CN106319670A - Method for producing a volatile organic compound slab for automotive use - Google Patents

Method for producing a volatile organic compound slab for automotive use Download PDF

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Publication number
CN106319670A
CN106319670A CN201510708233.1A CN201510708233A CN106319670A CN 106319670 A CN106319670 A CN 106319670A CN 201510708233 A CN201510708233 A CN 201510708233A CN 106319670 A CN106319670 A CN 106319670A
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China
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mentioned
voc
abatement
automobile
organic compound
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CN201510708233.1A
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Chinese (zh)
Inventor
李修南
金东煜
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NVH Korea Inc
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NVH Korea Inc
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Abstract

The present invention relates to a method for producing a volatile organic compound slab for automotive use, comprising: a meltblown nonwoven fabric layer forming step of melt-spun spinning a high molecular resin to form a dendritic layer having a diameter of 1 to 10 m and having a surface density of 20 to 500 g / m2 And a dispersing step of dispersing a volatile organic compound at a rate of 10 to 300 g / m2 in the nonwoven fabric layer formed thereon; and a step of laminating a surface layer in a nonwoven layer in which the volatile organic compound is dispersed a bonding step of laminating the prepared laminate by a heating roller; and a molding step of forming a laminated body bonded by a bonding step by a pressing jig. The volatile organic compound slab for automotive use prepared by the above process comprises a volatile organic compound-reducing powder which is decomposed by physical means or chemically decomposed to produce a volatile organic compound produced in a built-in component of an automobile.

Description

The automobile preparation method of VOC abatement plate
Technical field
The present invention relates to the preparation method of automobile VOC abatement plate, relate in more detail comprising volatility Organic compound abatement powder, is adsorbed by physical method or is decomposed in the build-in components constituting automobile by chemical method The VOC produced and the preparation method of plate showing abatement effect.
Background technology
Generally, the multiple build-in components constituting automobile are formed by macromolecule composite materials, are used for forming macromolecule and are combined former The various materials of material comprise harmful VOC, and during running car, above-mentioned waves The property sent out organic compound flows enters indoor, and threatens the safety of passenger.
Therefore, currently, various countries, with vehicle newly developed as object, are limited in the volatile organic compound that automotive interior produces Thing, and in order to meet the limit levels implemented in various countries, currently, automaker's each build-in components to constituting automobile Limit the generation amount of VOC.
Due to this restriction, automotive internal parts development business or use VOC and unrestricted Any materials, or use the material getting rid of a small amount of VOC to develop build-in components, but it practice, Not only along with fee of material rises, competitiveness deteriorates, even unmixed VOC or use a small amount of product, The most usually produce the problem adsorbing the VOC produced in outside in keeping and transfer, it is also difficult to carry out portion Part keeping.
(prior art literature)
(patent documentation)
Patent documentation 1: Korea S's special permission logs in No. 10-1329085 (2013.11.07.)
Patent documentation 2: Korea S's special permission logs in No. 10-1251262 (2013.04.01.)
Summary of the invention
It is an object of the invention to, it is provided that the automobile preparation method of VOC abatement plate, described automobile is used VOC abatement plate comprises VOC abatement powder, is adsorbed by physical method or by changing Method decomposes the VOC produced in the build-in components constituting automobile, and shows abatement effect.
The purpose of the present invention can provide the preparation method of automobile VOC abatement plate to realize, above-mentioned automobile It is characterised by by the preparation method of VOC abatement plate, including: melt-blown nonwoven layer of cloth forming step, molten Spray spinning macromolecule resin forms a diameter of 1 to 10 micron and have 20 to 500g/m2The nonwoven layer of surface density; Dispersion steps, disperses 10 to 300g/m in the nonwoven layer formed by above-mentioned melt-blown nonwoven layer of cloth forming step2Amount VOC abatement powder;Surface layer Stacking steps, is disperseing volatility organic by above-mentioned dispersion steps The upper side of the nonwoven layer of compound abatement powder and bottom surfaces laminate surface layer;Adhesion step, makes by above-mentioned surface Duplexer prepared by layer stackup step is bondd by heating roller;And forming step, utilize press fixture to make to pass through The duplexer of above-mentioned adhesion step bonding shapes.
According to preferred feature of the present invention, above-mentioned macromolecule resin comprises and selects from TPO, polyamide-based and polyesters More than one.
According to another preferred feature of the present invention, above-mentioned VOC abatement powder a diameter of 1 micron to 1 milli Rice, above-mentioned VOC abatement powder packets is containing organising from porous natural minerals, metal-oxide and amine In compound select more than one.
According to the another preferred feature of the present invention, above-mentioned porous natural minerals comprise from kieselguhr, zeolite, silicon dioxide, In kaolinite, galapectite, sericite, montmorillonite, bentonite and activated carbon select more than one.
According to the another preferred feature of the present invention, above-mentioned metal-oxide comprise from titanium dioxide, zinc oxide, niobium type oxide, In stannum oxide, zirconium oxide, titanate and tantalates select more than one.
According to the another preferred feature of the present invention, above-mentioned amine organic compound comprise from ammonium sulfate, tetramethyl thiourea, six times Tetramine, hexanediol acid and adipic acid hydrazides in select more than one.
According to the another preferred feature of the present invention, the surface density of above-mentioned surface layer is 10 to 50g/m2, above-mentioned surface layer comprises Select from TPO, polyamide-based and polyesters more than one.
According to the another preferred feature of the present invention, the temperature of above-mentioned heating roller is 160 to 200 DEG C.
It is organic that the preparation method of the automobile VOC abatement plate of the present invention has offer automobile volatility The prominent effect of compound abatement plate, above-mentioned automobile VOC abatement plate is because comprising volatile organic Compound is cut down powder and is adsorbed by physical method or decompose generation in the build-in components constituting automobile by chemical method VOC obtains cutting down effect.
Accompanying drawing explanation
Fig. 1 is the flow chart of the preparation method of the automobile VOC abatement plate representing the present invention.
Fig. 2 is to represent to cut down volatility prepared by the preparation method of plate by the automobile VOC of the present invention The exploded perspective view of organic compound abatement plate.
Fig. 3 is to represent to be suitable for the preparation being cut down plate by the automobile VOC of the present invention in the way of shooting The photo of the automobile top of VOC abatement plate prepared by method.
(explanation of reference)
10: nonwoven layer;11: VOC abatement powder;20: surface layer
S101: melt-blown nonwoven layer of cloth forming step;S103: dispersion steps;S105: surface layer Stacking steps
S107: adhesion step;S109: forming step
Detailed description of the invention
Hereinafter, describing the preferred embodiment of the present invention and the physical property of each composition in detail, this is simply so that technology belonging to the present invention is led The degree that the those of ordinary skill in territory can easily carry out an invention describes in detail, and the technological thought of the present invention and category are also The most therefore this it is confined to.
The preparation method of the automobile VOC abatement plate of the present invention includes: melt-blown nonwoven layer of cloth forming step S101, melt-spraying spinning macromolecule resin forms a diameter of 1 to 10 micron and have 20 to 500g/m2Surface density Nonwoven layer 10;Dispersion steps S103, in the nonwoven layer formed by above-mentioned melt-blown nonwoven layer of cloth forming step S101 10 to 300g/m is disperseed in 102The VOC abatement powder 11 of amount;Surface layer Stacking steps S105, By above-mentioned dispersion steps S103 disperseed VOC abatement powder 11 nonwoven layer 10 upper side and Bottom surfaces laminate surface layer 20;Adhesion step S107, makes the duplexer prepared by above-mentioned surface layer Stacking steps S105 Bondd by heating roller;And forming step S109, utilize press fixture to make by above-mentioned adhesion step S107 And the duplexer bondd shapes.
In above-mentioned melt-blown nonwoven layer of cloth forming step S101, it is micro-that melt-spraying spinning macromolecule resin forms a diameter of 1 to 10 Rice and there is 20 to 500g/m2The nonwoven layer 10 of surface density.
Above-mentioned macromolecule resin comprises more than one that select from TPO, polyamide-based and polyesters, by melt-blown Mode is with 20 to 500g/m2Surface density spinning, as it has been described above, a diameter of with the macromolecule resin of melt-blown mode spinning 1 to 10 micron, and it is denoted as the self-adhesive (self-bonding) of three-dimensional fiber aggregation, thus play and condense upon State scattered VOC in dispersion steps S103 and cut down powder 11 to suppress VOC to cut down Powder is to the effect of outside drain.
Now, if the surface density of nonwoven layer 10 is less than 20g/m2, then dispersion can be supported in above-mentioned dispersion steps S103 VOC abatement powder 11 ability decline, thus be not provided that the inside of automobile produce volatility The plate of the abatement excellent of organic compound, if the surface density of above-mentioned nonwoven layer 10 is more than 500g/m2, then system is increased The weight of standby VOC abatement plate and preparation expense.
In above-mentioned dispersion steps S103, in the nonwoven layer 10 formed by above-mentioned melt-blown nonwoven layer of cloth forming step S101 Middle dispersion 10 to 300g/m2The VOC abatement powder 11 of amount, and, by via above-mentioned melt-blown nothing Spin dispersing volatile organic compound abatement powder 11 in the nonwoven layer 10 that layer of cloth forming step S101 is formed, and utilize Physical method adsorbs or by chemical method decomposing volatile organic compound, thus gives abatement function.
If the amount of scattered VOC abatement powder 11 is less than 10g/m in above-mentioned dispersion steps S1032, The abatement effect of the VOC then produced at automotive interior reduces, if above-mentioned VOC abatement The dispersion amount of powder 11 is more than 300g/m2, then the non-woven fabrics prepared by above-mentioned melt-blown nonwoven layer of cloth forming step S101 The cohesive force of layer 10 declines, and likely produces and peeled off by the surface layer 20 of above-mentioned surface layer Stacking steps S105 stacking Phenomenon.
It addition, a diameter of 1 micron to 1 millimeter of above-mentioned VOC abatement powder 11, above-mentioned volatility Organic compound abatement powder 11 comprises selection from porous natural minerals, metal-oxide and amine organic compound More than one, mentioned component the VOC abatement powder 11 formed is adsorbed or by changing by physical method Method decomposing volatile organic compound, and make relief performance outstanding.
Now, it is preferable that above-mentioned porous natural minerals comprise from kieselguhr, zeolite, silicon dioxide, kaolinite, angstrom In Lip river stone, sericite, montmorillonite, bentonite and activated carbon select more than one, above-mentioned metal-oxide comprises from two In titanium oxide, zinc oxide, niobium type oxide, zirconium oxide, titanate and tantalates select more than one, above-mentioned amine Organic compound comprise from ammonium sulfate (CAS No.7783-20-2), tetramethyl thiourea (CAS No.2782-91-4), six Methine tetramine (CAS No.100-97-0), hexanediol acid (CAS No.124-04-9) and adipic acid hydrazides (CAS No. 1071-93-8) in select more than one.
In above-mentioned surface layer Stacking steps S105, disappeared by above-mentioned dispersion steps S103 dispersing volatile organic compound Subtract stacking surface layer 20 in the upper side of the nonwoven layer 10 of powder 11 and bottom surfaces, above-mentioned surface layer Stacking steps S105 Realize by the following method, i.e. cutting down powder by above-mentioned dispersion steps S103 dispersing volatile organic compound In the upper side of the nonwoven layer 10 of 11 and bottom surfaces, stacking surface density is 10 to 50g/m2And comprise from TPO, gather More than one the surface layer 20 selected in amide-type and polyesters.
If by above-mentioned surface layer Stacking steps S105 laminate surface layer 20, then can suppress to be scattered in waving of nonwoven layer 10 The property sent out organic compound abatement powder 11 flows out to outside, and improves the automobile volatile organic prepared by the present invention The presentation quality of compound abatement plate.
Now, if the surface density of above-mentioned surface layer 20 is less than 10g/m2, then the volatility of above-mentioned nonwoven layer 10 it is scattered in Organic compound abatement powder 11 is likely to the outside outflow of plate, if the surface density of above-mentioned surface layer 20 is more than 50g/m2 Weight, then prepare VOC abatement plate during can reduce and the bonding of above-mentioned nonwoven layer 10 Power, and likely it is peeling phenomenon.
In above-mentioned adhesion step S107, the duplexer prepared by above-mentioned surface layer Stacking steps S105 is made to pass through heating roller Bond, and, make the duplexer prepared by above-mentioned surface layer Stacking steps S105 pass through with 160 to 200 DEG C The warmed-up roller of temperature, bond above-mentioned nonwoven layer 10 and above-mentioned surface layer 20.
If above-mentioned duplexer passes through the warmed-up roller of temperature with 160 to 200 DEG C via above-mentioned adhesion step S107, then go up State nonwoven layer 10 and the melt surface of above-mentioned surface layer 20 and show cohesive force, by above-mentioned nonwoven layer 10 and above-mentioned Surface layer 20 bonding is got up.
Now, if the temperature of above-mentioned roller is less than 160 DEG C, the surface of the most above-mentioned nonwoven layer 10 and above-mentioned surface layer 20 is not Melted, and reduce the effectiveness of bonding process, if the temperature of above-mentioned roller is higher than 200 DEG C, then can be because of above-mentioned nonwoven layer 10 Area excessively melted, adsorbable VOC reduce, the effectiveness of VOC abatement plate Decline, and the phenomenon that the form likely producing plate deforms.
In above-mentioned forming step S109, utilize press fixture to make by the duplexer of above-mentioned adhesion step S107 bonding and shape, Further, utilize the fixture of easily dimmable pressure to make by the duplexer of above-mentioned adhesion step S107 bonding and shape, and make above-mentioned Duplexer has regulation shape.
Now, by the form of the products formed of above-mentioned forming step S109 molding according to being suitable for the form of top of plate and suitable Different with position, above-mentioned fixture is used for automobile sheetsteel, as long as easily dimmable pressure, is just not particularly limited, can use Any one.
Hereinafter, enumerate the preparation method of the automobile VOC abatement plate of the embodiment explanation present invention and pass through The physical property of automobile VOC abatement plate prepared by above-mentioned preparation method.
Embodiment 1
With surface density as 230g/m2And the mode melt-spraying spinning acrylic resin of thick (bulky) prepares nonwoven layer, 200g/m is disperseed in prepared nonwoven layer2Measure, average diameter is that the VOC of 0.1 millimeter disappears Subtract powder (zeolite of 20 weight portions, the activated carbon of 20 weight portions, the silicon dioxide of 5 weight portions, the dioxy of 5 weight portions Change titanium, the tetramethyl thiourea (CAS No.2782-91-4) of 40 weight portions, ammonium sulfate (the CAS No. of 5 weight portions Hexanediol acid (CAS No.124-04-9) of 7783-20-2) He 5 weight portions), and disperseing volatile organic compound The upper side of the nonwoven layer of thing abatement powder and bottom surfaces spinning pet resin, it is thin for carrying out stacking Film form and be 15g/m by surface density2The surface layer that formed of spun bond nonwoven fabric, thus cambium layer stack, make formation Duplexer is bondd by the warmed-up roller of temperature with 180 DEG C, and utilizes press fixture to crimp molding bonding Duplexer, thus be prepared for automobile VOC and cut down plate.
Comparative example 1
Identical with above-described embodiment 1 method is carried out, and omits the process of dispersing volatile organic compound abatement powder It is prepared for automobile sheetsteel.
The volatile organic of the automobile sheetsteel prepared by above-described embodiment 1 and comparative example 3 is illustrated in lower list 1 The measurement result of compound abatement effect.
Wherein, as in figure 2 it is shown, be attached by above-described embodiment 1 and ratio at automobile top back side hot-melt adhesive After the plate of relatively example 1 preparation, determine above-mentioned VOC abatement effect, and according to as volatile organic The determination of test method of the MS300-57 of the compound discharge capacity bioassay standard generation amount of VOC.
Table 1
As shown in Table 1 above, it is known that be suitable for the automobile VOC prepared by embodiments of the invention 1 The discharge capacity of the VOC of the automobile top of abatement plate is significantly less than and is suitable for the plate prepared by comparative example 1 The discharge capacity of VOC of automobile top.
Therefore, the preparation method of the automobile VOC abatement plate of the present invention has offer such as the effect of lower plate Really, above-mentioned plate comprises VOC abatement powder, is adsorbed by physical method or is decomposed by chemical method Constitute the VOC produced in the build-in components of automobile and show abatement effect.

Claims (8)

1. the automobile preparation method of VOC abatement plate, it is characterised in that including:
Melt-blown nonwoven layer of cloth forming step, melt-spraying spinning macromolecule resin forms a diameter of 1 to 10 micron and have 20 To 500g/m2The nonwoven layer of surface density;
Dispersion steps, disperses 10 to 300g/m in the nonwoven layer formed by above-mentioned melt-blown nonwoven layer of cloth forming step2 The VOC abatement powder of amount;
Surface layer Stacking steps, at the non-woven fabrics having been disperseed VOC abatement powder by above-mentioned dispersion steps Stacking surface layer in the upper side of layer and bottom surfaces;
Adhesion step, makes the duplexer prepared by above-mentioned surface layer Stacking steps be bondd by heating roller;And
Forming step, utilizes press fixture to make the duplexer bondd by above-mentioned adhesion step shape.
The preparation method of automobile VOC the most according to claim 1 abatement plate, it is characterised in that Above-mentioned macromolecule resin comprises more than one that select from TPO, polyamide-based and polyesters.
The preparation method of automobile VOC the most according to claim 1 abatement plate, it is characterised in that A diameter of 1 micron to 1 millimeter of above-mentioned VOC abatement powder, above-mentioned VOC is cut down Powder packets containing from porous natural minerals, metal-oxide and amine organic compound select more than one.
The preparation method of automobile VOC the most according to claim 3 abatement plate, it is characterised in that Above-mentioned porous natural minerals comprise from kieselguhr, zeolite, silicon dioxide, kaolinite, galapectite, sericite, illiteracy take off In stone, bentonite and activated carbon select more than one.
The preparation method of automobile VOC the most according to claim 3 abatement plate, it is characterised in that Above-mentioned metal-oxide comprises from titanium dioxide, zinc oxide, niobium type oxide, stannum oxide, zirconium oxide, titanate and tantalum In hydrochlorate select more than one.
The preparation method of automobile VOC the most according to claim 3 abatement plate, it is characterised in that Above-mentioned amine organic compound comprises from ammonium sulfate, tetramethyl thiourea, hexamethylenetetramine, hexanediol acid and adipic acid acyl In hydrazine select more than one.
The preparation method of automobile VOC the most according to claim 1 abatement plate, it is characterised in that The surface density of above-mentioned surface layer is 10 to 50g/m2, above-mentioned surface layer comprises from TPO, polyamide-based and polyesters More than one of middle selection.
The preparation method of automobile VOC the most according to claim 1 abatement plate, it is characterised in that The temperature of above-mentioned heating roller is 160 to 200 DEG C.
CN201510708233.1A 2015-07-02 2015-10-27 Method for producing a volatile organic compound slab for automotive use Pending CN106319670A (en)

Applications Claiming Priority (2)

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KR10-2015-0094472 2015-07-02
KR20150094472 2015-07-02

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1114825A (en) * 1993-09-17 1996-01-10 哈索·冯布吕歇尔 Process and materials for cleansing areas affected by pollutants
JP2004313860A (en) * 2003-04-14 2004-11-11 Toray Ind Inc Gas adsorbing sheet
JP2007000181A (en) * 2005-06-21 2007-01-11 Toyobo Co Ltd Protective material and protective clothing
CN103025941A (en) * 2010-07-07 2013-04-03 3M创新有限公司 Patterned air-laid nonwoven fibrous webs and methods of making and using same
CN103736467A (en) * 2014-01-10 2014-04-23 浙江朝晖过滤技术股份有限公司 Preparation method of activated carbon fiber net of air purifier
DE102013013163A1 (en) * 2013-07-18 2015-01-22 Kautex Textron Gmbh & Co. Kg Multilayer composite material and articles comprising same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1114825A (en) * 1993-09-17 1996-01-10 哈索·冯布吕歇尔 Process and materials for cleansing areas affected by pollutants
JP2004313860A (en) * 2003-04-14 2004-11-11 Toray Ind Inc Gas adsorbing sheet
JP2007000181A (en) * 2005-06-21 2007-01-11 Toyobo Co Ltd Protective material and protective clothing
CN103025941A (en) * 2010-07-07 2013-04-03 3M创新有限公司 Patterned air-laid nonwoven fibrous webs and methods of making and using same
DE102013013163A1 (en) * 2013-07-18 2015-01-22 Kautex Textron Gmbh & Co. Kg Multilayer composite material and articles comprising same
CN103736467A (en) * 2014-01-10 2014-04-23 浙江朝晖过滤技术股份有限公司 Preparation method of activated carbon fiber net of air purifier

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
刘岩: ""胺类甲醛固定剂清除挥发甲醛的研究"", 《应用化工》 *
周永香: ""含氨基聚合物游离甲醛捕获剂的合成"", 《中国皮革》 *
姚仲鹏: "《空气净化原理、设计与应用》", 30 September 2014, 中国科学技术出版社 *
廖中文: "《汽车装饰与美容技术》", 31 May 2013, 哈尔滨工业大学出版社 *
艾小红: ""新型甲醛吸收剂的制备与应用研究"", 《广州大学学报》 *

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