CN100497807C - High-combustion-proof artificial leather and making method thereof - Google Patents
High-combustion-proof artificial leather and making method thereof Download PDFInfo
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- CN100497807C CN100497807C CNB2005100074504A CN200510007450A CN100497807C CN 100497807 C CN100497807 C CN 100497807C CN B2005100074504 A CNB2005100074504 A CN B2005100074504A CN 200510007450 A CN200510007450 A CN 200510007450A CN 100497807 C CN100497807 C CN 100497807C
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Abstract
The invention relates to a artificial skin that has high flame retardant that is made up from coating a PU resin layer containing flame retardant agent onto the surface of base material, and concreting, washing in water, and drying. The PU skin film could adhere to base material to form artificial skin that has excellent handle and softness.
Description
Technical field
The invention relates to the artificial leather and the method for making thereof of high anti-combustion, particularly about a kind of PU epithelium with anti-combustion effect, this PU epithelium can with choose from Nonwovens, elastical cloth, split leather, weave cotton cloth, the ground of material such as super fibre fits to form the artificial leather of a high anti-combustion.
Background technology
Now, artificial leather has been made in a large number and has been applied in comprises that clothing, shoes, furniture and vehicle are with in the material.The manufacturing of artificial leather generally is to use by general fiber, superfine fibre or general fiber and the mixed Nonwovens of forming of superfine fibre as base cloth, and on this base cloth surface, insert polyurethane (POLYURETHANE, to call PU in the following text) resin combination, after impose the processing of attrition process or embossing or impose the processing of fitting with release liners coating polyurethane resin, and constitute the cladding that the surface has elasticity and corium lines.
Make artificial leather have characteristics such as elasticity, ABRASION RESISTANCE, good hand touch, general as long as just can reach at substrate surface coating polyurethane (PU) resin combination or applying PU epithelium; And if make artificial leather have flame resistance, in located by prior art, then be to finish with the base material of anti-the combustion, in other words, in the fiber that constitutes base material, add flame retardant exactly and reach.
As shown in Figure 1, disclose the making flow process of the general cladding of anti-combustion the at present, it is directly coating polyurethane (PU) resin combination of weaving cotton cloth to handle through anti-combustion, through solidify, wash, dry and form semi-finished product, after imposing the processing of fitting by the release liners that is coated with a liquid type PU constituent and is used as the two-liquid type PU constituent of following layer coating, peel off release liners and a leather finished product that anti-combustion effect arranged.
With the leather finished product of above-mentioned method for making gained, though existing good anti-combustion effect.But when the washing after applying polyurethane (PU) resin combination, baking step, the flame retardant of having handled on the base material of anti-the combustion will be by the part flush away, thereby can reduce the anti-combustion effect of this cladding of anti-the combustion; Moreover in the application of artificial leather, the article that need have anti-combustion effect are various, and different article often will use different base materials, cause will prepare the different base materials of anti-combustion the half product and individually carry out the coating of PU coating with the need in response to different article.In addition, up to now, also all lack anti-flammability and do not have anti-combustion effect, when fire takes place, burnt easily and produce fatal dense smoke in order to the PU epithelium that provides base material to fit.
Be with, under the prerequisite of the feel that does not influence artificial leather, soft durometer and one sense, how the flame resistance of PU epithelium and artificial leather is improved effectively, real-valuedly must research and develop design.
Summary of the invention
Main purpose of the present invention is to provide a kind of anti-combustion PU epithelium, can produce the effect of fire-retardant and anti-combustion to reduce the danger that fire takes place when being burnt by the made artificial leather of this anti-combustion PU epithelium.
Another purpose of the present invention be to provide a kind of can with the anti-combustion PU epithelium of choosing from Nonwovens, elastical cloth, split leather, weaving cotton cloth, the ground of material such as super fibre is fitted, it is reached at least and can prepare the multiple difference base material of anti-the combustion and make the artificial leather of anti-the combustion.
Another object of the present invention is to provide a kind of artificial leather and method for making thereof of high anti-combustion, the popular favourable selection of taking at the artificial leather of anti-the combustion perhaps is provided at least.
A further object of the present invention is to provide a kind of high artificial leather of anti-combustion the with characteristics such as superior feel, soft durometer and one senses.
The present invention is the concrete means that reach above-mentioned purpose and other effect, and its method for making comprises following steps:
One substrate layer is provided;
The high molecular polymer that contains fire prevention incombustible agent and fire retardant at surface coated one deck of substrate layer;
Carry out a coagulation step, use making the high molecular polymer coating layer form an open multi-cellular structure;
Carry out a water-washing step, use the solvent that flush away residues in high molecular polymer;
Carry out a baking step; And
With high molecular polymer and base cloth release and an anti-combustion PU epithelium; And
One ground further is provided, and this ground is attached to the back side of PU epithelium, to form the artificial leather of a high anti-combustion.
In one embodiment, above-mentioned substrate layer is dry again and form a surface and have the elastomeric material of film to constitute through the impregnation aqueous polymer by fabric; This aqueous polymer be for by polyurethane resin, water-based acryl resin, poly-vinegar ammonia resin, polyolefin resin with and composition thereof the colony that formed select.
In an alternative embodiment, substrate layer is directly to constitute with plastic film.
The thickness of above-mentioned substrate layer is preferably the scope at 0.01mm to 1.0mm.
The high molecular polymer that is coated on the substrate layer surface is a liquid type PU resin bed preferably, perhaps can use other connatural elastomeric polymer as this coating layer; The thickness of this coating layer is preferably the scope of 0.1mm～1.0mm again.
The fire prevention incombustible agent that high molecular polymer added comprises the compound of bromine series and phosphorus series, and the scope of this fire prevention incombustible agent addition is 1～30%, and optimum range is 5～15%.
The fire retardant that high molecular polymer added comprises the compound of antimony series, and the scope of this fire retardant addition is 1～20%, and optimum range is 2～12%.
It is 2～50% that the fire prevention incombustible agent that high molecular polymer added and fire retardant merge the addition scope, and optimum range is 7～27%, and fire prevention incombustible agent and fire retardant must merge use for two kinds.
The above-mentioned step that high molecular polymer is coated on the substrate layer surface is to be undertaken by an apparatus for coating, this high molecular polymer is to utilize high molecular polymer to be dissolved in the solvent according to special ratios and form solution, wherein this high molecular polymer is a liquid type PU, and this high molecular polymer solvent is dimethyl amide (DIMETHYL FORMAMIDA is called for short DMF).
Above-mentioned coagulation step is that the substrate layer that will be covered with high molecular polymer is delivered to inside and is equipped with in the coagulating basin of fluid,matching and carries out, the composition of this fluid,matching is solvent (DMF) and non-solvent (water), the deal of solvent can be from 0～30%, and non-solvent accounts for major part, when the base cloth that is coated with high molecular polymer passes through coagulating basin, utilize the compatibility feature of water and solvent (DMF), make the solvent in the high molecular polymer and the non-solvent of fluid,matching can produce displacement reaction (combined action), to form an open multi-cellular structure in inside.
Above-mentioned water-washing step is to carry out sending into a rinsing bowl by the substrate layer that is coated with high molecular polymer of coagulating basin output, composition in the rinsing bowl is solvent (DMF) and non-solvent (water), the deal of solvent can be from 0～30%, and non-solvent accounts for major part (deal of solvent can be 0), and it act as the solvent that flush away residues in high molecular polymer.
Above-mentioned baking step is to carry out sending into a drying unit by the substrate layer that is coated with high molecular polymer of rinsing bowl output, and using the solvent that makes in the high molecular polymer can volatilize fully.
Above-mentioned with high molecular polymer and the release step of base cloth, be to form a Wet-type polyurethane resin bed on the base cloth surface by the oven dry back, again that base cloth and this urethane resin layer is release.
Can further form a dry type polyurethane resin layer according to need in above-mentioned high molecular polymerization surface and have the natural grain of similar corium and preferable feel.This urethane resin layer is preferably coated earlier on the release liners and is transferred on the high molecular polymer layer again.
The ground at the above-mentioned PU of the being fitted in epithelium back side be comprise be selected from Nonwovens, elastical cloth, split leather, weave cotton cloth, the base cloth of material such as super fibre; Perhaps can select Nonwovens, elastical cloth, the split leather handled through anti-combustion for use, weave cotton cloth, base cloth such as super fibre is as ground.
According to the made cladding of anti-combustion of said method of the present invention,, except having superior feel, soft durometer and one sense, and can provide splendid flame resistance via demonstrate,proving after the actual tests; Again if the anti-combustion PU epithelium that the present invention is made release just can be with Nonwovens, elastical cloth, split leather, weave cotton cloth, the ground that base material constituted applying such as super fibre to be individually to provide the various article of anti-combustion use, reach can prepare the different base materials of anti-the combustion partly product individually carry out the coating of PU coating with required in response to different article.
Description of drawings
Fig. 1 shows in order to make the flow chart of one of leather of anti-combustion traditional methods;
Fig. 2 shows the cutaway view of the present invention one PU epithelium embodiment;
Fig. 3 shows the combine cutaway view of the formed artificial leather of anti-combustion of a release back of the PU epithelium of second figure and a ground; And
Fig. 4 shows the forward and backward photo figure that the artificial leather of anti-combustion of one of the present invention embodiment is done anti-combustion test;
Fig. 5 shows that the artificial leather of anti-combustion of one of the present invention comparative example is done anti-combustion tests photo figure afterwards.
[figure number explanation]
1, the artificial leather of anti-the combustion
11, substrate layer
12, the high molecular polymer layer that contains incombustible agent and fire retardant
13, ground
14, dry type polyurethane resin layer
The specific embodiment
Manufacture method of the present invention, will be via only for example but non-in order to the embodiment of restriction and with reference to appended graphic being described further, wherein:
Show one among Fig. 2 by fabric dry again and substrate layer 11 of constituting behind the impregnation aqueous polymer, this substrate layer surface coated has one deck to contain the high molecular polymer 12 of fire prevention incombustible agent and fire retardant.Wherein the thickness of substrate layer is preferably the scope at 0.01mm to 1.0mm, and the thickness of coating layer is preferably the scope of 0.1mm～1.0mm.
Constitute the processing procedure of substrate layer 11 through the impregnation aqueous polymer by fabric, be with impregnation aqueous polymer in the base cloth warp let-off one groove, through the thickness of pressure rolling wheel pressure rolling with impregnation fluid,matching on the control base cloth, and unnecessary fluid,matching flowed back in the groove, the base cloth of impregnation fluid,matching enters in the drying unit and heats subsequently, makes its surface that one film be arranged the moisture content oven dry.
The high molecular polymer 12 that is coated on substrate layer 11 surfaces is polyurethane (PU) resin bed of a liquid type PU for example preferably, perhaps can use other suitable elastomeric polymer as this coating layer, for example polyolefin resin, poly-vinegar ammonia resin, poly-acryl resin with and composition thereof the colony that formed select.
The fire prevention incombustible agent that high molecular polymer added comprises the compound of bromine series and phosphorus series, and the scope of its addition is 1～30%, and optimum range is 5～15%.
The scope of its addition of compound of the fire retardant antimony series that high molecular polymer added is 1～20%, and optimum range is 2～12%.
The scope that the fire prevention incombustible agent that high molecular polymer added and fire retardant merge addition is 2～50%, and optimum range is 7～27%, and fire prevention incombustible agent and fire retardant must merge use for two kinds.
The above-mentioned high molecular polymer that is coated on substrate layer 11 surfaces can be by a coagulation step to form an open multi-cellular structure; This coagulation step is that the substrate layer 11 that will be covered with high molecular polymer is delivered to inside and is equipped with in the coagulating basin of fluid,matching and carries out, when the substrate layer that is coated with high molecular polymer passes through coagulating basin, solvent in the high molecular polymer disengages and is dissolved in the non-solvent (water) from inside, and solvent disengages formed space, back and can be inserted by non-solvent (water), so that high molecular polymer solidifies and forms an open multi-cellular structure.
After above-mentioned coagulation step, then carry out a water-washing step residues in high molecular polymer with flush away solvent; Afterwards, carrying out a baking step again dries.
Among Fig. 2 and be presented at high molecular polymer 12 surface and further form dry type polyurethane resin layers 14, the PU epitheliums that have lines and preferable feel with formation.
Above-mentioned urethane resin layer 14 is to coat earlier to transfer on the release liners on 12 layers of the high molecular polymers again, and this release liners is preferably and has lines, uses forwarding the lines on the release liners to this polyurethane resin laminar surface.
Show among Fig. 3 with the substrate layer 11 of Fig. 2 release and PU epithelium and a ground 13 combine, to form an artificial leather 1 with the anti-PU of combustion epithelium.
Be applicable to that the material as ground 13 comprises Nonwovens, elastical cloth, split leather, weaves cotton cloth and super fibre etc.; Perhaps can select Nonwovens, elastical cloth, the split leather handled through anti-combustion for use, weave cotton cloth, base cloth such as super fibre is as ground.About the choosing of base material as this ground 13 is to depend on the various difference article of anti-combustion that will make, and this also makes the present invention need not prepare the multiple difference cladding of anti-combustion the half product provides the various difference article of anti-the combustion to use.
To further specify embodiments of the invention by following example.
[embodiment 1]
Weaving cotton cloth with nylon (nylon), (75D * 75D/176T) is a base material, this nylon is weaved cotton cloth with 100% water-base resin constituent impregnation earlier, and dry down to form the flexible material of tool at 140 ℃; This base material is sent into an apparatus for coating, and the polyurethane resin solution of 10% fire prevention incombustible agent (bromide) and 5% fire retardant (antimony oxide) is added in coating one; The base material that again this is covered with the PU resin solution is delivered to inside and was equipped with in the coagulating basin of fluid,matching 8 minutes, and wherein the ratio of the composition of this fluid,matching is dimethyl amide: water=15:85; And then the base material that will be covered with high molecular polymer is sent into a rinsing bowl that water is housed residues in high molecular polymer with flush away solvent; Afterwards, the base cloth that is covered with high molecular polymer is inserted a drying unit, under 130 ℃, dried 10 minutes, again that base material is release to form semi-finished product; After imposing the processing of fitting by the release liners that is coated with a liquid type PU constituent and is used as the two-liquid type PU constituent of following layer coating, peel off release liners and form a PU epithelium finished product; Weaving cotton cloth and form a high artificial leather of anti-combustion the after the anti-combustion of again this finished product being fitted is handled.To be shown in following table 1 about this height artificial leather of anti-the combustion through feel, soft durometer and the one sense of testing.
[comparative example 1]
Through weaving cotton cloth that anti-combustion is handled via direct coating polyurethane (PU) resin combination, through solidify, wash, drying and form semi-finished product; After imposing the processing of fitting by the release liners that is coated with a liquid type PU constituent and is used as the two-liquid type PU constituent of following layer coating, peel off release liners and form the cladding of anti-a combustion finished product.Commonly use the cladding of anti-the combustion about this and will be shown in following table 1 in the lump through feel, soft durometer and the one sense of testing.
＜table 1 〉
| Feel | Anti-combustion effect | Soft durometer | The one sense | |
| Embodiment one | 5 | 5 | 5 | 5 |
| Comparative example one | 4 | 1 | 4 | 5 |
It is superior to annotate 1:5=; 4=is good; 3=can; 2=slightly can; 1=is poor
Annotate 2: feel and one sense are directly tested with hand, anti-combustion method of testing FMVSS302, and test data sees Table 2 and table 3.
＜table 2〉anti-combustion test FMVSS302 (comparative example)
＜table 3〉anti-combustion test FMVSS302 (embodiment)
With regard to the present invention with the artificial leather of distinct methods manufacturing with commonly use leather and compare down getable effect, can fully show by the comparative result of testing with regard to every rerum naturas such as the feel of the two, anti-combustion effect, soft durometer and one senses in the table 1, wherein: aspect feel, the artificial leather of anti-combustion the of the present invention has more excellent feel than the artificial leather of commonly using of anti-the combustion; Aspect the one sense, the both has superior one sense; Aspect pliability, the artificial leather of anti-combustion the of the present invention has more excellent flexibility than the artificial leather of commonly using of anti-the combustion; Aspect anti-combustion effect, should demonstrate,prove (table 2, table 3) by the FMVSS302 testing standard, artificial leather of the present invention has preferable anti-combustion effect than the artificial leather of commonly using of anti-the combustion, in addition, it is impaired also to confirm that by anti-combustion test result shown in Figure 4 artificial leather of the present invention still can not burn after fierce fiery cigarette calcination, do not add the anti-combustion of the artificial leather of flame retardant with Fig. 5 and test relatively down, anti-flammability spy of the present invention has the effect of high anti-combustion well.
The present invention sneaks into the fire prevention incombustible agent and the fire retardant of predetermined ratio and composition in the high molecular polymer earlier, forms the cortex or the stamen layer of PU epithelium with coated substrate and release mode, fits with ground and makes the artificial leather of anti-the combustion.Cause the flame retardant can be so artificial leather of the present invention there is no following process, and as long as add a spot of fire prevention incombustible agent and fire retardant just can reach quite high anti-combustion effect by the problem of part flush away.
Simultaneously, anti-combustion PU epithelium according to the inventive method manufacturing, as long as with choose from Nonwovens, elastical cloth, split leather, weave cotton cloth, the ground of material such as super fibre combines with regard to shoes, furniture or the vehicle of the anti-combustion effect of applicable making needs with article such as materials, reach can prepare the multiple difference base cloth of anti-the combustion the various difference article of anti-combustion uses are provided.
Aforementioned is for the present invention's description that above embodiment does, and can do multiple variation or modify embodiment according to design spirit of the present invention, be with, for being familiar with obvious replacement and the modification that this skill personage can do, will be incorporated in the claim that the present invention advocates.
Claims (11)
1, a kind of artificial leather method for making of high anti-combustion is characterized in that it comprises following steps:
The substrate layer of one thickness in 0.01mm to 1.0mm scope is provided, and this substrate layer is to be made of through impregnation aqueous high molecular coating and drying plastic film or fabric;
Surface coated one deck at substrate layer contains fire prevention incombustible agent and fire retardant and the thickness high molecular polymer in 0.1mm to 1.0mm scope; And the urethane resin layer of The high molecular polymer As one liquid type PU;
Described fire prevention incombustible agent is a monobromide, and described fire retardant comprises the compound of antimony series;
High molecular polymer and substrate layer is release to get an anti-combustion PU epithelium; And
Provide and one choose, weave cotton cloth or the ground of super fine material, and this ground is attached to the above-mentioned epithelium back side to form the artificial leather of anti-the combustion from Nonwovens, elastical cloth, split leather.
2, the artificial leather method for making of the anti-combustion of height as claimed in claim 1, the incombustible agent addition scope of wherein preventing fires is 1 to 30%.
3, the artificial leather method for making of the anti-combustion of height as claimed in claim 1, wherein fire retardant addition scope is 1 to 20%.
4, as the artificial leather method for making of claim 1, the anti-combustion of 2 or 3 described height, it is 2～50% that wherein prevent fires incombustible agent and fire retardant merge the addition scope.
5, the artificial leather method for making of the anti-combustion of height as claimed in claim 1, wherein the high molecular polymer upper surface further is formed with a dry type polyurethane resin layer.
6, the artificial leather method for making of the anti-combustion of height as claimed in claim 1 is characterized in that: this epithelium of anti-the combustion is a PU epithelium, and the method for making that obtains an anti-combustion PU epithelium comprises following steps:
One substrate layer is provided, and this substrate layer through impregnation aqueous high molecular coating drying or directly constitute with plastic film, and has the thickness of 0.01mm to 1.0mm scope by fabric;
Contain the high molecular polymer of fire prevention incombustible agent and fire retardant at surface coated one deck of substrate layer, this high molecular polymer layer is made of the urethane resin layer of thickness in 0.1～1.0mm scope;
Carry out a coagulation step, use making the high molecular polymer coating layer form an open multi-cellular structure;
Carry out a water-washing step, use the solvent that flush away residues in high molecular polymer;
Carry out a baking step; And
With high molecular polymer and base cloth release and an anti-combustion PU epithelium.
7, the artificial leather method for making of the anti-combustion of height as claimed in claim 6, in the method for making of wherein anti-combustion PU epithelium, fire prevention incombustible agent addition scope is 1～30%.
8, the artificial leather method for making of the anti-combustion of height as claimed in claim 6, in the method for making of wherein anti-combustion PU epithelium, fire retardant addition scope is 1～20%.
9, as the artificial leather method for making of claim 6, the anti-combustion of 7 or 8 described height, in the method for making of wherein anti-combustion PU epithelium, it is 2～50% that fire prevention incombustible agent and fire retardant merge the addition scope.
10, a kind of artificial leather of high anti-combustion, it is characterized in that: it comprises:
One contains the PU epithelium of the high molecular polymer layer of fire prevention incombustible agent and fire retardant, and the urethane resin layer of The high molecular polymer As one liquid type PU;
Described fire prevention incombustible agent is a monobromide, and described fire retardant comprises the compound of antimony series; The thickness of this high molecular polymer layer is in 0.1mm to 2.0mm scope; And
One is attached to the ground at this PU epithelium back side, and this ground is chosen from Nonwovens, elastical cloth, split leather, weaved cotton cloth, super fine material.
11, the artificial leather of the anti-combustion of height as claimed in claim 10, wherein this anti-combustion PU epithelium comprises:
One thickness is at the substrate layer of 0.01mm to 1.0mm scope, and this substrate layer is to be made of through impregnation aqueous high molecular coating and drying plastic film or fabric;
One is coated on substrate layer surface and contains the high molecular polymer layer of fire prevention incombustible agent and fire retardant, and this high molecular polymerization body thickness is in 0.1mm to 1.0mm scope; And
One is formed on the dry type polyurethane resin layer of high molecular polymerization surface.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100074504A CN100497807C (en) | 2005-02-21 | 2005-02-21 | High-combustion-proof artificial leather and making method thereof |
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| CNB2005100074504A CN100497807C (en) | 2005-02-21 | 2005-02-21 | High-combustion-proof artificial leather and making method thereof |
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| CN100497807C true CN100497807C (en) | 2009-06-10 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100458010C (en) * | 2007-03-09 | 2009-02-04 | 浙江禾欣实业集团股份有限公司 | Process of producing fireproof sofa artificial leather |
| CN102774101B (en) * | 2012-07-18 | 2014-03-05 | 华伦皮塑（苏州）有限公司 | Production method of flame retardant and environment-friendly TPU (thermoplastic polyurethanes) leather for outdoors |
| CN105662101A (en) * | 2016-01-08 | 2016-06-15 | 邵恩华 | Preparing method for flame-retardant PU material and flame-retardant cotton wadded curtain |
| CN105821676B (en) * | 2016-04-13 | 2017-11-28 | 浙江阿波罗皮革制品有限公司 | The preparation method that noise reduction damping noise-reducing synthesizes sofa artificial leather |
| CN107287918B (en) * | 2017-07-06 | 2020-01-17 | 江苏华峰超纤材料有限公司 | Flame-retardant superfine fiber suede leather with excellent dyeing performance and preparation method thereof |
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Granted publication date: 20090610 Termination date: 20170221 |