, poor plasticization, a rough wire appearance, and non-smoothness.

The present invention is illustrated in detail by the examples described above, but the present invention is not limited to the details described above, i.e., it is not intended that the present invention be implemented by relying on the details described above. 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.