CN109852043B - Nylon material special for magic tape and preparation method thereof - Google Patents

Abstract

The invention provides a nylon material special for a magic tape and a preparation method thereof, and the nylon material special for the magic tape comprises the following components in percentage by weight: 67-88% of polyamide, 10-25% of toughening agent, 0.3-1% of dendritic polymer, 0.1-3% of nucleating agent, 0.5-5% of release agent, 0.2-1% of antioxidant and 0-3% of other auxiliary agents, wherein the toughening agent is polyolefin containing polar branched chains. The nylon material special for the magic tape adopts a toughening system which has little influence on the crystallization rate of polyamide; the polyamide is quickly crystallized at a higher temperature under the action of the nucleating agent, and is suitable for preparing nylon magic tapes in an extrusion/molding mode; under the dual function of release agent, can guarantee that the material is at smooth drawing of patterns of extrusion calendering molding in-process, to the mould adhesion not, the hook is not split in the magic subsides ejection hook, does not draw the wound, and drawing of patterns is small in noise, and the nylon magic subsides of preparation have excellent cold resistance, heat resistance, and the appearance is pleasing to the eye and durable.

Description

Nylon material special for magic tape and preparation method thereof

Technical Field

The invention relates to the field of nylon materials, in particular to a nylon material special for a magic tape and a preparation method thereof.

Background

The magic tape, also called as a fastening tape, is composed of a hook surface and a hair surface, commonly used materials are nylon and polypropylene, and the traditional magic tape is formed by weaving or weaving. For example, patent CN1393189A discloses a method for manufacturing a fastening tape, which comprises the steps of firstly, performing water-proof treatment on the surface of nylon filaments by using a water-proof agent, and then, drying and burning; then, polyurethane resin is adopted to coat, spray or soak the surface of the waterproof layer, and a water pressure resistant layer is formed; finally, the treated nylon yarn is woven into a plurality of annular bodies arranged at equal intervals, and the annular bodies are cut into hook-shaped buckle ends on the proper side. The method for preparing the fastening tape has the advantages of complex process and low production efficiency, and the produced fastening tape has poor low-temperature resistance and can be hardened below minus 10 ℃ and cannot be used.

At present, the hook surface of the novel magic tape can be formed by extrusion/molding, which can greatly reduce the production cost and improve the performance and aesthetic feeling of the magic tape. For example, patent CN101596034A discloses a process for producing a plastic hook sheet fastening tape by extrusion/molding, which comprises melting and extruding toughened nylon through an extruder, forming a continuous sheet through a smooth sheet mold, feeding the continuous sheet into a traction mechanism, rolling hook teeth through a tooth making roller, then rolling and shaping through a flat pressing roller, and finally cutting into fastening tape products through a splitting machine. The method can complete the manufacture of the magic tape at one time through mechanization, and the produced magic tape can be normally used under the cold or high temperature condition of-40 ℃ to 40 ℃, and has long service life and high production efficiency. However, in the magic tape production process by adopting the extrusion/molding method, the phenomenon that the crystallization behavior of the material is influenced due to the addition of the amorphous toughening agent is found to be long in material forming period and poor in demolding property, so that the demolding noise is high if the material is light, the yield of finished products is influenced if a small amount of hook teeth are dragged, deformed or broken in a mold, the mold is adhered if the material is heavy, the normal production cannot be realized, and the influence is larger if the vitrification temperature of the amorphous toughening agent is lower.

Most of the existing reports on the preparation of the magic tape are focused on the design of a mold, and the development of material design is only rarely related. Therefore, when the nylon material with the toughened and modified is used for preparing the magic tape by adopting an extrusion/molding method, the problem that the crystallization behavior and the demolding property of the material are affected and deteriorated by the amorphous toughening agent exists, so that the application of the nylon material with the toughened and modified in the extrusion/molding magic tape is limited, and how to solve the problem is always the appeal of the industry.

Disclosure of Invention

In order to solve the technical problems, the invention provides a nylon material special for a magic tape and a preparation method thereof, wherein the nylon material special for the magic tape comprises the following components in percentage by weight:

polyamide: 67% -88%;

a toughening agent: 10% -25%;

dendritic polyester: 0.3 to 1 percent

Nucleating agent: 0.1% -3%;

releasing agent: 0.5% -5%;

antioxidant: 0.2% -1%;

other auxiliary agents: 0 to 3 percent.

Wherein the toughening agent is polyolefin containing polar branched chains.

Further, the polyamide is at least one of nylon 6, nylon 66 and nylon 6/nylon 66 copolymer; the relative viscosity of the polyamide is 2.0-3.0.

Further, the toughening agent is at least one of ethylene-octene copolymer grafted maleic anhydride (POE-g-MAH), ethylene propylene diene monomer grafted maleic anhydride (EPDM-g-MAH), polypropylene grafted maleic anhydride (PP-g-MAH), polyethylene grafted maleic anhydride (PE-g-MAH), linear low density polyethylene grafted maleic anhydride (LLDPE-g-MAH) and hydrogenated styrene-butadiene-styrene block copolymer grafted maleic anhydride (SEBS-g-MAH).

Further, the toughening agent is a composition of ethylene-octene copolymer grafted maleic anhydride (POE-g-MAH), ethylene propylene diene monomer grafted maleic anhydride (EPDM-g-MAH), polyethylene grafted maleic anhydride (PE-g-MAH) and linear low density polyethylene grafted maleic anhydride (LLDPE-g-MAH).

Further, the dendritic polymer is a specially functionalized polymer; preferably Waishan original CYD-701 series and Guangzhou Jianda HL-10 series.

Further, the nucleating agent is at least one of an inorganic nucleating agent and an organic nucleating agent.

Further, the inorganic nucleating agent is at least one of talcum powder, calcium carbonate, montmorillonite, alumina, kaolin, silicon dioxide, graphite, zinc fluoride and calcium fluoride; the organic nucleating agent is at least one of benzoic acid, alkali metal, alkaline earth metal or ammonium salt of benzoic acid, fatty carboxylic acid metal soap, dibenzylidene sorbitol and derivatives thereof, aromatic carboxylate, montanate and organic phosphate.

Further, the release agent is at least one of an inorganic release agent, an organic release agent and a high polymer release agent.

Further, the inorganic release agent is at least one of talcum powder and mica powder; the organic release agent is at least one of fatty acid, fatty acid ester, fatty acid alcohol, fatty acid amide, fatty acid soap and paraffin; the high polymer release agent is at least one of organic silicon, PE wax, polyethylene glycol and fluoropolymer.

Further, the antioxidant is at least one of hindered phenols, hindered amines, thioesters, phosphites and composite antioxidants.

Further, the other auxiliary agent is at least one of an antistatic agent, a coupling agent, a heat stabilizer, a lubricant, an anti-hydrolysis agent, a plasticizer and a pigment.

The invention provides a preparation method of the nylon material special for the magic tape, which comprises the following steps:

step 1, adding a toughening agent, a dendritic polymer, a nucleating agent, a release agent, an antioxidant and other auxiliaries into a high-speed stirrer in proportion, and uniformly stirring to prepare a premix;

and 2, adding the premix and the polyamide resin obtained in the step 1 from a main feeding weight loss type metering scale of a double-screw extruder, melting and extruding material strips by using the double-screw extruder, cooling by using a cooling water tank and drying by using an air dryer, and cutting and granulating by using a granulator to obtain the nylon material special for the magic tape.

Further, the processing temperature of each zone of the twin-screw extruder is set as follows: the first zone is 150-.

The invention provides a nylon material special for magic tapes, and provides a nylon modified material which solves the problem that the crystallization behavior and the demoulding property of the material are affected and deteriorated by an amorphous toughening agent in the preparation of the nylon magic tapes by an extrusion/molding mode.

The nylon material special for the magic tape has small influence of a toughening system on the polyamide crystallization rate, can realize rapid crystallization at higher temperature under the action of the nucleating agent, is particularly suitable for the nylon magic tape prepared by adopting an extrusion/molding mode, can ensure smooth demolding of the material in the extrusion calendaring molding process under the dual action of the demolding agent, has no adhesion to a mold, does not break and pull a hook ejected by the magic tape, has small demolding noise, and has excellent cold resistance, heat resistance, attractive appearance and durability. In addition, the dendritic polymer is added into the components, so that the fluidity of nylon can be improved, the regular arrangement and crystallization of molecular chains of the nylon are facilitated, and meanwhile, the problem that the manufactured magic tape is easy to dirty and glue dust when exposed outside for a long time is found because the polyolefin toughening agent with the polar branched chain is introduced in a large proportion, and the influence of the polar branched chain on the toughening agent on the surface energy of the material can be shielded by adding the dendritic polymer, so that the surface energy is reduced, and the degree that the manufactured magic tape is easy to dirty and glue dust is reduced to a great extent.

Drawings

FIG. 1 is a DSC thermogram of example 1;

FIG. 2 is a DSC thermogram of example 2;

FIG. 3 is a DSC thermogram of example 3;

FIG. 4 is a DSC profile of example 4;

FIG. 5 is a DSC analysis map of comparative example 1;

FIG. 6 is a DSC analysis map of comparative example 2;

FIG. 7 is a DSC analysis map of comparative example 3;

FIG. 8 is a DSC analysis map of comparative example 4;

FIG. 9 is a standard graph of the ash adhesion rating.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

It should be noted that the examples are intended to illustrate the present invention and should not be construed as limiting the present invention, and the examples do not indicate any particular technique or condition, and are performed according to the techniques or conditions described in the literature in the art or according to the product specification, and the reagents or apparatuses used are not indicated by the manufacturer, and are all conventional products commercially available.

In the embodiment of the invention, the raw materials are noted as follows:

polyamide:

PA6 η ═ 2.4, xinemeda M2400;

PA6 η ═ 2.8, miln SC 28;

PA6, η ═ 3.3, miln SM 33.

A toughening agent:

POE-g-MAH: easy to use 5805L;

PP-g-MAH: easy CMG 9801;

PE-g-MAH: dupont E100;

EPDM-g-MAH: dupont N416.

Nucleating agent:

organic and inorganic compound nucleating agent: brungelmann P22;

inorganic nucleating agent: montmorillonite, Zhejiang Fenghong DK 4;

organic nucleating agent: calcium montanate, colaine CAV102, dibenzylidene sorbitol and its derivatives, Millad 3988.

Dendritic polymer: wehaichen Source CYD-701 series.

Releasing agent: talcum powder, white oil, calcium stearate, pentaerythritol stearate and silicone.

Antioxidant: n, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine.

The invention provides the raw material proportions (in percentage by weight) of the following examples 1-4 shown in the table 1:

TABLE 1

Components	Example 1	Example 2	Example 3	Example 4
					Polyamide	67％	74.7％	79.7％	88％
Toughening agent	25％	20％	15％	10％
					Dendritic polymers	1％	0.8％	0.8％	0.5％
Nucleating agent	3％	1％	0.8％	0.1％
					Release agent
	1％	2.5％	3％	0.5％
					Antioxidant agent	1％	0.5％	0.5％	0.4％
Other auxiliaries	2％	0.5％	0.2％	0.5％

Wherein, the polyamide of the embodiment 1 is selected from PA6, eta is 2.4, Xinhui Meida M2400; the toughening agent is preferably 5805L; the dendritic polymer is CYD-701D; the nucleating agent is montmorillonite; the release agent is talcum powder; the antioxidant is N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine; other additives include 0.5% antistatic agent, 0.5% coupling agent and 1% heat stabilizer.

The polyamide of the embodiment 2 is selected from PA6, eta is 2.8, and middle school SC 28; the toughening agent is selected from 10% of easily-accessible CMG9801 and 10% of Dupont E100; the dendritic polymer is CYD-701M; the nucleating agent is Bruggeman P22; 2 percent of white oil and 0.5 percent of calcium stearate are selected as the release agent; the antioxidant is N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine; other adjuvants include 0.1% anti-hydrolysis agent, 0.2% coupling agent and 0.2% plasticizer.

The polyamide of the embodiment 3 is selected from PA6, eta is 2.8, and middle school SC 28; the toughening agent is DuPont E100; the dendritic polymer is CYD-701D; the nucleating agent is calcium montanate CAV 102; the release agent is calcium stearate; the antioxidant is N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine; other adjuvants include 0.1% coupling agent and 0.1% lubricant.

The polyamide of the embodiment 4 is selected from PA6, eta is 2.4, Xinhui Mei is M2400; the toughening agent is DuPont N416; the dendritic polymer is CYD-701D; the nucleating agent is calcium montanate CAV 102; the release agent is selected from silicone powder; the antioxidant is N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine; other adjuvants include 0.2% hydrolysis resistance agent, 0.1% plasticizer and 0.2% pigment.

The invention also provides the raw material proportions (the components are calculated by weight percent) of comparative examples 1-4 shown in the table 2:

TABLE 2

Wherein the polyamide of comparative example 1 is selected from: PA6, η 2.4, xinhuidi M2400; the release agent is selected from: 1% of white oil and 0.5% of calcium stearate; the antioxidant is selected from: n, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine; other adjuvants include: 0.1% of antistatic agent, 0.2% of coupling agent and 0.1% of heat stabilizer.

Comparative example 2 the polyamide was selected from: PA6, η ═ 3.3, miln SM 33; the toughening agent is selected from: dupont 5805L; the nucleating agent is selected from: montmorillonite; the release agent is selected from: calcium stearate; the antioxidant is selected from: n, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine; other adjuvants include: 0.1% of hydrolysis resistant agent, 0.2% of coupling agent and 0.2% of plasticizer.

The polyamide of comparative example 3 was selected from: PA6, η ═ 2.8, miln SC 28; the toughening agent is selected from: 3% dupont E100 and 12% dupont N416; the dendritic polymer is CYD-701D; the release agent is selected from: calcium stearate; the antioxidant is selected from: n, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine; other adjuvants include: 0.1% of coupling agent, 0.2% of heat stabilizer and 0.2% of lubricant.

The polyamide of comparative example 4 was selected from: PA6, η 2.4, xinhuidi M2400; the toughening agent is selected from: dupont N416; the antioxidant is selected from: n, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine; other adjuvants include: 0.8% of hydrolysis resistant agent, 1% of plasticizer and 1.7% of pigment.

The following are the preparation methods of the above examples and comparative examples (the components of each example are weighed according to the weight percentages in tables 1 and 2):

step 1, adding a toughening agent, a dendritic polymer, a nucleating agent, a release agent, an antioxidant and other auxiliaries into a high-speed stirrer in proportion, and uniformly stirring to prepare a premix;

step 2, the polyamide resin obtained in the step is weighed and added from a main feeding port of a double-screw extruder in a weight loss manner; feeding the premix obtained in the step 1 from a side feeding port of a double-screw extruder; and melting and extruding the material strips by using a double-screw extruder, cooling by using a cooling water tank and drying by using an air dryer, and then cutting and granulating by using a granulator to obtain the nylon material special for the magic tape.

In the specific embodiment, the rotating speed of the high-speed stirrer is controlled to be 50-60HZ, and the mixture is mixed for 2 min; the processing temperature of each area of the double-screw extruder is set as follows: the first zone is 150-.

The invention adopts the nylon modified materials of the examples 1-4 and the comparative examples 1-4 to prepare the magic tape by an extrusion/molding mode, and carries out corresponding performance tests on the magic tape product and a demoulding stage in the preparation process:

the crystallization performance of the magic tape product is characterized by adopting DSC, the temperature control rate of the DSC program is 20 ℃/min, the heat history is eliminated by firstly carrying out temperature programming in the first stage, and the crystallization performance is characterized by carrying out temperature programming in the second stage, wherein the higher the initial crystallization temperature is, the narrower the half-peak width of the crystallization is, the easier the material is to crystallize, and the faster the crystallization rate is (the test result is shown in figures 1-8).

The mucosa condition is divided into 3 grades, wherein the grade 1 represents that the mucosa is serious, more than 4 mould-sticking hook-breaking tooth defects appear in each 1000m length magic tape, the grade 2 represents that the mucosa occasionally appears, 1-2 mould-sticking hook-breaking tooth defects appear in each 1000m length magic tape, the grade 3 represents that the mucosa does not appear, and the mould-sticking hook-breaking tooth phenomenon does not appear in the production process.

The size of the demolding noise is used for representing the difficulty of demolding of the material, the demolding is more difficult as the noise is larger, and the demolding is tested by adopting a decibel tester, and the demolding noise is fixed at a position 30cm away from a mold for testing.

And (3) ash adhesion test: the magic tape product is placed on the fixing plate, the magic tape product is placed outdoors for 1 day in an inclined manner at an angle of 80 degrees, the pressure sensitive adhesive tape is pressed at the middle position of the magic tape and is rapidly peeled off, the dust adhesion condition on the pressure sensitive adhesive tape is visually observed and is compared with the designed dust adhesion standard grade (divided into 1-5 grades), so that the dust adhesion condition is judged (the nearest dust adhesion standard grade is taken as the dust adhesion grade), and the designed dust adhesion standard grade is shown as 9.

The results of the performance tests of the examples and comparative examples are shown in table 3:

TABLE 3

	Onset crystallization temperature/. degree.C	Crystallization half-Width/deg.C	Mucosal grade	Demold noise/dB	Ash sticking rating
						Example 1	187.98	7.49	3	60	Stage 2
Example 2	186.06	5.55	3	55	Stage 2
						Example 3	186.71	5.63	3	58	Stage 2
Example 4	189.59	7.65	3	63	Stage 2
						Comparative example 1	173.26	12.47	1	75	Grade 3
Comparative example 2	189.85	8.96	2	68	Grade 5
						Comparative example 3	166.81	12.95	2	72	Stage 2
Comparative example 4	176.61	11.65	1	77	4 stage

From table 3, it can be seen that the nylon material specially used for the magic tape of the embodiment has an initial crystallization temperature significantly higher than that of the comparative example, a narrow crystallization half-peak width, which indicates that the crystallization rate is fast, and from the view point of the adhesion effect to the mold, the embodiment has small adhesion to the mold and low demolding noise, and therefore, the polyamide composite material obtained by the present invention is particularly suitable for preparing the nylon magic tape by adopting an extrusion/molding manner. Further, according to the comparison of examples 1 to 4 with comparative examples 2 and 3, it was found that the gray scale of examples 1 to 4 was significantly lower than that of comparative examples 2 and 4, and examples 1 to 4 were each added with a dendritic polymer while comparative examples 2 and 4 were not added with a dendritic polymer, whereby it was known that the gray scale of the velcro tape could be reduced by adding a dendritic polymer.

In addition, the invention also makes experimental comparison on the preparation method by adopting the raw materials with the same mixture ratio in the examples 1-4:

the preparation method comprises the following steps: premixing a toughening agent, a nucleating agent, a release agent, an antioxidant and other auxiliary agents through a high-speed stirrer, and then adding polyamide resin from a main feeding port of a double-screw extruder; feeding the premix from a side feed port of a double-screw extruder; extruding and granulating to obtain a nylon material special for the magic tape;

the second preparation method comprises the following steps: the polyamide resin, the toughening agent, the dendritic polymer, the nucleating agent, the release agent, the antioxidant and other auxiliary agents are premixed by a high-speed stirrer, and then the premix is fed from a main feed of a double-screw extruder and extruded and granulated to obtain the nylon material special for the magic tape.

The experimental result shows that the average value of the notch impact strength performance indexes of the simply supported beam of the nylon material special for the magic tape obtained by the first preparation method is 90KJ/m²The average value of the notch strength performance index of the simply supported beam of the nylon material special for the magic tape obtained by the second preparation method is 80KJ/m²Therefore, the nylon material special for the magic tape obtained by the preparation method I effectively improves the strength of the material.

Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (2)

1. The utility model provides a magic subsides with special nylon materials preparation of magic subsides which characterized in that: the composite material comprises the following components in percentage by weight:

polyamide: 74.7 percent;

a toughening agent: 20 percent;

dendritic polymer: 0.8 percent

Nucleating agent: 1 percent;

releasing agent: 2.5 percent;

antioxidant: 0.5 percent;

other auxiliary agents: 0.5 percent;

wherein, the polyamide is selected from PA6, eta =2.8 and Chinese hamster SC 28; the toughening agent is polyolefin containing polar branched chains, and 10% of preferably easy-to-use CMG9801 and 10% of DuPont E100 are selected; the dendritic polymer is CYD-701M; the nucleating agent is Bruggeman P22; 2 percent of white oil and 0.5 percent of calcium stearate are selected as the release agent; the antioxidant is N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine; other adjuvants include 0.1% anti-hydrolysis agent, 0.2% coupling agent and 0.2% plasticizer.

2. The magic tape made of nylon material specially used for magic tape according to claim 1, characterized in that: the preparation method of the nylon material special for the magic tape comprises the following steps:

step 1, adding a toughening agent, a dendritic polymer, a nucleating agent, a release agent, an antioxidant and other auxiliaries into a high-speed stirrer in proportion, and uniformly stirring to prepare a premix;

and 2, adding the premix and the polyamide resin obtained in the step 1 from a main feeding weight loss type metering scale of a double-screw extruder, melting and extruding material strips by using the double-screw extruder, cooling by using a cooling water tank and drying by using an air dryer, and cutting and granulating by using a granulator to obtain the nylon material special for the magic tape.

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