CN100485119C - Thermoplastic polyurethane artificial leather - Google Patents

Abstract

The invention provides a formula of thermoplastic polyurethane artificial leather, which adopts thermoplastic polyurethane elastomer resin as a main material, replaces the traditional artificial leather main material PU or PVC synthetic leather, and is prepared by blending acrylic resin, a plasticizer, a dispersing agent, a filling material and the like, wherein the plasticizer replaces toxic phthalate ester by nontoxic polyol derivative, so that the prepared artificial leather has the characteristics of environmental protection, no toxicity and degradability. The invention also provides a preparation method of the thermoplastic polyurethane artificial leather, which is prepared by adopting a calendering method and comprises the following steps: (1) sizing the base fabric; (2) compounding a TPU bottom material and a TPU surface material by adopting a calendering method; (3) compounding the backing material and the fabric, and then attaching the backing material and the fabric to the base fabric; (4) the calendering method can be applied to a conventional calendering production line without using a blown film or T-die casting production line.

Description

A kind of thermoplastic polyurethane artificial leather

technical field

The invention relates to a formula of artificial leather and a manufacturing method thereof, in particular to an all-environmental-friendly thermoplastic polyurethane (TPU, Thermoplastic Polyurethane) artificial leather and a calendering manufacturing method thereof.

Background technique

The production of traditional artificial leather mainly uses PU synthetic leather and PVC synthetic leather as the main body. The main raw materials used to manufacture PU synthetic leather are PU resin and dilution solvent containing high solvent. The main raw material used to manufacture PVC synthetic leather is PVC powder. And liquid plasticizer, the plasticizer adopts phthalates, and the manufacturing method is coating method, pasting method, blown film method or T-die casting method, etc. The formula and manufacturing method of traditional artificial leather have the following disadvantages:

(1) When PU synthetic leather is used as the main body and the coating method is used to manufacture artificial leather, since the semi-finished product after condensation and water washing needs to be dried in the coating process, the solvent used in the PU resin formula will be derived during the drying process. Become waste water, waste gas, and pollute the environment; moreover, the hydrolysis resistance of PU synthetic leather is poor. If you want to improve its hydrolysis resistance, its peel strength and surface abrasion resistance will be relatively poor, especially when the base fabric is made of nylon. When weaving, the peel strength is less than 0.5Kg/3cm. When used in high friction and impact applications, the surface wear resistance and peel strength quality are difficult to meet market requirements, and the practicability is not great.

(2) When PVC synthetic leather is used as the main body and lamination method is used to manufacture artificial leather, in the process of kneading and calendering, due to long-term operation in a high-temperature open system, dust and plasticizer volatilization waste gas are easily generated, which is very polluting to the environment In addition, when PVC products are incinerated, toxic gases such as dioxin, chlorine, and heavy metal particles will be produced; PVC synthetic leather has poor low-temperature bending resistance and impact resistance. The abnormal phenomenon of adding additives to spit out,

(3) Phthalate esters are toxic reagents. As plasticizers, the manufactured artificial leather contains toxic formulas, which are used in daily life and endanger people's health.

Therefore, in order to solve the above-mentioned various problems, the present invention provides an environmentally friendly, non-toxic and degradable artificial leather formulation using thermoplastic polyurethane as a main ingredient, and a method for manufacturing the artificial leather.

Contents of the invention

The object of the present invention is to provide an environmentally friendly, non-toxic and degradable artificial leather with thermoplastic polyurethane as the main material, and a method for manufacturing the artificial leather: calendering.

A thermoplastic polyurethane (Thermoplastic Polyurethane, TPU) artificial leather is formed by compounding base material, fabric and base fabric, and the base material components include at least: thermoplastic polyurethane resin, acrylic resin, plasticizer, foaming stabilizer, foam control agent and a foaming agent, wherein the plasticizer is a polyol derivative plasticizer. The formula ingredients and weight ratio of the fabric and base material are as follows:

Fabric:

Thermoplastic Polyurethane Resin 100

Acrylic resin 2----10

Polyol derivative plasticizer 1----50

Dispersant 0----1

Reinforced filling material 0----30

Stearic acid 0----1

Antioxidant 0----1

UV absorber 0----1

Pigment 0----5

Bottom material:

Thermoplastic Polyurethane Resin 100

Acrylic resin 2----10

Polyol derivative plasticizer 1----50

Foam stabilizer 2----3

Foam control agent 0.5---1.5

Foaming agent 4----6

Reinforced filling material 0----50

Pigment 0----5.

Among them, the dispersant is a polymer fatty acid dispersant, the foaming stabilizer is Ba/Zn foaming stabilizer, the foaming agent is AC, and the polyol derivative is propylene glycol ester.

The present invention also provides a method for making thermoplastic polyurethane artificial leather, which is made by calendering, comprising the following steps:

(1) Sizing the base cloth;

(2) Composite TPU base material and fabric by calendering method;

(3) Composite the base material and the fabric, and then attach it to the base fabric;

(4) Carry out aftertreatment to artificial leather, promptly make described thermoplastic polyurethane artificial leather;

Among them, in step (2), the process flow of preparing TPU fabric and bottom material by calendering method is as follows: stirring—>banbury—>opening—>filtering—>calendering—>extraction.

In step (3), the base fabric is selected from any one of knitted fabric, ginned cotton, woven fabric, imitation leather, impregnated fabric or non-woven fabric.

Compared with the prior art, a thermoplastic polyurethane artificial leather of the present invention adopts thermoplastic polyurethane elastomer resin as the main material, replaces the traditional artificial leather main material PU synthetic leather or PVC synthetic leather, blends acrylic resin, plasticizer, dispersion It is made of non-toxic polyol derivatives instead of toxic phthalates, so that the artificial leather is environmentally friendly, non-toxic and degradable.

In addition, the present invention adopts calendering method to prepare thermoplastic polyurethane artificial leather, can apply conventional calendering production line, does not need to use blown film or T-die casting production line, like this, can make the calendering equipment originally used in the production of polyurethane (PVC) artificial leather There will be no investment loss due to the market shrinkage of PVC due to environmental protection factors, and the calender does not need any mechanical changes. This production method can greatly reduce the production cost of TPU artificial leather, and make the market more accept TPU as an environmentally friendly material. In the preparation process, the main material polyurethane resin and various additives and auxiliary materials are added at the same time in a high-speed mixer, without pre-heating or pre-granulation. By controlling the proportion of additives and the temperature during mixing and stirring, acrylic resin, dispersant Polymer fatty acid esters and stearic acid reduce the friction between raw material molecules in the production process, and reduce the melting temperature of the melt, thereby improving thermal stability, and preventing the melt from sticking to the metal wheel surface, reducing machine load and power consumption consume.

Description of drawings

Fig. 1 is the preparation flowchart of a kind of thermoplastic polyurethane artificial leather of the present invention;

Fig. 2 is a flowchart of preparation of a thermoplastic polyurethane artificial leather composite TPU base material and fabric by calendering method of the present invention.

Detailed ways

The formulation of the thermoplastic polyurethane artificial leather of the present invention is further set forth below.

Artificial leather is made by laminating the calendered fabric and base material with the base fabric. The artificial leather fabric and base material are made of thermoplastic polyurethane resin as the main material. The base material formula also includes auxiliary materials: plasticizer, foaming Stabilizers, foam control agents, reinforced filling materials; fabric formulations also include auxiliary materials: plasticizers, dispersants, reinforced filling materials, antioxidants, ultraviolet absorbers and colorants. In the present invention, plasticizer selects polyalcohol derivative plasticizer for use; Dispersant selects polymer fatty acid dispersant for use; Foaming stabilizer selects Ba/Zn foaming stabilizer for use; Foaming agent selects foaming agent AC for use; Active light calcium carbonate can be selected as the material; PU color chips can be selected as the color material; propylene glycol ester can be selected as the polyol derivative. The base fabric can be selected from various kinds of fabrics such as knitted fabric, ginned cotton, woven fabric, imitation leather, impregnated fabric or non-woven fabric. The color of artificial leather is determined by the selection of coloring material, which can be colored or colorless, and the thickness range is 0.05mm-5.00mm.

The formula of primer is as follows (weight ratio):

Thermoplastic Polyurethane 100

Acrylic resin 2---10

Polyol derivative plasticizer 1----50

Foam stabilizer 2----3

Foam control agent 0.5---15

Foaming agent AC 4----6

Reinforced filling material 0-----50

Pigment 0-----5

The formula of the fabric is as follows (weight ratio):

Thermoplastic Polyurethane Resin 100

Acrylic resin 2---10

Polyol derivative plasticizer 1----50

Dispersant 0----1

Reinforced filling material 0----30

Stearic acid 0-----1

Antioxidant 0-----1

UV absorber 0-----1

Pigment 0-----5

Below in conjunction with Fig. 1-2 specifically set forth artificial leather manufacturing method of the present invention:

Step 1) sizing the base cloth and producing it on a size cloth machine:

Equipment used: pulp cloth machine, paste wheel (generally use 30-60 mesh gravure wheel), coating knife;

Process flow: Squeeze the glue with a knife and apply it on the base fabric using the scraping method. Among them, the glue generally uses two-component polyurethane glue.

Process conditions: drying temperature: 120-135°C; drying time: 1-2 minutes

Purpose: To make the base cloth and rubber stick firmly.

Step 2) Composite TPU primer by calendering;

Equipment used: high-speed mixer, internal mixer, open mill, filter, 4-roller calender, take-off wheel, laminating wheel, cooling wheel and coiling wheel. Among them, the calendering method adopts a conventional calendering production line and does not need to use The blown film or T-die casting production line is suitable for the manufacture of polyvinyl chloride (PVC) artificial leather and thermoplastic polyurethane (TPU) artificial leather.

Technological process: Stirring —> Banbury —> Open refining —> Filtration —> Calendering —> Extraction The preparation steps are as follows:

Step 21) Throw base materials (polyurethane resin, acrylic resin, polyol derivative plasticizer, Ba/Zn foam stabilizer, foam control agent, reinforced filling material) into the high-speed mixer according to the above ratio, and carry out high-speed stirring mix;

Process conditions: Stir at low speed for 30 seconds, then stir at high speed for 5-6 minutes, and the temperature range is 102-108°C.

Purpose: To fully mix various materials.

Step 22) The base material after high-speed stirring and mixing falls into the internal mixer, and after half of the material is dropped in the high-speed mixer, foaming agent AC and coloring material are added, and then the base material is continued to be cast;

Process conditions: banburying time 4.5-5.5 minutes

Purpose: To further mix and initially gel the material.

Step 23) Put the bottom material through banburying into the mills A and B in sequence, and process through two millings;

Process conditions: refining temperature 110-130°C

Purpose: To fully gel the material and feed it.

Step 24) putting the bottom material through the refining into a filter for filtering to remove impurities;

Process conditions: Die head temperature 90-130°C; filter mesh 8 mesh × 20 mesh

Purpose: To remove impurities.

Step 25) putting the filtered base material into a 4-roller calender for calendering;

Process conditions: calendering temperature 115-145°C

Purpose: To press the rubber into a sheet and adjust the thickness.

Step 26) sending the calendered base material into the take-up wheel;

Process conditions: temperature is 120-145°C

Purpose: To adjust the ideal thickness of the film by stretching the take-off wheel.

Step 3) Composite the TPU fabric by calendering; the equipment and process used are the same as those of the composite TPU bottom material.

The preparation steps are as follows:

Step 31) Throw the fabric (polyurethane resin, acrylic resin, polyol derivative plasticizer, polymer fatty acid ester dispersant, stearic acid, antioxidant and ultraviolet absorber) into the high-speed mixer according to the above ratio, and carry out high-speed mixing. Stir and mix;

Process conditions: first stir at low speed for 30 seconds, then stir at high speed for 5-6 minutes

Purpose: To fully mix various materials.

Step 32) The fabric after high-speed stirring and mixing falls into the internal mixer, and then puts in the coloring material;

Process conditions: banburying time 4.5-5.5 minutes

Purpose: To further mix and initially gel the material.

Step 33) put the fabrics through internal mixing into the mills A and B in sequence, and process through two times of refining;

Process conditions: refining temperature 110-130°C

Purpose: To fully gel the material and feed it.

Step 34) Putting the refined fabric into a filter to filter and remove impurities;

Process conditions: Die head temperature 90-130°C; filter mesh 20×40×80 mesh

Purpose: To remove impurities.

Step 35) putting the filtered fabric into a 4-roll calender for calendering;

Process conditions: calendering temperature 140-165°C

Purpose: To press the rubber into a sheet and adjust the thickness.

Step 36) sending the calendered fabric into the take-up wheel;

Process conditions: temperature is 140-165°C

Purpose: To adjust the ideal thickness of the film by stretching the take-off wheel.

Step 4) Composite the base material and the fabric, and then attach it to the base fabric;

At this time, the calendered and extracted bottom material and fabric together with the bottom cloth are sent to the laminating wheel to be pressed into artificial leather under normal temperature conditions, with a thickness of 0.05mm-5.00mm, and then the semi-finished artificial leather is cooled by the cooling wheel , and finally taken out by the take-up wheel;

Step 5) foaming the artificial leather;

Equipment used: foaming furnace. Foaming furnaces generally have 3-5 heating zones. When using 3 heating zones for foaming, the heating time will be longer due to the less heating of the furnace body; The heating time is shorter. The present invention completes the foaming process with 4 heating zones.

4 Zones Oil Heated Foaming Furnace:

1# Area 180-210℃

District 2 190-220℃

Area 3# 180-190℃

4# District 170-180℃

Speed 12-22mpm

Step 6) carry out surface treatment to artificial leather;

Equipment used: processor, mesh: 80-120 mesh

Surface treatment agent: polyurethane surface treatment agent

Step 7) Finally, the artificial leather is cut and packaged into rolls, which is the finished thermoplastic polyurethane artificial leather.

A kind of manufacturing method of thermoplastic polyurethane artificial leather of the present invention is specifically illustrated by an embodiment below.

Specifications of TPU artificial leather:

Embossing: DN2 (light leather) Color: U5175 (black) Luminosity: T6W1 (non-slip)

Product name: TPU black 130g gin cotton Thickness: 1.4mm

Width: 1370mm Quantity: 500 yards Application: baseball glove

The manufacturing steps are as follows:

Step 1) Sizing the base cloth with two liquid polyurethane glue;

Process conditions: Drying temperature: 135°C Sizing wheel mesh: 40 mesh

Sizing times: 2 Production line speed: 25mpm

Step 2) Composite TPU base material (adhesive thickness: 0.42mm; adhesive width: 1422mm)

Step 21) Feed into the high-speed mixer according to the ratio of the following base materials, and perform high-speed stirring and mixing;

Process conditions: Stir at low speed for 30 seconds, then stir at high speed for 5 minutes, and the temperature reaches 105°C.

Base material ratio (weight ratio)

Thermoplastic polyurethane resin 100kg

Acrylic resin 2.3kg

Polyol derivatives 20kg

Ba/Zn foam stabilizer 2.3kg

Foam control agent 1.2kg

Reinforced filling material 35kg

Black film 0.35kg

Step 22) The base material after high-speed stirring and mixing falls into the internal mixer, and after half of the material is dropped in the high-speed mixer, 5.8 kg of foaming agent AC and 0.35 kg of colorant black flakes are added, and then the remaining base material is continued to be cast;

Process conditions: Mixing time: 5 minutes; Blanking current: 352A

Step 23) Put the bottom material through banburying into the mills A and B in sequence, and process through two millings;

Process conditions: opening temperature 120°C

Step 24) putting the bottom material through the refining into a filter for filtering to remove impurities;

Process conditions: Die head temperature 110°C; filter mesh 8 mesh × 20 mesh

Step 25) putting the filtered base material into a 4-roller calender for calendering;

Process conditions: front wheel temperature: 134°C; upper wheel temperature: 134°C;

Middle wheel temperature: 126°C; Lower wheel temperature: 126°C

Step 26) sending the calendered base material into the take-up wheel;

 Process conditions: temperature is 128°C

Step 3) Composite the TPU fabric by calendering; the equipment and process used are the same as those of the composite TPU bottom material. (Adhesive thickness: 0.18mm; Adhesive width: 1422mm)

The preparation steps are as follows:

Step 31) Feed materials into the high-speed mixer according to the proportion of the following fabrics, and perform high-speed stirring and mixing;

Process conditions: first stir at low speed for 30 seconds, then stir at high speed for 6 minutes; the temperature reaches 102°C

Fabric ratio (weight ratio)

Thermoplastic Polyurethane Resin 100kg

Acrylic resin 11.6kg

Polyol derivatives 20kg

Polymer fatty acid 0.58kg

Reinforced filling material 28kg

Black film 1.6kg

Step 32) The fabric after high-speed stirring and mixing is dropped into the internal mixer, and then 1.6 kg of black flakes of coloring material are dropped into;

Process conditions: mixing time 4 minutes; blanking current: 281A

Step 33) put the fabrics through internal mixing into the mills A and B in sequence, and process through two times of refining;

Process conditions: opening temperature 120°C

Step 34) Putting the refined fabric into a filter to filter and remove impurities;

Process conditions: Die head temperature 120°C; Filter mesh: 20×40×80 mesh

Step 35) putting the filtered fabric into a 4-roll calender for calendering;

Process conditions: front wheel temperature: 160°C; upper wheel temperature: 160°C;

  Middle wheel temperature: 154°C; Lower wheel temperature: 154°C

Step 36) sending the calendered fabric into the take-up wheel;

 Process conditions: temperature is 154°C

Step 4) composite base material and fabric;

At this time, the calendered and extracted base material and fabric are sent to the laminating wheel to press the artificial leather under normal temperature conditions, and then the semi-finished artificial leather is cooled by the cooling wheel, and finally taken out by the coiling wheel.

Step 5) foaming the artificial leather;

Equipment used: foaming furnace

4 Zones Oil Heated Foaming Furnace:

Zone 1: 200℃ Embossing wheel: DN2

Zone 2: 200℃ Speed: 20.6mpm

Zone 3: 190°C Pressure: 2kgf/cm ²

Area 4#: 188°C

Step 6) carry out surface treatment to artificial leather;

Equipment used: Processor

Surface treatment agent: anti-slip polyurethane surface treatment agent

Mesh: 80 mesh

Processing times: 1 time

Step 7) Finally, the artificial leather is cut and packaged into rolls, which is the finished thermoplastic polyurethane artificial leather.

The above disclosures are only preferred embodiments of the present invention, and certainly cannot be used to limit the scope of rights of the present invention. Therefore, equivalent changes made according to the patent scope of the present invention still fall within the scope of the present invention.

Claims (5)

1. A thermoplastic polyurethane artificial leather, composed of a base material, a fabric and a base fabric, the base material components at least include: thermoplastic polyurethane resin, acrylic resin, plasticizer, foaming stabilizer, foam control agent and foaming agent , wherein the plasticizer is a polyol derivative plasticizer, characterized in that: the composition and weight ratio of the fabric and base material are as follows: Fabric: Thermoplastic Polyurethane Resin 100 Acrylic resin 2----10 Polyol derivative plasticizer 1----50 Dispersant 0----1 Reinforced filling material 0----30 Stearic acid 0----1 Antioxidant 0----1 UV absorber 0----1 Pigment 0----5 Bottom material: Thermoplastic Polyurethane Resin 100 Acrylic resin 2----10 Polyol derivative plasticizer 1----50 Foam stabilizer 2----3 Foam control agent 0.5---1.5 Foaming agent 4----6 Reinforced filling material 0----50 Pigment 0----5. 2. A kind of thermoplastic polyurethane artificial leather according to claim 1, characterized in that: the dispersant is a high-molecular fatty acid dispersant. 3. A thermoplastic polyurethane artificial leather according to claim 1, characterized in that: the foaming stabilizer is selected from Ba/Zn foaming stabilizer, and the foaming agent is selected from foaming agent AC. 4. A thermoplastic polyurethane artificial leather according to claim 1, characterized in that: polyol derivatives are selected from propylene glycol esters. 5. A thermoplastic polyurethane artificial leather, composed of a base material, a fabric and a base fabric, the base material components at least include: thermoplastic polyurethane resin, acrylic resin, plasticizer, foaming stabilizer, foam control agent and foaming agent , wherein the plasticizer is a polyol derivative plasticizer, characterized in that: the composition and weight ratio of the fabric and base material are as follows: Fabric: Thermoplastic Polyurethane Resin 100 Acrylic resin 11.6 Polyol derivative plasticizer 20 Polymer fatty acid lipid dispersant 0.58 Reinforced filling material 28 Black film 1.6 Bottom material: Thermoplastic Polyurethane Resin 100 Acrylic resin 2.3 Polyol derivative plasticizer 20 Ba/Zn foam stabilizer 2.3 Foam control agent 1.2 Foaming agent AC 5.8 Reinforced filling material 35 Black flakes 0.35.

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