CN113322683B - Hard composite artificial leather capable of being embossed and preparation method thereof - Google Patents
Hard composite artificial leather capable of being embossed and preparation method thereof Download PDFInfo
- Publication number
- CN113322683B CN113322683B CN202110449517.9A CN202110449517A CN113322683B CN 113322683 B CN113322683 B CN 113322683B CN 202110449517 A CN202110449517 A CN 202110449517A CN 113322683 B CN113322683 B CN 113322683B
- Authority
- CN
- China
- Prior art keywords
- parts
- foaming layer
- artificial leather
- layer coating
- hard composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
- D06N3/0095—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by inversion technique; by transfer processes
- D06N3/0097—Release surface, e.g. separation sheets; Silicone papers
-
- 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
-
- 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
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0059—Organic ingredients with special effects, e.g. oil- or water-repellent, antimicrobial, flame-resistant, magnetic, bactericidal, odour-influencing agents; perfumes
-
- 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
- D06N3/007—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by mechanical or physical treatments
- D06N3/0077—Embossing; Pressing of the surface; Tumbling and crumbling; Cracking; Cooling; Heating, e.g. mirror finish
-
- 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
- D06N3/146—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 characterised by the macromolecular diols used
-
- 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
- D06N3/147—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 characterised by the isocyanates used
Abstract
The invention discloses a method for preparing hard composite artificial leather capable of embossing, which comprises the following steps: coating a first foaming layer coating on the release paper, and curing; coating a second foaming layer coating, and heating for gelation; attaching a substrate, solidifying, cooling and separating release paper; then heating and embossing, and cooling to obtain the finished product. Correspondingly, the invention also discloses the hard composite artificial leather capable of embossing. The grain with good decorative effect can be directly obtained by embossing, the decorative grain has good plumpness, strong stereoscopic impression, straightness and vividness, and can be directly used without later sewing.
Description
Technical Field
The invention relates to the technical field of artificial leather, in particular to hard composite artificial leather capable of being embossed and a preparation method thereof.
Background
The polyurethane synthetic leather has excellent wear resistance, solvent resistance, aging resistance and other performances, excellent hand feeling and soft surface gloss, is the most ideal substitute of natural leather, and can be widely applied to the fields of shoes, leather bags, sofas, automotive interiors and the like.
Polyurethane synthetic leather is generally divided into solvent type and solvent-free type, wherein a large amount of solvent is required to be introduced in the production process of solvent type polyurethane synthetic leather, and the environmental pollution is serious. The solvent-free polyurethane synthetic leather does not introduce an organic solvent, and has the advantage of environmental protection. However, the solvent-free polyurethane synthetic leather does not contain a solvent in a production system, so that the through-type micropores of a foaming layer are few, the softness is poor, and the direct embossing or pattern absorption is difficult, so that the solvent-free polyurethane synthetic leather is often processed in a later stage and needs to be further sewn to endow decorative patterns.
In order to solve the above problems, the applicant proposed a method for preparing a composite polyurethane film (CN 104369516B) in the prior application, in which a substrate layer with decorative grains is used for pressing to endow the synthetic leather with decorative grains. However, when some soft substrates are employed, it is often difficult to carry a pattern. And the hard substrate is easy to cause softening of the decorative lines due to heating in the attaching process, and the decorative effect is not ideal.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of hard composite artificial leather capable of embossing, which can realize solvent-free production and is environment-friendly; and the shaping is easy, and the product has strong integrity.
The invention also aims to solve the technical problem of providing the hard composite artificial leather capable of being embossed.
In order to solve the technical problems, the invention provides a method for preparing an embossable hard composite artificial leather, which comprises the following steps:
(1) Providing release paper;
(2) Coating a first foaming layer coating on the surface of the release paper, and heating and curing;
(3) Coating a second foaming layer coating on the first foaming layer, and heating to gelatinize the second foaming layer coating;
(4) Attaching the substrate to the gelled second foaming layer coating to obtain an intermediate material;
(5) Heating the intermediate material to cure the second foaming layer coating;
(6) Cooling the intermediate material obtained in the step (5), and separating the release paper to obtain a semi-finished product;
(7) Heating the semi-finished product, and embossing the heated semi-finished product;
(8) And cooling the embossed semi-finished product to obtain the embossed hard composite artificial leather finished product.
As an improvement of the technical scheme, the first foaming layer coating comprises the following components in parts by weight:
60-65 parts of graft modified isocyanate, 30-50 parts of polyol, 20-30 parts of filler, 0.05-0.1 part of catalyst and 20-50 parts of thermoplastic powder;
the second foaming layer coating comprises the following components in parts by weight:
65-80 parts of polyol, 18-35 parts of graft modified isocyanate, 20-50 parts of filler, 0.05-1 part of catalyst and 0.5-30 parts of thermoplastic powder;
the grafting modified isocyanate is mainly prepared from the following raw materials in parts by weight:
80-100 parts of isocyanate, 80-120 parts of polyol and 0.05-0.5 part of catalyst.
As an improvement of the above technical solution, the second foamed layer coating further includes: 1-2 parts of a foam stabilizer.
As the improvement of the technical proposal, the filler is diatomite and/or light calcium carbonate;
the polyester polyol is polycarbonate polyol;
the isocyanate is one or more of 4, 4-diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate.
As an improvement of the technical scheme, the step (7) comprises the following steps:
(7.1) forming a top layer on the second foamed layer;
(7.2) heating the semi-finished product with the surface layer, and embossing the heated semi-finished product.
As an improvement of the technical scheme, in the step (2), the heating temperature is 80-120 ℃; in the step (3), the heating temperature is 60-100 ℃; in the step (5), the heating temperature is 60-100 ℃.
As an improvement of the technical scheme, in the step (7), the heating temperature is 180-240 ℃;
in the step (8), a cooling roller is adopted for cooling, and the surface temperature of the cooling roller is 20-30 ℃.
As an improvement of the above technical solution, the coating amount of the first foaming layer coating is: the coating amount of the second foaming layer coating =1: (5-8).
As an improvement of the above technical means, in the step (8), cooling is performed after 6 to 15 seconds after the embossing.
Correspondingly, the invention also discloses the hard composite artificial leather capable of being embossed, which is prepared by the preparation method of the hard composite artificial leather capable of being embossed.
The implementation of the invention has the following beneficial effects:
1. the formula of the second foaming layer of the hard composite artificial leather capable of being embossed in the invention comprises 65-80 parts of polyol, 18-35 parts of graft modified isocyanate, 20-50 parts of filler, 0.05-1 part of catalyst and 0.5-30 parts of thermoplastic powder; through adding the thermoplastic powder among the formula, can effectively reduce the hardness of second foaming layer and first foaming layer for it can produce the line that decorative effect is good through the impressed watermark, and this decorative line plumpness is good, and the third dimension is strong, and is straight lifelike, need not later stage sewing and can directly use.
2. The coating adopted by the hard composite artificial leather capable of being embossed is a solvent-free system, and is green and environment-friendly.
Drawings
Fig. 1 is a flowchart of a method for manufacturing embossable hard composite artificial leather of the present invention;
FIG. 2 is a scanning electron micrograph of a second foamed layer of example 1;
FIG. 3 is a scanning electron micrograph of a second foamed layer of example 2;
FIG. 4 is a scanning electron micrograph of a second foamed layer of example 3;
FIG. 5 is a scanning electron micrograph of a second foamed layer of example 4;
FIG. 6 is a thermogravimetric analysis of the second foamed layer coating in example 4.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the accompanying drawings and embodiments.
Referring to fig. 1, the present invention provides a method for preparing embossable hard composite artificial leather, comprising the steps of:
s1: providing release paper;
s2: coating a first foaming layer coating on the surface of the release paper, and heating and curing;
specifically, a first foaming layer coating is coated on any surface of the release paper, and the release paper is heated to enable the first foaming layer to be completely foamed and cured. The heating temperature is, for example, 80 to 120 ℃ and is, for example, 82 ℃, 90 ℃, 100 ℃ or 112 ℃, but is not limited thereto. Preferably, the heating temperature is 80 to 100 ℃.
The first foaming layer coating comprises the following components in parts by weight:
60-65 parts of graft modified isocyanate, 30-50 parts of polyol, 20-30 parts of filler, 0.05-0.1 part of catalyst and 20-50 parts of thermoplastic powder.
Wherein, the graft modified isocyanate is a product of prepolymerization reaction of isocyanate and polyol. Specifically, the feed additive is prepared from the following raw materials in parts by weight: 80-100 parts of isocyanate, 80-120 parts of polyol and 0.05-0.5 part of catalyst.
The isocyanate may be selected from 4, 4-diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, p-isopropylphenyl isocyanate, and one or more of 4, 4-diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and p-isopropylphenyl isocyanate modified by introducing uretdione, urethane, carbodiimide, and isocyanurate groups, but is not limited thereto. The isocyanate is used in an amount of 80 to 100 parts, illustratively 85 parts, 92 parts, 95 parts, 98 parts, or 100 parts, but is not limited thereto.
The polyester polyol is polycarbonate polyol or polyester polyol, but not limited thereto. Preferably, the polyester polyol is polycarbonate polyol, and the relative molecular weight of the polyester polyol is more than or equal to 2000; the artificial leather prepared from the polyalcohol has excellent mechanical property and hydrolysis resistance. Specifically, in the prepolymerization, the amount of the polyhydric alcohol is 80 to 120 parts, illustratively 80 parts, 83 parts, 88 parts, 95 parts, 100 parts or 115 parts, but is not limited thereto. The amount of the polymeric polyol in the first foam layer coating is 30 to 50 parts, illustratively 35 parts, 42 parts, 46 parts, or 48 parts, but is not limited thereto. In the first foam layer coating, when the amount of the polymeric polyol is less than 30 parts, the first foam layer is too hard to be embossed or sucked.
The catalyst is an organotin catalyst or an organozinc catalyst, but is not limited thereto. In the prepolymerization, the catalyst is used in an amount of 0.05 to 0.5 parts, illustratively 0.1 part, 0.3 part, or 0.5 part, but is not limited thereto. The catalyst is used in the first foaming layer paint in an amount of 0.05 parts to 0.1 parts, illustratively 0.05 parts, 0.07 parts, or 0.08 parts, but is not limited thereto.
Wherein, the filler can be selected from the group consisting of calcium carbonate, diatomaceous earth, etc., but is not limited thereto. Preferably, the filler is selected from diatomite and/or light calcium carbonate. The two fillers can improve the air permeability of the artificial leather and improve the sanitary performance. Preferably, the filler is light calcium carbonate, and the light calcium carbonate can effectively adjust the microscopic pore size in the first foaming layer to form the first foaming layer with uniform pore size, so that the mechanical property is improved. Specifically, the filler is used in an amount of 20 to 30 parts, illustratively 22 parts, 24 parts, 25 parts, or 29 parts, but is not limited thereto.
The thermoplastic plastic powder can effectively reduce the hardness of the first foaming layer coating system, so that the first foaming layer coating system has certain plasticity, and decorative patterns can be endowed by the first foaming layer coating system through an embossing or embossing process; in addition, the thermoplastic plastic powder can also improve the production efficiency. Specifically, the amount of the thermoplastic powder is 20-50 parts, and when the amount is less than 20 parts, the plasticity of the first foaming layer is poor and embossing is difficult; when the amount is more than 50 parts, the mechanical properties such as tear strength, tensile strength, etc. of the artificial leather are reduced. Preferably, the thermoplastic powder is used in an amount of 20 to 30 parts, illustratively 20 parts, 22 parts, 25 parts, or 27 parts, but is not limited thereto.
It should be noted that the thermoplastic material has strong plasticity and is easy to shape, and can be used for preparing lines with good decorative effect, but the whole mechanical property is poor, and the use requirement is difficult to meet. Although the thermosetting material has strong performance, the thermosetting material is difficult to deform and is difficult to endow better decorative lines. According to the invention, through reasonable formula adjustment, the mechanical property of the thermosetting first foaming layer coating is maintained, and the thermosetting first foaming layer coating is endowed with excellent high-temperature plasticity, so that the thermosetting first foaming layer coating can be directly decorated by adopting an embossing or embossing absorption process, and does not need to be decorated by sewing and other processes in the later stage.
The raw materials of the first foam layer coating material in the present invention are not limited to the above graft-modified isocyanate, polymeric polyol, filler, catalyst and thermoplastic powder; the person skilled in the art can also add the usual auxiliaries such as pigments, UV absorbers, matting agents, etc., to the formulation as required.
S3: coating a second foaming layer coating on the first foaming layer, and heating to gelatinize the second foaming layer coating;
wherein the heating temperature is 60 to 100 deg.C, illustratively 65 deg.C, 70 deg.C, 85 deg.C or 90 deg.C, but is not limited thereto. The second foaming layer coating is gelled through heating so as to have certain adhesive force, and the first foaming layer and the substrate are further effectively adhered.
Wherein, the coating amount of the second foaming layer is: coating amount of the first foam layer coating = (5 to 8): 1; the first foaming layer and the second foaming layer with different thicknesses and different hardness are formed by controlling the coating amount of the first foaming layer and the coating amount of the second foaming layer, and the decoration effect can be optimized by matching the first foaming layer and the second foaming layer.
The second foaming layer coating comprises the following components in parts by weight:
65-80 parts of polyol, 18-35 parts of graft modified isocyanate, 20-50 parts of filler, 0.05-1 part of catalyst and 0.5-30 parts of thermoplastic powder;
the polyester polyol is polycarbonate polyol or polyester polyol, but not limited thereto. The second foaming layer prepared from the two kinds of polyol has more foaming holes, is uniformly distributed, contains more through micropores, and is convenient for embossing in the later period. Preferably, the polyester polyol is polycarbonate polyol, and the relative molecular weight of the polyester polyol is more than or equal to 2000; the artificial leather prepared from the polyalcohol has excellent mechanical property and hydrolysis resistance. Specifically, the polymeric polyol is used in an amount of 65 to 80 parts, illustratively 66 parts, 69 parts, 72 parts, 75 parts, or 79 parts, but is not limited thereto. When the amount of the polyhydric alcohol is less than 65 parts, the second foamed layer is too hard to be embossed or embossed. When the amount is more than 80 parts, mechanical properties such as tear strength, tensile strength and the like are poor.
Wherein, the grafted modified isocyanate is a product of prepolymerization reaction of isocyanate and polyhydric alcohol polymer. Specifically, the feed additive is prepared from the following raw materials in parts by weight: 80-100 parts of isocyanate, 80-120 parts of polyol and 0.05-0.5 part of catalyst. Specifically, in the second foamed layer coating, the graft-modified isocyanate is used in an amount of 18 to 35 parts, illustratively 20 parts, 25 parts, 30 parts or 34 parts, but is not limited thereto. By controlling the dosage of the grafted modified isocyanate and the polyol, the reaction index (NCO/OH) can be controlled to be more than 1.1, so that the second foaming layer is endowed with excellent mechanical property, and the second foaming layer can be maintained not to be decomposed before 276 ℃, so that a good foundation is provided for later-stage heating embossing.
Wherein, the filler can be selected from the group consisting of calcium carbonate, diatomaceous earth, etc., but is not limited thereto. Preferably, the filler is selected from diatomite and/or light calcium carbonate. The two fillers can improve the air permeability of the artificial leather and improve the sanitary performance. Preferably, the filler is light calcium carbonate, and the light calcium carbonate can homogenize micropores in the second foaming layer, so that the mechanical property is improved. Specifically, the filler is used in an amount of 20 to 50 parts, illustratively 25 parts, 30 parts, 35 parts, or 45 parts, but is not limited thereto. Preferably, the filler is used in an amount of 25 to 35 parts.
The catalyst is an organotin catalyst or an organozinc catalyst, but is not limited thereto. The catalyst is used in an amount of 0.05 to 1 part, illustratively 0.1 part, 0.5 part, 0.7 part, or 0.8 part, but is not limited thereto. The preferred amount of catalyst is 0.1 to 0.5 parts.
The thermoplastic plastic powder can effectively reduce the hardness of the second foaming layer coating system, so that the second foaming layer coating system has certain plasticity, and decorative patterns can be endowed by the embossing or embossing absorption process; in addition, the production efficiency can be improved by the thermoplastic powder. Specifically, the amount of the thermoplastic powder is 0.5-30 parts. Preferably, the thermoplastic powder is used in an amount of 10 to 20 parts, illustratively 10 parts, 15 parts, 16 parts, or 28 parts, but is not limited thereto.
Further, the second foamed layer coating of the present invention further includes 1 to 2 parts of a foam stabilizer, illustratively, 1.1 parts, 1.3 parts, or 1.5 parts, but is not limited thereto. Specifically, the foam stabilizer may be polyether modified silicone oil, but is not limited thereto.
The raw materials of the second foamed layer coating material in the present invention are not limited to the above graft-modified isocyanate, polyhydric alcohol, filler, catalyst, foam stabilizer and thermoplastic powder; the person skilled in the art can also add the usual auxiliaries such as pigments, UV absorbers, matting agents, etc., to the formulation as required.
S4: attaching the substrate to the gelled second foaming layer coating to obtain an intermediate material;
specifically, the substrate may be selected from textile, leather fiber, metal foil, plastic, or cross-linked, but not limited thereto. Preferably, the substrate is a polyester fiber non-woven fabric, and the adhesion between the polyester fiber non-woven fabric and the second foaming layer is better.
S5: heating the intermediate material to cure the second foaming layer coating;
wherein the heating temperature is 60 to 100 deg.C, illustratively 65 deg.C, 70 deg.C, 75 deg.C, 80 deg.C or 95 deg.C, but not limited thereto. Preferably, the heating temperature is 60 to 80 ℃.
S6: cooling the intermediate material obtained in the step S5, and separating release paper to obtain a semi-finished product;
specifically, the semi-finished product may be coiled after cooling.
S7: heating the semi-finished product, and embossing the heated semi-finished product;
specifically, S7 includes:
s71: forming a surface layer on the second foaming layer;
specifically, the top layer may be formed by coating a leather top coating (e.g., a top coating of H-R-skin type manufactured by Otsu Green materials technologies, inc.) commonly used in the art, or by attaching a protective film commonly used in the art, but is not limited thereto. Can give the synthetic leather abundanter color effect through the surface course, promote its decorative ability.
S72: and heating the semi-finished product with the surface layer, and embossing the heated semi-finished product.
Specifically, the heating temperature is 180-240 ℃, and when the heating temperature is less than 180 ℃, decorative lines cannot be extruded; when the temperature is higher than 240 ℃, the structures of the first foaming layer and the second foaming layer are damaged, and the mechanical property is greatly reduced. Preferably, the heating temperature is 200 to 220 ℃, exemplary 200 ℃, 205 ℃, 210 ℃ or 215 ℃, but not limited thereto.
S8: cooling the semi-finished product after embossing to obtain a hard composite artificial leather finished product capable of embossing;
specifically, the cooling is carried out by adopting a cooling roller, the temperature of the surface of the cooling roller is controlled to be 20-30 ℃, and 2/3-3/4 of the cooling roller is in contact with the artificial leather (even if the artificial leather is wrapped by 2/3-3/4 of the cooling roller in the circumferential direction of the cooling roller).
Further, in order to optimize the decorative texture effect, cooling is carried out in 6-15 s of embossing.
The invention is further illustrated by the following specific examples:
example 1
The embodiment provides a preparation method of hard composite artificial leather capable of embossing, which comprises the following steps:
(1) Providing release paper;
(2) Coating a first foaming layer coating on the surface of the release paper, and heating at 110 ℃ until the release paper is completely cured;
wherein, the formula of the first foaming layer coating is as follows:
65 parts of graft modified isocyanate, 35 parts of polyester polyol (C1120, xian Lei Ming chemical technology Co., ltd.), 25 parts of diatomite, 0.08 part of catalyst and 50 parts of thermoplastic powder;
wherein, the grafting modified isocyanate is prepared by the reaction of 100 parts of TDI, 100 parts of polyester polyol and 0.2 part of catalyst at 120 ℃.
(3) Coating a second foaming layer coating on the first foaming layer, and heating at 80 ℃ to gelatinize the second foaming layer coating;
the formula of the second foaming layer coating is as follows:
20 parts of graft modified isocyanate, 80 parts of polyester polyol, 30 parts of light calcium carbonate, 0.1 part of catalyst, 20 parts of thermoplastic powder and 0.5 part of foam stabilizer (LM 2003, xian Lei Ming chemical science and technology Co., ltd.);
(4) Attaching the substrate to the gelled second foaming layer coating to obtain an intermediate material;
wherein the substrate is polyester fiber type non-woven fabric;
(5) Heating the intermediate material at 80 ℃ to cure the second foam layer coating;
(6) Cooling the intermediate material obtained in the step (5) to room temperature, and separating the release paper to obtain a semi-finished product;
(7) Coating a surface layer coating (H-R-Skin, shanghai lan Sheng green material science and technology limited) on one side of a second foaming layer of the semi-finished product, and curing;
(8) Heating the semi-finished product with the surface layer to 180 ℃, and embossing the heated semi-finished product;
(9) Cooling the semi-finished product after embossing to obtain a hard composite artificial leather finished product capable of embossing;
specifically, the artificial leather is cooled by a cooling roller within 10s after embossing, the temperature of the cooling roller is 25 ℃, and 3/4 of the cross section of the cooling roller is in contact with the artificial leather.
Example 2
This example provides a method for preparing embossable hard composite artificial leather, which is different from example 1 in that polycarbonate polyol (C1136, west ampere bud, chemical technology ltd) is used as the polyol.
Example 3
This example provides a method for preparing embossable hard composite artificial leather, which is different from example 1 in that light calcium carbonate is used as the filler.
Example 4
The embodiment provides a preparation method of hard composite artificial leather capable of being embossed, which comprises the following steps:
(1) Providing release paper;
(2) Coating a first foaming layer coating on the surface of the release paper, and heating at 100 ℃ until the first foaming layer coating is completely cured;
wherein, the formula of the first foaming layer coating is as follows:
62 parts of graft modified isocyanate, 38 parts of polycarbonate polyol (C1136, xian Lei Ming chemical technology Co., ltd.), 20 parts of light calcium carbonate, 0.1 part of catalyst and 45 parts of thermoplastic powder;
wherein, the graft modified isocyanate is prepared by the reaction of 100 parts of MDI, 80 parts of polycarbonate polyol and 0.2 part of catalyst at 110 ℃.
(3) Coating a second foam layer coating on the first foam layer and heating at 90 ℃ to gel the second foam layer coating;
the formula of the second foaming layer coating is as follows:
23 parts of graft modified isocyanate, 77 parts of polycarbonate polyol (C1136, xian Lei Ming chemical technology Co., ltd.), 30 parts of light calcium carbonate, 0.1 part of catalyst, 25 parts of thermoplastic powder and 0.5 part of foam homogenizing agent (LM 2003, xian Lei Ming chemical technology Co., ltd.);
(4) Attaching the substrate to the gelled second foaming layer coating to obtain an intermediate material;
wherein the substrate is polyester fiber type non-woven fabric;
(5) Heating the intermediate material at 80 ℃ to cure the second foam layer coating;
(6) Cooling the intermediate material obtained in the step (5) to room temperature, and separating the release paper to obtain a semi-finished product;
(7) Coating a surface layer coating (H-R-Skin, shanghai Lansheng green materials science and technology Co., ltd.) on one side of the second foaming layer of the semi-finished product, and curing;
(8) Heating the semi-finished product with the surface layer to 200 ℃, and embossing the heated semi-finished product;
(9) Cooling the semi-finished product after embossing to obtain an embossable hard composite artificial leather finished product;
specifically, the artificial leather is cooled by a cooling roller within 10s after embossing, the temperature of the cooling roller is 25 ℃, and 3/4 of the cross section of the cooling roller is in contact with the artificial leather.
The embossable hard composite artificial leather of examples 1 to 4 was tested by the following specific method:
(1) Testing the tensile strength and the elongation at break according to the method of GB/T528;
(2) Tear force was tested according to method GB 16799;
(3) A leather softness tester (HD-2045, haidao instruments Co., ltd., dongguan) is adopted to test the softness;
(4) Measuring air permeability by adopting a QB/T2799 method;
(5) Observing the microstructure of the second foamed layer by using a scanning electron microscope (Hitachi S4800);
(6) The second foam layer coating in example 4 was measured using a thermogravimetric analyzer (Q500, TA).
The specific results are as follows:
as can be seen from the table, the tensile strength of the hard composite artificial leather is more than or equal to 6.5MPa, the elongation at break is more than or equal to 380.4 percent, the tearing force is more than or equal to 42.1N, the softness is less than or equal to 5.13mm, and the air permeability is more than or equal to 8365 mL-cm -1 ·h -1 The artificial leather of the invention has good mechanical property and sanitary property.
While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not to be limited to the disclosed embodiment, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
Claims (8)
1. A preparation method of hard composite artificial leather capable of being embossed is characterized by comprising the following steps:
(1) Providing release paper;
(2) Coating a first foaming layer coating on the surface of the release paper, and heating and curing;
(3) Coating a second foaming layer coating on the first foaming layer, and heating to gelatinize the second foaming layer coating;
(4) Attaching the substrate to the gelled second foaming layer coating to obtain an intermediate material;
(5) Heating the intermediate material to cure the second foaming layer coating;
(6) Cooling the intermediate material obtained in the step (5), and separating the release paper to obtain a semi-finished product;
(7) Heating the semi-finished product, and embossing the heated semi-finished product; wherein the heating temperature is 180 to 240 ℃;
(8) Cooling the semi-finished product after embossing to obtain a hard composite artificial leather finished product capable of embossing;
the first foaming layer coating comprises the following components in parts by weight:
60-65 parts of graft modified isocyanate, 30-50 parts of polyol, 20-30 parts of filler, 0.05-0.1 part of catalyst and 20-50 parts of thermoplastic powder;
the second foaming layer coating comprises the following components in parts by weight:
65-80 parts of polyol, 18-35 parts of graft modified isocyanate, 20-50 parts of filler, 0.05-1 part of catalyst and 0.5-30 parts of thermoplastic powder;
the grafted modified isocyanate is mainly prepared from the following raw materials in parts by weight:
80-100 parts of isocyanate, 80-120 parts of polyol and 0.05-0.5 part of catalyst.
2. The method of manufacturing embossable hard composite artificial leather according to claim 1, wherein said second foaming layer coating further comprises: 1 to 2 parts of foam stabilizer.
3. The method of manufacturing embossed hard composite artificial leather according to claim 1, wherein the filler is selected from diatomaceous earth and/or light calcium carbonate;
the polyester polyol is polycarbonate polyol;
the isocyanate is one or more of 4, 4-diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate.
4. The method for preparing the embossable hard composite artificial leather according to claim 1, wherein in the step (2), the heating temperature is 80 to 120 ℃; in the step (3), the heating temperature is 60 to 100 ℃; in the step (5), the heating temperature is 60 to 100 ℃.
5. The method for preparing an embossable hard composite artificial leather according to claim 1, wherein in the step (8), the cooling is carried out by using a cooling roll, and the surface temperature of the cooling roll is 20 to 30 ℃.
6. The method of manufacturing embossable hard composite artificial leather according to claim 1, wherein the coating amount of said first foam layer coating is: the coating amount of the second foaming layer coating =1: (5 to 8).
7. The method of producing an embossable hard composite artificial leather according to claim 1, wherein in the step (8), cooling is performed 6 to 15s after embossing.
8. An embossable hard composite artificial leather, which is prepared by the preparation method of the embossable hard composite artificial leather according to any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110449517.9A CN113322683B (en) | 2021-04-25 | 2021-04-25 | Hard composite artificial leather capable of being embossed and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110449517.9A CN113322683B (en) | 2021-04-25 | 2021-04-25 | Hard composite artificial leather capable of being embossed and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113322683A CN113322683A (en) | 2021-08-31 |
| CN113322683B true CN113322683B (en) | 2022-11-22 |
Family
ID=77413712
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110449517.9A Active CN113322683B (en) | 2021-04-25 | 2021-04-25 | Hard composite artificial leather capable of being embossed and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113322683B (en) |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11256031A (en) * | 1998-03-11 | 1999-09-21 | Kuraray Co Ltd | Foamable polyurethane composition and foam obtained therefrom |
| CN102444030B (en) * | 2011-08-31 | 2013-10-02 | 佛山市飞凌皮革化工有限公司 | Method for producing synthetic leather by using solvent-free double-component polyurethane scraping and coating method |
| CN102582304A (en) * | 2012-03-01 | 2012-07-18 | 杭州鹰自达塑业有限公司 | Method for forming foaming product on release paper by adopting printing technology |
| CN103361988A (en) * | 2012-03-28 | 2013-10-23 | 广州市宏伟皮革有限公司 | Ecological type water-based synthetic leather |
| CN104369516B (en) * | 2013-08-12 | 2017-01-25 | 佛山市高明区业晟聚氨酯有限公司 | Preparation method of composite polyurethane film |
| CN103696274B (en) * | 2013-12-27 | 2015-11-18 | 四川大学 | A kind of foaming synthetic leather manufacture method based on water-base resin and TPU resin |
| CN104032587B (en) * | 2014-05-14 | 2016-06-29 | 浙江禾欣实业集团股份有限公司 | The manufacture method of uninanned platform leather can be embossed |
| CN105992847B (en) * | 2015-05-28 | 2018-12-18 | 鹤山市新科达企业有限公司 | A kind of production method of non-solvent foamed type polyurethane synthetic leather |
| BE1024723B1 (en) * | 2016-11-10 | 2018-06-11 | Ivc Bvba | Floor panel and method for manufacturing a floor panel. |
-
2021
- 2021-04-25 CN CN202110449517.9A patent/CN113322683B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113322683A (en) | 2021-08-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10815613B2 (en) | Artificial leather with three-dimensional pattern and manufacturing method thereof | |
| TWI359890B (en) | Manufacturing method for leather-like sheet | |
| US8288006B2 (en) | Artificial leather | |
| CN101591420B (en) | Spraying plastic polyurethane composition as well as preparation method and application thereof | |
| DE102008041987A1 (en) | Solvent-free polyurethane-based artificial leather with the structure of human skin and method for producing the same | |
| CN105694430B (en) | TPU foamed material and preparation method thereof | |
| AU2022279422A1 (en) | Curative | |
| KR20100107328A (en) | Microsphere dispersed waterborne polyurethane and process for preparing the same | |
| CN113322684B (en) | Artificial leather capable of being embossed directly and preparation method thereof | |
| CN113322683B (en) | Hard composite artificial leather capable of being embossed and preparation method thereof | |
| CN111647132A (en) | Preparation method and application of low-elasticity polyurethane resin | |
| KR100985513B1 (en) | The composition and manufacturing method for solventborne type polyurethane resin has good emboss moulding | |
| CN107778827A (en) | TPU expanded materials and its production technology | |
| JP2019123847A (en) | Aqueous surface treatment agent and skin material | |
| CN111304931A (en) | Wear-resistant flame-retardant floor leather for vehicles and preparation method thereof | |
| KR101883876B1 (en) | Fabric with three-dimensional design for vehicle | |
| JPH0261181A (en) | Leather-like sheet and production thereof | |
| CN112622392B (en) | Thermoplastic polyurethane foam product with surface coating and preparation method thereof | |
| US2321047A (en) | Artificial leather | |
| CN110373910A (en) | A kind of high-permeability PVC artificial leather and its application | |
| CN114349999B (en) | TPO male die skin with special effect produced by direct embossing and preparation method thereof | |
| JP7223032B2 (en) | Polyurethane urea aqueous dispersion, matte paint and surface treatment agent | |
| CN111139658A (en) | Synthetic leather solvent-free microfiber high-gloss finish polyurethane and preparation method thereof | |
| KR102397250B1 (en) | Composition for surface treatment having improved anti-pollution and manufacturing method of fabric with three-dimensional pattern | |
| KR810001014B1 (en) | Method of preparing a synthetic leather |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |