CN108285634B - TPU (thermoplastic polyurethane) foaming material, preparation method thereof and TPU synthetic leather - Google Patents
TPU (thermoplastic polyurethane) foaming material, preparation method thereof and TPU synthetic leather Download PDFInfo
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- CN108285634B CN108285634B CN201711466373.8A CN201711466373A CN108285634B CN 108285634 B CN108285634 B CN 108285634B CN 201711466373 A CN201711466373 A CN 201711466373A CN 108285634 B CN108285634 B CN 108285634B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers
- D06N3/005—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers obtained by blowing or swelling agent
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/145—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes two or more layers of polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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Abstract
The invention provides a TPU (thermoplastic polyurethane) foaming material, a preparation method thereof and TPU synthetic leather. The TPU foaming material comprises, by weight, 100 parts of TPU, 0.1-5 parts of lubricant, 2-8 parts of foaming agent and 10-30 parts of plasticizing auxiliary agent. By the synergistic cooperation of the TPU, the lubricant, the foaming agent and the plasticizing auxiliary agent in specific parts by weight, the raw material mixture can obtain a hand feeling similar to that of PVC synthetic leather with the same formula through foaming, so that the application value of the TPU foaming material in the aspects of home decoration and automotive decoration materials is improved.
Description
Technical Field
The invention relates to the field of home decoration materials, in particular to a TPU (thermoplastic polyurethane) foaming material, a preparation method thereof and TPU synthetic leather.
Background
The TPU is thermoplastic polyurethane, is divided into polyester type and polyether type, has wide hardness range (40A-85D), is wear-resistant, oil-resistant, transparent and good in elasticity, and can be widely applied to the fields of daily necessities, sports goods, toys and decorative materials. The halogen-free flame retardant TPU can also replace soft PVC to meet more and more environmental protection requirements.
However, in the current market of TPU synthetic leather in home decoration or automobile, because the hand feeling is hard, the TPU synthetic leather with the same hand feeling as PVC is difficult to obtain at present.
Disclosure of Invention
The invention mainly aims to provide a TPU foaming material, a preparation method thereof and TPU synthetic leather, and aims to solve the problem that the TPU synthetic leather in the prior art is hard in handfeel.
In order to achieve the above object, according to one aspect of the present invention, there is provided a TPU foam, which comprises the following raw materials in parts by weight: 100 parts of TPU, 0.1-5 parts of lubricant, 2-8 parts of foaming agent and 10-30 parts of plasticizing auxiliary agent.
Further, the TPU foaming material comprises the following raw materials in parts by weight: 100 parts of TPU, 0.2-2 parts of lubricant, 2-6 parts of foaming agent and 10-25 parts of plasticizing auxiliary agent; preferably, the TPU has a hardness of from 60A to 45D.
Further, the lubricant is a metal soap lubricant; more preferably, the lubricant is cadmium stearate.
Further, the blowing agent is an AC blowing agent.
Further, the plasticizing aid is ACR.
Furthermore, the TPU foaming material also comprises 1-5 parts by weight of a foaming promoter, preferably 1-2 parts by weight of the foaming promoter.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method of preparing a TPU foam, the method comprising: carrying out calendaring molding on the raw material of any foaming material to obtain a TPU film precursor; and foaming the TPU film precursor at 130-230 ℃ to obtain the TPU foaming material. And further, placing the TPU film precursor into a foaming furnace for foaming, and controlling the temperature of the foaming furnace in four sections, wherein the temperature sections sequentially passing through the foaming furnace are 135 +/-10 ℃, 200 +/-10 ℃, 220 +/-10 ℃ and 180 +/-10 ℃ according to the foaming sequence of the TPU film precursor, and the total foaming time is 1-2 min, so as to obtain the TPU foaming material.
According to one aspect of the invention, the TPU synthetic leather comprises a base fabric, a TPU foaming layer and a TPU surface layer which are sequentially overlapped, wherein the TPU foaming layer is made of any one of the foaming materials.
Further, the TPU surface layer comprises the following raw materials in parts by weight: 100 parts of TPU, 0.1-5 parts of lubricant and 5-20 parts of plasticizing auxiliary agent; preferably, the TPU surface layer comprises the following raw materials in parts by weight: 100 parts of TPU, 0.3-2 parts of lubricant and 6-18 parts of plasticizing auxiliary agent; more preferably, the lubricant is a metal soap lubricant; the plasticizing auxiliary agent is ACR; preferably, the TPU has a hardness of from 60A to 45D.
By applying the technical scheme of the invention, the TPU is cooperated with the lubricant, the foaming agent and the plasticizing auxiliary agent in specific weight parts, so that the raw material mixture can obtain a hand feeling similar to that of PVC synthetic leather with the same formula through foaming, thereby improving the application value of the TPU foaming material in the aspects of home decoration and vehicle decoration materials.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As mentioned in the background art, TPU has excellent tensile property and good wear resistance, but pure TPU has harder hand feeling than PVC and generally has the defect of harder hand feeling when being applied to home decoration or synthetic leather for vehicles. In order to improve the defect, in an exemplary embodiment of the present application, a TPU foam is provided, which comprises the following raw materials in parts by weight: 100 parts of TPU, 0.1-5 parts of lubricant, 2-8 parts of foaming agent and 10-30 parts of plasticizing auxiliary agent.
In the TPU foaming material, the TPU is matched with the lubricant, the foaming agent and the plasticizing auxiliary agent in a synergistic manner in a specific weight part, so that the raw material mixture can obtain a hand feeling similar to that of PVC synthetic leather with the same formula through foaming, and the application value of the TPU foaming material in the aspects of home decoration and automotive decoration materials is improved.
In the TPU foaming material, the lubricant, the foaming agent and the plasticizing auxiliary agent are controlled within the weight part range, so that the foaming performance of the TPU can be synergistically improved, the TPU is relatively soft in hand feeling, and the application value of the TPU foaming material in the aspects of home decoration and automobile synthetic leather is improved. In order to further optimize the synergistic interaction between the raw materials, in a preferred embodiment of the present application, the raw materials of the TPU foaming material comprise, by weight: 100 parts of TPU, 0.2-3 parts of lubricant, 2-6 parts of foaming agent and 15-25 parts of plasticizing auxiliary agent; preferably, the TPU has a hardness of from 60A to 45D, more preferably from 60A to 75A.
In the preferred embodiment, the amounts of the lubricant, the foaming agent and the plasticizing auxiliary agent are controlled in the above more preferable range, so that the synergistic effect of the lubricant, the foaming agent and the plasticizing auxiliary agent can be further improved, and the foaming performance of the TPU can be further improved. In a more preferable embodiment, the raw materials of the TPU foaming material comprise, by weight, 100 parts of TPU, 0.4 to 1 part of lubricant, 2.5 to 4.5 parts of foaming agent and 15 to 25 parts of plasticizing auxiliary agent. The TPU foam in this preferred embodiment has the best hand.
Because the properties of the TPU raw materials from different sources are different, in order to further improve that the TPU from different sources can obtain relatively good hand feeling after being foamed, the properties of the TPU from each source are preferably detected in the actual production and processing process. Through numerous tests, the TPU foamed material obtained by foaming has soft hand feeling and is relatively stable when the hardness of the TPU is 60A-45D, and more preferably 60A-75A.
In the TPU foaming material, the lubricant can be well compatible with the TPU, plays a role in internal lubrication in the processing process, and can also play a role in stabilizing the TPU so as to prevent the TPU from being decomposed in the plasticizing or foaming process. In a preferred embodiment of the present application, the lubricant is a metal soap lubricant. The lubricant has lubricating effect. For certain metal soaps, the longer the fatty acid carbon chain incorporated, the better the lubricity. Calcium stearate, zinc stearate, lead stearate, etc. are commonly used. More preferably, the lubricant herein is cadmium stearate. The metal soap lubricant is applied to the TPU foaming material, not only plays a role in lubricating, but also plays a role in stabilizing the TPU, and the metal soap lubricant and the plasticizing auxiliary agent play a synergistic role in improving the strength of TPU melt and expanding the temperature range of TPU processing, so that the foaming performance of the TPU is easier to regulate and control.
In the TPU foaming material, the foaming agent is the foaming agent commonly used for PVC foaming. In a preferred embodiment herein, the blowing agent is an AC blowing agent.
In the TPU foaming material, the main function of the plasticizing auxiliary agent is to enhance the melt strength, and in addition, the plasticizing auxiliary agent can also play a role in shortening the plasticizing time and expanding the applicable processing temperature range, so that any plasticizing auxiliary agent with the functions is suitable for the application. In a preferred embodiment of the present application, the plasticizing aid is ACR.
In order to further promote the foaming performance of the foaming agent on the basis of the foaming material, in a preferred embodiment of the application, the raw material of the TPU foaming material further comprises 1 to 5 parts by weight of a foaming promoter, preferably 1 to 2 parts by weight of the foaming promoter. A foaming promoter, preferably an AC foaming agent, such as zinc stearate, as a foaming aid can lower the decomposition temperature of the foaming agent.
In another exemplary embodiment of the present application, there is provided a method for preparing a TPU foam, the method comprising: carrying out calendaring molding on the raw material of any foaming material to obtain a TPU film precursor; and foaming the TPU film precursor at 130-230 ℃ to obtain the TPU foaming material. The TPU foaming material obtained by foaming the raw materials at the foaming temperature has the hand feeling equivalent to that of PVC with the same formula.
The foaming material can be reasonably adjusted within the foaming temperature range. In a preferred embodiment of the application, the TPU film precursor is placed in a foaming furnace for foaming, and the foaming furnace is divided into four sections for temperature control, wherein the temperature sections sequentially passing through according to the foaming sequence of the TPU film precursor are 135 +/-10 ℃, 200 +/-10 ℃, 220 +/-10 ℃ and 180 +/-10 ℃, and foaming is carried out for 1-2 min, so as to obtain the TPU foaming material.
In the preferred embodiment, the foaming temperature of the second temperature section is controlled within the range of 200 +/-10 ℃, and the foam obtained by foaming is fine and uniform and has soft hand feeling.
In a third exemplary embodiment of the present application, there is provided a TPU synthetic leather, which includes a base fabric, a TPU foaming layer and a TPU surface layer, which are sequentially disposed, wherein the TPU foaming layer is made of any one of the above foaming materials. The TPU synthetic leather prepared by adopting the TPU foaming layer disclosed by the application is soft in hand feeling, and the practical application value is higher than that of PVC synthetic leather with the same formula.
In the TPU synthetic leather, the specific raw materials of the TPU surface layer are not limited. In a preferred embodiment of the present application, the TPU facing layer comprises the following raw materials in parts by weight: 100 parts of TPU, 0.1-5 parts of lubricant and 5-20 parts of plasticizing auxiliary agent; preferably, the TPU surface layer comprises the following raw materials in parts by weight: 100 parts of TPU, 0.3-2 parts of lubricant and 6-18 parts of plasticizing auxiliary agent; more preferably, the lubricant is a metal soap lubricant, and even more preferably the lubricant is cadmium stearate; the plasticizing auxiliary agent is ACR. Preferably, the TPU has a hardness of from 60A to 45D, more preferably from 60A to 75A. The functions of the above materials are the same as those mentioned above, and are not described in detail herein. The TPU surface layer prepared by adopting the content proportion has more excellent tensile property and wear resistance.
The advantageous effects of the present application will be further described with reference to specific examples. In the following examples, the starting materials were all commercially available products.
Example 1
The TPU foaming layer comprises the following raw materials in parts by weight: 100 parts of TPU, 0.1 part of lubricant, 2 parts of foaming agent and 10 parts of plasticizing assistant.
The TPU surface layer comprises the following raw materials in parts by weight: 100 parts of TPU, 0.1 part of lubricant and 5 parts of plasticizing assistant.
Wherein the hardness of the TPU is 60A; the lubricant is cadmium stearate; the foaming agent is an AC foaming agent; the plasticizing auxiliary agent is ACR.
The raw materials of the foaming layer are subjected to calendering molding at the temperature of 110 ℃ to obtain a TPU foaming film precursor; and (3) rolling and molding the raw materials of the surface layer at 120 ℃ to obtain the TPU surface layer.
Arranging the TPU foaming film precursor on a knitted fabric, and arranging a TPU surface layer on the TPU foaming precursor to obtain a TPU synthetic leather precursor;
and (2) placing the TPU synthetic leather precursor into a foaming furnace for foaming, wherein the foaming furnace is controlled by four sections of temperature, and the TPU synthetic leather is obtained by foaming for 2min according to the foaming sequence of the TPU film precursor and the temperature sections of 125 ℃, 190 ℃, 210 ℃ and 170 ℃ in sequence.
Example 2
The TPU foaming layer comprises the following raw materials in parts by weight: 100 parts of TPU, 5 parts of lubricant, 8 parts of foaming agent and 30 parts of plasticizing assistant.
The TPU surface layer comprises the following raw materials in parts by weight: 100 parts of TPU, 5 parts of lubricant and 20 parts of plasticizing assistant.
Wherein the hardness of the TPU is 45D; the lubricant is cadmium stearate; the foaming agent is an AC foaming agent; the plasticizing auxiliary agent is ACR.
The raw materials of the foaming layer are subjected to roll forming at 135 ℃ to obtain a TPU foaming film precursor; and (3) rolling and molding the raw materials of the surface layer at 118 ℃ to obtain the TPU surface layer.
Arranging the TPU foaming film precursor on a knitted fabric, and arranging a TPU surface layer on the TPU foaming precursor to obtain a TPU synthetic leather precursor;
and (2) placing the TPU synthetic leather precursor into a foaming furnace for foaming, wherein the foaming furnace is controlled by four sections of temperature, and the TPU synthetic leather is obtained by foaming for 1min according to the foaming sequence of the TPU film precursor and the temperature sections of 145 ℃, 210 ℃, 230 ℃ and 180 ℃ which are sequentially passed.
Example 3
The TPU foaming layer comprises the following raw materials in parts by weight: 100 parts of TPU, 3 parts of lubricant, 6 parts of foaming agent and 25 parts of plasticizing auxiliary agent;
the TPU surface layer comprises the following raw materials in parts by weight: 100 parts of TPU, 2 parts of lubricant and 18 parts of plasticizing assistant;
wherein the hardness of the TPU is 65A; the lubricant is cadmium stearate; the foaming agent is an AC foaming agent; the plasticizing auxiliary agent is ACR.
The raw materials of the foaming layer are subjected to rolling molding at 115 ℃ to obtain a TPU foaming film precursor; and (3) carrying out calendering molding on the raw materials of the surface layer at 122 ℃ to obtain the TPU surface layer.
Arranging the TPU foaming film precursor on a knitted fabric, and arranging a TPU surface layer on the TPU foaming precursor to obtain a TPU synthetic leather precursor;
and (2) placing the TPU synthetic leather precursor into a foaming furnace for foaming, wherein the foaming furnace is controlled by four sections of temperature, and the TPU synthetic leather is obtained by foaming for 1.5min according to the foaming sequence of the TPU film precursor and the temperature sections of 135 ℃, 200 ℃, 220 ℃ and 180 ℃ which are sequentially passed through.
Example 4
The TPU foaming layer comprises the following raw materials in parts by weight: 100 parts of TPU, 0.2 part of lubricant, 2 parts of foaming agent and 15 parts of plasticizing auxiliary agent;
the TPU surface layer comprises the following raw materials in parts by weight: 100 parts of TPU, 0.3 part of lubricant and 6 parts of plasticizing assistant;
wherein the hardness of the TPU is 75A; the lubricant is cadmium stearate; the foaming agent is an AC foaming agent; the plasticizing auxiliary agent is ACR.
The raw materials of the foaming layer are subjected to calendering molding at 118 ℃ to obtain a TPU foaming film precursor; and (3) rolling and molding the raw materials of the surface layer at 125 ℃ to obtain the TPU surface layer.
Arranging the TPU foaming film precursor on a knitted fabric, and arranging a TPU surface layer on the TPU foaming precursor to obtain a TPU synthetic leather precursor;
and (2) placing the TPU synthetic leather precursor into a foaming furnace for foaming, wherein the foaming furnace is controlled by four sections of temperature, and the TPU synthetic leather is obtained by foaming for 2min according to the foaming sequence of the TPU film precursor and the temperature sections of 135 ℃, 200 ℃, 220 ℃ and 180 ℃ which are sequentially passed through.
Example 5
The TPU foaming layer comprises the following raw materials in parts by weight: 100 parts of TPU, 0.2 part of lubricant, 2 parts of foaming agent, 1 part of foaming promoter zinc stearate and 15 parts of plasticizing auxiliary agent;
the TPU surface layer comprises the following raw materials in parts by weight: 100 parts of TPU, 0.3 part of lubricant and 6 parts of plasticizing assistant;
wherein the hardness of the TPU is 75A; the lubricant is cadmium stearate; the foaming agent is an AC foaming agent; the plasticizing auxiliary agent is ACR.
The raw materials of the foaming layer are subjected to calendering molding at 118 ℃ to obtain a TPU foaming film precursor; and (3) rolling and molding the raw materials of the surface layer at 120 ℃ to obtain the TPU surface layer.
Arranging the TPU foaming film precursor on a knitted fabric, and arranging a TPU surface layer on the TPU foaming precursor to obtain a TPU synthetic leather precursor;
and (2) placing the TPU synthetic leather precursor into a foaming furnace for foaming, wherein the foaming furnace is controlled by four sections of temperature, and the TPU synthetic leather is obtained by foaming for 2min according to the foaming sequence of the TPU film precursor and the temperature sections of 135 ℃, 200 ℃, 220 ℃ and 180 ℃ which are sequentially passed through.
Example 6
The TPU foaming layer comprises the following raw materials in parts by weight: 100 parts of TPU, 0.2 part of lubricant, 2 parts of foaming agent, 5 parts of foaming promoter zinc stearate and 15 parts of plasticizing auxiliary agent;
the TPU surface layer comprises the following raw materials in parts by weight: 100 parts of TPU, 0.3 part of lubricant and 6 parts of plasticizing assistant;
wherein the hardness of the TPU is 75A; the lubricant is cadmium stearate; the foaming agent is an AC foaming agent; the plasticizing auxiliary agent is ACR.
The raw materials of the foaming layer are subjected to calendering molding at 118 ℃ to obtain a TPU foaming film precursor; and (3) rolling and molding the raw materials of the surface layer at 120 ℃ to obtain the TPU surface layer.
Arranging the TPU foaming film precursor on a knitted fabric, and arranging a TPU surface layer on the TPU foaming precursor to obtain a TPU synthetic leather precursor;
and (2) placing the TPU synthetic leather precursor into a foaming furnace for foaming, wherein the foaming furnace is controlled by four sections of temperature, and the TPU synthetic leather is obtained by foaming for 2min according to the foaming sequence of the TPU film precursor and the temperature sections of 135 ℃, 200 ℃, 220 ℃ and 180 ℃ which are sequentially passed through.
Example 7
The TPU foaming layer comprises the following raw materials in parts by weight: 100 parts of TPU, 5 parts of lubricant, 8 parts of foaming agent and 30 parts of plasticizing assistant.
The TPU surface layer comprises the following raw materials in parts by weight: 100 parts of TPU, 5 parts of lubricant and 20 parts of plasticizing assistant.
Wherein the hardness of the TPU is 45D; the lubricant is cadmium stearate; the foaming agent is an AC foaming agent; the plasticizing auxiliary agent is ACR.
The raw materials of the foaming layer are subjected to roll forming at 135 ℃ to obtain a TPU foaming film precursor; and (3) rolling and molding the raw materials of the surface layer at 118 ℃ to obtain the TPU surface layer.
Arranging the TPU foaming film precursor on a knitted fabric, and arranging a TPU surface layer on the TPU foaming precursor to obtain a TPU synthetic leather precursor;
and (2) placing the TPU synthetic leather precursor into a foaming furnace for foaming, wherein the foaming furnace is controlled by four sections of temperature, and the TPU synthetic leather is obtained by foaming for 1min according to the foaming sequence of the TPU film precursor and the temperature sections of 150 ℃, 230 ℃ and 190 ℃ which are sequentially passed through.
Example 8
The TPU foaming layer comprises the following raw materials in parts by weight: 100 parts of TPU, 5 parts of lubricant, 8 parts of foaming agent and 30 parts of plasticizing assistant.
The TPU surface layer comprises the following raw materials in parts by weight: 100 parts of TPU, 5 parts of lubricant and 20 parts of plasticizing assistant.
Wherein the hardness of the TPU is 55A; the lubricant is lead stearate; the foaming agent is an AC foaming agent; the plasticizing auxiliary agent is ACR.
The raw materials of the foaming layer are subjected to calendering molding at the temperature of 110 ℃ to obtain a TPU foaming film precursor; and (3) rolling and molding the raw materials of the surface layer at 120 ℃ to obtain the TPU surface layer.
Arranging the TPU foaming film precursor on a knitted fabric, and arranging a TPU surface layer on the TPU foaming precursor to obtain a TPU synthetic leather precursor;
and (2) placing the TPU synthetic leather precursor into a foaming furnace for foaming, wherein the foaming furnace is controlled by four sections of temperature, and the TPU synthetic leather is obtained by foaming for 1min according to the foaming sequence of the TPU film precursor and the temperature sections of 150 ℃, 230 ℃ and 190 ℃ which are sequentially passed through.
Comparative example 1
The TPU foaming layer comprises the following raw materials in parts by weight: 100 parts of TPU, 0 part of lubricant, 2 parts of foaming agent and 10 parts of plasticizing assistant.
The TPU surface layer comprises the following raw materials in parts by weight: 100 parts of TPU, 0.1 part of lubricant and 5 parts of plasticizing assistant.
Wherein the hardness of the TPU is 60A; the foaming agent is an AC foaming agent; the plasticizing auxiliary agent is ACR.
The raw materials of the foaming layer are subjected to calendering molding at the temperature of 110 ℃ to obtain a TPU foaming film precursor; and (3) rolling and molding the raw materials of the surface layer at 120 ℃ to obtain the TPU surface layer.
Arranging the TPU foaming film precursor on a knitted fabric, and arranging a TPU surface layer on the TPU foaming precursor to obtain a TPU synthetic leather precursor;
and (2) placing the TPU synthetic leather precursor into a foaming furnace for foaming, wherein the foaming furnace is controlled by four sections of temperature, and the TPU synthetic leather is obtained by foaming for 2min according to the foaming sequence of the TPU film precursor and the temperature sections of 125 ℃, 190 ℃, 210 ℃ and 170 ℃ which are sequentially passed through.
Comparative example 2
The TPU foaming layer comprises the following raw materials in parts by weight: 100 parts of TPU, 0.1 part of lubricant, 1 part of foaming agent and 10 parts of plasticizing assistant.
The TPU surface layer comprises the following raw materials in parts by weight: 100 parts of TPU, 0.1 part of lubricant and 5 parts of plasticizing assistant.
Wherein the hardness of the TPU is 60A; the lubricant is cadmium stearate; the foaming agent is an AC foaming agent; the plasticizing auxiliary agent is ACR.
The raw materials of the foaming layer are subjected to calendering molding at the temperature of 110 ℃ to obtain a TPU foaming film precursor; and (3) rolling and molding the raw materials of the surface layer at 120 ℃ to obtain the TPU surface layer.
Arranging the TPU foaming film precursor on a knitted fabric, and arranging a TPU surface layer on the TPU foaming precursor to obtain a TPU synthetic leather precursor;
and (2) placing the TPU synthetic leather precursor into a foaming furnace for foaming, wherein the foaming furnace is controlled by four sections of temperature, and the TPU synthetic leather is obtained by foaming for 2min according to the foaming sequence of the TPU film precursor and the temperature sections of 125 ℃, 190 ℃, 210 ℃ and 170 ℃ which are sequentially passed through.
Comparative example 3
The TPU foaming layer comprises the following raw materials in parts by weight: 100 parts of TPU, 0.1 part of lubricant, 2 parts of foaming agent and 32 parts of plasticizing assistant.
The TPU surface layer comprises the following raw materials in parts by weight: 100 parts of TPU, 0.1 part of lubricant and 5 parts of plasticizing assistant.
Wherein the hardness of the TPU is 60A; the lubricant is cadmium stearate; the foaming agent is an AC foaming agent; the plasticizing auxiliary agent is ACR.
The raw materials of the foaming layer are subjected to rolling molding at 110 ℃ to obtain a TPU foaming layer precursor; and (3) rolling and molding the raw materials of the surface layer at 120 ℃ to obtain the TPU surface layer.
Arranging the TPU foaming film precursor on a knitted fabric, and arranging a TPU surface layer on the TPU foaming precursor to obtain a TPU synthetic leather precursor;
and (2) placing the TPU synthetic leather precursor into a foaming furnace for foaming, wherein the foaming furnace is controlled by four sections of temperature, and the TPU synthetic leather is obtained by foaming for 2min according to the foaming sequence of the TPU film precursor and the temperature sections of 125 ℃, 190 ℃, 210 ℃ and 170 ℃ which are sequentially passed through.
Comparative example 4
The PVC foaming layer comprises the following raw materials in parts by weight: 100 parts of PVC, 0.1 part of lubricant, 2 parts of foaming agent and 30 parts of plasticizing auxiliary agent.
The PVC surface layer comprises the following raw materials in parts by weight: 100 parts of PVC, 0.1 part of a lubricant and 5 parts of a plasticizing adjuvant.
The foaming agent is an AC foaming agent; the plasticizing auxiliary agent is ACR.
The raw materials of the foaming layer are subjected to roll forming at 116 ℃ to obtain a PVC foaming layer precursor; and (3) rolling and molding the raw materials of the surface layer at 120 ℃ to obtain the PVC surface layer.
Arranging the TPU foaming film precursor on a knitted fabric, and arranging a TPU surface layer on the TPU foaming precursor to obtain a TPU synthetic leather precursor;
and (2) placing the PVC synthetic leather precursor into a foaming furnace for foaming, wherein the foaming furnace is controlled by four sections of temperature, and the PVC synthetic leather is obtained by foaming for 2min according to the foaming sequence of the PVC film precursor and the temperature sections of 125 ℃, 190 ℃, 210 ℃ and 170 ℃ which pass through in sequence.
The performance of the TPU synthetic leather or the PVC synthetic leather prepared in each embodiment and each comparative example is detected, and the uniformity of the cells is detected in a visual inspection mode of 100 persons; detecting the tensile load according to GB/T1646-2007; tear load was detected according to GB/T2710-2005. The results are shown in Table 1 below.
Table 1:
| cell uniformity | Tensile Strength/N | Tear Strength/N | |
| Example 1 | ++++ | 581 | 59 |
| Example 2 | ++++ | 580 | 58 |
| Example 3 | +++++ | 585 | 56 |
| Example 4 | +++++ | 586 | 57 |
| Example 5 | ++++++ | 595 | 56 |
| Example 6 | ++++++ | 589 | 58 |
| Example 7 | +++ | 577 | 61 |
| Example 8 | +++ | 576 | 62 |
| Comparative example 1 | ++ | 570 | 60 |
| Comparative example 2 | + | 600 | 70 |
| Comparative example3 | ++ | 572 | 62 |
| Comparative example 4 | +++ | 580 | 65 |
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: by the synergistic cooperation of the TPU, the lubricant, the foaming agent and the plasticizing auxiliary agent in specific parts by weight, the raw material mixture can obtain a hand feeling similar to that of PVC synthetic leather with the same formula through foaming, so that the application value of the TPU foaming material in the aspects of home decoration and automotive decoration materials is improved.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (14)
1. A preparation method of a TPU foaming material is characterized by comprising the following steps:
carrying out calendaring molding on the raw material of the foaming material to obtain a TPU film precursor;
placing the TPU film precursor into a foaming furnace for foaming, and controlling the temperature of the foaming furnace in four sections, wherein the temperature sections sequentially pass through the foaming sequence of the TPU film precursor are 135 +/-10 ℃, 200 +/-10 ℃, 220 +/-10 ℃ and 180 +/-10 ℃, and the total foaming time is 1-2 min, so as to obtain the TPU foaming material;
the TPU foaming material comprises the following raw materials in parts by weight: 100 parts of TPU, 0.1-5 parts of lubricant, 2-8 parts of foaming agent and 10-30 parts of plasticizing auxiliary agent, wherein the plasticizing auxiliary agent is ACR.
2. The preparation method according to claim 1, wherein the TPU foaming material comprises the following raw materials in parts by weight: 100 parts of TPU, 0.2-2 parts of lubricant, 2-6 parts of foaming agent and 10-25 parts of plasticizing auxiliary agent.
3. The process according to claim 1, wherein the TPU has a hardness of from 60A to 45D.
4. The method of claim 1 or 2, wherein the lubricant is a metal soap lubricant.
5. The method of claim 1 or 2, wherein the lubricant is cadmium stearate.
6. The production method according to claim 1 or 2, characterized in that the blowing agent is an AC blowing agent.
7. The preparation method of claim 1 or 2, wherein the TPU foaming material further comprises 1-5 parts by weight of a foaming promoter.
8. The preparation method of claim 7, wherein the raw material of the TPU foaming material further comprises 1-2 parts of the foaming promoter.
9. The TPU synthetic leather comprises a base cloth, a TPU foaming layer and a TPU surface layer which are sequentially overlapped, and is characterized in that the TPU foaming layer is prepared by the preparation method of any one of claims 1 to 8.
10. The TPU synthetic leather of claim 9, wherein the TPU facing layer comprises, in parts by weight: 100 parts of TPU, 0.1-5 parts of lubricant and 5-20 parts of plasticizing auxiliary agent.
11. The TPU synthetic leather of claim 10, wherein the TPU facing layer comprises, in parts by weight: 100 parts of TPU, 0.3-2 parts of the lubricant and 6-18 parts of the plasticizing auxiliary agent.
12. The TPU synthetic leather of claim 10, wherein the lubricant is a metal soap lubricant.
13. The TPU synthetic leather of claim 10, wherein the plasticizing aid is ACR.
14. The TPU synthetic leather of claim 12, wherein the TPU has a hardness of 60A to 45D.
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| CN114369357A (en) * | 2022-01-12 | 2022-04-19 | 刘堂连 | Composition for foaming material |
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| KR20070110626A (en) * | 2006-05-15 | 2007-11-20 | 진양화학 주식회사 | Thermoplastic polyurethane composition |
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