CA1138588A - Composite material compositions using wastepaper and method of producing same - Google Patents
Composite material compositions using wastepaper and method of producing sameInfo
- Publication number
- CA1138588A CA1138588A CA000330990A CA330990A CA1138588A CA 1138588 A CA1138588 A CA 1138588A CA 000330990 A CA000330990 A CA 000330990A CA 330990 A CA330990 A CA 330990A CA 1138588 A CA1138588 A CA 1138588A
- Authority
- CA
- Canada
- Prior art keywords
- wastepaper
- parts
- weight
- thermoplastic resin
- composition
- 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.)
- Expired
Links
- 239000010893 paper waste Substances 0.000 title claims abstract description 85
- 239000000203 mixture Substances 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 32
- 238000000465 moulding Methods 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000004898 kneading Methods 0.000 claims abstract description 13
- 238000005520 cutting process Methods 0.000 claims abstract description 9
- 239000011256 inorganic filler Substances 0.000 claims abstract description 8
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 13
- 238000010009 beating Methods 0.000 claims description 9
- 229920001971 elastomer Polymers 0.000 claims description 8
- 238000005469 granulation Methods 0.000 claims description 8
- 230000003179 granulation Effects 0.000 claims description 8
- 230000006911 nucleation Effects 0.000 claims description 8
- 238000010899 nucleation Methods 0.000 claims description 8
- 239000005060 rubber Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- 238000009775 high-speed stirring Methods 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims 1
- 239000000654 additive Substances 0.000 abstract description 16
- 229920003002 synthetic resin Polymers 0.000 abstract description 13
- 239000000057 synthetic resin Substances 0.000 abstract description 13
- 238000001035 drying Methods 0.000 abstract description 11
- 238000002844 melting Methods 0.000 abstract description 9
- 230000008018 melting Effects 0.000 abstract description 9
- 230000000996 additive effect Effects 0.000 abstract description 6
- 229920001169 thermoplastic Polymers 0.000 description 16
- 239000004416 thermosoftening plastic Substances 0.000 description 16
- 239000000126 substance Substances 0.000 description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 239000000123 paper Substances 0.000 description 6
- 244000043261 Hevea brasiliensis Species 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920003051 synthetic elastomer Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 4
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- -1 corrugated board Substances 0.000 description 4
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 4
- 229920001903 high density polyethylene Polymers 0.000 description 4
- 239000004700 high-density polyethylene Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 229920003052 natural elastomer Polymers 0.000 description 4
- 229920001194 natural rubber Polymers 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 229920006026 co-polymeric resin Polymers 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000005061 synthetic rubber Substances 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000008235 industrial water Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000010899 old newspaper Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 102100024133 Coiled-coil domain-containing protein 50 Human genes 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 101000910772 Homo sapiens Coiled-coil domain-containing protein 50 Proteins 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000000817 Petroleum-derived resin Substances 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920002125 Sokalan® Chemical class 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004584 polyacrylic acid Chemical class 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229940075065 polyvinyl acetate Drugs 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Paper (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
This invention provides a composite material compositions comprising wastepaper, a thermoplastic resin and/or other additive(s), said compositions having higher heat resistance, flame retardance and mechanical strength and smaller linear shrinkage in molding than the conventional compositions of synthetic resins alone or blended with woodmeal or an inorganic filler. There is also provided a method of producing said compositions comprising a wastepaper cutting step, a step of mixing cut wastepaper with a thermoplastic resin and/or other additive(s) while drying said wastepaper, a blend melting step, a blend kneading step and a blend granulating step. In an embodiment of this invention, scraps of moldings from the composite material compositions using wastepaper may be mixed with wastepaper, a thermoplastic resin and/or other additives(s) and similarly treated and molded into a new composition.
This invention provides a composite material compositions comprising wastepaper, a thermoplastic resin and/or other additive(s), said compositions having higher heat resistance, flame retardance and mechanical strength and smaller linear shrinkage in molding than the conventional compositions of synthetic resins alone or blended with woodmeal or an inorganic filler. There is also provided a method of producing said compositions comprising a wastepaper cutting step, a step of mixing cut wastepaper with a thermoplastic resin and/or other additive(s) while drying said wastepaper, a blend melting step, a blend kneading step and a blend granulating step. In an embodiment of this invention, scraps of moldings from the composite material compositions using wastepaper may be mixed with wastepaper, a thermoplastic resin and/or other additives(s) and similarly treated and molded into a new composition.
Description
~38S~8 BACKGROUND OF THE INVENTION
Field of the Invention This invention relates to a composite material com-position using wastepaper obtained by first cutting wastepaper with no pretreatment and then mixing it with a thermoplastic resin, and a method of producing such composition.
Description of Prior Art Heretofore, synthetic resins either with or without an inorganic filler or woodmeal and compressed boards using regenerated wastepaper have been available as boarding material for interior parts of automobilesO
However, synthetic resin moldings are generally un-suited for use as interior parts of automobiles because of poor heat resistance and flame retardancy.
The woodmeal-incorporated synthetic resins have had problems in mechanical strength such as tensile strength, bending modulus of elasticity, bending strength and impact - strength.
In the case of synthetic resins provided with an inorganic filler such as talc or calcium carbonate, for improv-ing said defective properties of said synthetic resins alone or woodmeal-incorporated synthetic resins, although heat resistance and flame retardancy as well as mechanical strength are improved, linear shrinkage in molding such resins (0.8 - 1.5%) is not much different from that of the normal synthetic ~' _ ;~ _ 1~3~588 resins (1-2%), so that the molded parts therefrom, particularly those exceeding 1,000 mm in length such as for example front boards for automobiles, are elevated in dimensional tolerance to discommode mating or combined use of moldings.
s As for the compressed boards utilizing regenerated wastepaper, they are variable in water content as they absorb moisture from the air, and they are also subject to extention or shrinkage in accordance with the change of water content, resulting in irregular deformations such as warp or torsion.
~urther, such compressed boards, as compared with synthetic resins, have a certain limitation in bending or drawing work and are unsuitable for use to make the moldings with an in-tricate configuration.
Generally, such compressed boards have been produced by first beating wastepaper in water, subjecting the beaten wastepaper to a paper-making process, drying the thus processed wastepaper and then subjecting dried wastepaper to compression molding. According to this method, large equipment must be provided for performing such beating, paper processing and drying, and naturally high equipment costs result. Also, a large volume of industrial water is required for beating and paper processing of wastepaper, and this necessitates anti-pollution equipment for treating waste water released from said processes.
~ ~ 3 ~
1~3~88 SUMMARY OF THE INVENTION
This invention provides a composite material composition by utilizing wastepaper such as old newspaper, corrugated board, cardboard, and scrap paper, which usually are thown away in huge volumes every day, so as to contribute to saving of pulp resources as well as saving of petroleum resources by lessening the amount of use of petroleum-derived resins for said type of compositions.
The present invention principally provides a composite material composition using wastepaper which composition has the properties suited for use in the manufacture of automobile parts.
The present invention also provides a composite material composition using wastepaper which composition is free of the deficiencies of heat resistance and flame retardancy of synthetic resins, mechanical strength of woodmeal-blended synthetic resins and linear shrinkage in molding of inorganic filler-incorporated synthetic resins.
The present invention also provides a composite material composition using wastepaper which composition does not absorb moisture from the air as do compressed boards using regenerated wastepaper and hence is free from deformation such as warp or torsion after molding, and also has a same degree of moldability as normal synthetic resins.
3Q The composite material composition according to this invention comprises 3~
q~r ~ - 4 -~3~s~s adding about 70 to about 150 parts by weight of a thermo-plastic resin to 100 parts by weight of wastepaper. The composition may suitably also contain synthetic or natural rubber, an inorganic filler or there additives so as to provide the composition with the properties that are suitable for use as moldings.
The present invention also provides a method of producing a composite material composition using wastepaper which method avoids the steps of beating, paper processing and drying which require great volumes of industrial water.
The present invention further provides a method of producing a composite material composition using wastepaper in a short time and with high efficiency by using only a small amount of e~uipment for cutting the wastepaper and mixing and granulation of the blend.
According to this invention there is provided a method of producing a composite material composition using waste-paper which method comprises a wastepaper cutting step, a mixing and drying step in which cut wastepaper, a thermoplastic resin and/or other additives are mixed under stirring at high speed in a mixer while water contained in wastepaper is removed by frictional heat generated during the mixing to dry the mixture, a melting step în which high-speed stirring is further continued in the mixer to develop frictional heat thereby to melt the ,~
thermoplastic resin and additives, a kneading step in which high-speed stirring is still continued in the mixer to beat wastepaper in the melt phase so that wastepaper is impregnated with the melt, and a granulation step in which the kneaded composition is granulated. This method may further comprise preheating of the mixer for effecting the process in a shorter period of time with higher efficiency, incorporation of a nu-cleation step between the kneading and granulation steps, and employment of a controlling means.
The method of this invention can be applied for pro-ducing of a new composite material composition from a used one by pulverizing the scraps of the moldings from the composition of this invention and adding the pulverized material to the mix-ture of wastepaper, thermoplastic resin and/or additives.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The composite material composition according to this invention comprises 100 parts by weight of wastepaper and about70 to 150 parts by weight of a thermoplastic resin. The wastepaper used here is, for example, newspaper, corrugated board, cardboard and scraps thereof. Any sort of paper that is available in bulk at low cost may be used. Such wastepaper may be used with no such pretreatment as washing, tempering or drying. Therefore, the wastepaper, when used, may contain a size, filler, pigment, ink and other like substances.
It also contains moisture of usually about 10 to 15% when it is in an equilibrium state. Since large-sized wastepaper re-~uires a substantial time for mixing an~ milling with the ther-moplastic resin and other additives, wastepaper is usually cut-out small pieces with a size of less than 30 mm, preferablyabout 5 mm and then mixed and milled with the resin, etc.
The thermoplastic resin used in this invention may be of any type of thermoplastic polymer. Examples of such thermo-plastic resins are polyethylene, polypropylene, ethylene/propy-len~ copol~ymer, polybutene, polyvinyl chloride, polyvinyl ace-tate, polymethacrylic acid esters (particularly methyl esters), polyacrylic acid esters and polystyrene. These thermoplastic resins may be used singly, or they may be used in combination for imparting the properties that suit the intended use of the moldings. Also, the thermoplastic resin used in the process of this invention may be in the form of either pellets or powder.
The mixing ratio of the thermoplastic resin may be suitably selected within the range of about 70 to about 150 parts by weight per 100 parts by weight of wastepaper. If the amount of the thermoplastic resin mixed exceeds about 150 parts by weight, the properties of the resultantly produced composition appro-ximate to those of the thermoplastic resin per se, resulting in poor heat resistance and flame retardancy. On the other hand, if the amount of the thermoplastic resin mixed is less than about 75 parts ~.
1~,~8588 by weight~ mechanical strength, particularly impact strength, of the resultant composition is excessively lowered. For this reason, the most preferred mixing ratio of thermoplastic resin to wastepaer is 100:100 by weight part~
The composite material composition using wastepaper according to this invention may be blended with an additive or additives to provide the properties that are required of the moldings. ~enerally, if the mixing ratio of thermoplastic resin to wastepaper is lessened, mechanical strength (impact strength) of the moldings is deteriorated. In order to overcome such problem, æynthetic or natural rubber may be added in an amount of up to 20 parts by weight, together with about 70 to about 150 parts by weight of a thermoplastic resin, to 100 parts by weight of wastepaper. Addition of such rubber leads to a marked improvement of impact strength of the composition.
Synthetic rubber used for this purpose ~ay be suitably selected from the thermoplastic synthetic rubbers ~uch as styrene rubber, polybutadiene rubber, butyl rubber, nitrile rubber, ethylene/propylene rubber and ethylene/vinyl acetate rubber.
Such syntheti~ or natural rubber may be used in the form of either pellets or powder. Also, such rubber may be previously blended with a thermoplastic resin and used in the form of a comp~und.
In order to ~urther improve impact strength of the composition, an inorganic filler may be ~lended in an ~ 8 --113~S88 amount of up to 25 parts by weight to 100 parts by weight of wastepaper, about 50 to 150 parts by weight of a thermoplastic resin and up to 20 parts by weight of synthetic or natural rub-ber. Such înorganic filler may be calcium carbonate, talc, calcium sulfate, barium sulfate or the like.
It is also possible to blend stearic acid as lubri-cant so as to improve compatibility of wastepaper with thermo-plastic resin and/or other additives to facilitate mixing and kneading thereof and to thereby further improve the properties of the moldings.
rJe will now describe the method of producing the com-posite material composition using wastepaper that has been discussed above.
In the following description, the te~m "materials"
refers to wastepaper, thermoplastic resin and/or other addi-tives. Also, the term "thermoplastic substances" refers to thermoplastic resins and other thermoplastic materials in gen-eral, such as synthetic rubber among the additives.
First, wastepaper is cut into small pieces with size of less than 30 mm in the wastepaper cutting step for allowing efficient mlxingand kneading of the wastepaper, thermoplastic resin and/or other additive(s). Such cutting of wastepaper may be effected in various ways. For example, wastepa2er is first cut longitudinally and crosswise by a cutter and then the thus cut paper is crushed by a mill. This method is favorable as it allows obtention of cut pieces r ~1~
at high efficiency.
Then the cut peices of wastepaper are mixed with a thermoplastic resin and/or other additive(s) in a mixer. In this case, the thermoplastic resin, synthetic or natural rubber and an inorganic filler may be fed into the mixer independently in the form of pellets or powders, or all of these materials may be pre-compounded and then fed into the mixer. As the materials are thus supplied into the mixer, they are then agitated therein at high speed, whereby the materials are well mixed up and at the same time the water content of wastepaper is reduced to about 0.3 to 1.0~ by dint of frictional heat that is generated during said mixing, thus effecting drying of wastepaper.
As high-speed agitation of the materials in the mixer is further continued, the temperature in the mixer is raised by the frictional heat of mixing to a thermoplastic substance melting temperature, whereupon the thermoplastic substances be-gin to melt. Heating of the materials in the mixer is effected by said frictional heat until reaching the melt temperature, but since heating by such frictional heat alone takes a long time for raising the temperature from ambient to melt starting temperature, it is desirable to preheat the mixer by using a heating medium to a temperature suited for drying of wastepaper and then effect further drying of wastepaper and melting of the thermoplastic substances by ,.
~138S0 frictional heat of the materials. This can appreciably shorten the production time.
When high-speed stirring of the materials in the mixer is further continued, the wastepaper begins to beat into the melted thermoplastic substances to effect kneading of the wastepaper, thermoplastic resin and other additives. This kneading should not be continued for a long time because the material temperature in the mixer rises so high as to cause thermal decomposition of the wastepaper, etc., in the materials.
Also, too long time of beating and kneading excessively pro-motes beating of the wastepaper, resulting in reduced mechani-cal strength of the composition moldings.
.
Then the kneaded mass of materials is granulated by using a known granulator to form a composite material composi-tion. Molding of this composition into a form of use may be accomplished by using a known molding means. For example, said composition can be molded by a vented injection molding machine in the same was as molding of an ordinary thermoplastic resin.
In a preferred mode of practice of this invention, stirring in the mixer is decelerated to a medium speed for a short period of time upon completion of material kneading and then stirring of the materials is further continued to effect nucleation in the early stage of granulation. This can reduce the time required for the next granulation step.
No waste of material is suffered if the scraps of the ~r 11385~8 moldings from said composition are asain crushed into powder and mixed in the fresh feed of materials.
Now, the composite material composition using waste-paper according to this invention and the method of producing such composition are described in further detail by way of the embodiments thereof.
Described first is a preferred example of the compo-sition production method according to this invention.
First, old newspapers (wastepaper) are cut into square pieces with size of 7 cm x 7 cm, and the cut pieces of newspaper are further cut into smaller pieces by a turbo-mill.
Only those of the finely cut newspaper pieces which have pas-sed a 5 mm x 5 mm mesh screen are used as the ~astepaper ma-terial for the process. Used in the process of this example are 42.5 kg of the thus obtained newspaper cut pieces, 34 kg of ethylene-propylene copolymer resin as therr.~oplastic resin, 4.25 kg of high-density polyethylene resin, 4.25 kg of ethylene-propylene rubber and 0.04 kg of 2,6-di-t-butyl-4-methylphenol (BHT~ as antioxidant (these materials are hereinafter referred to as blend). This blend is supplied into a mixer which has been previously heated to 75-80C by a heating medium,and then is continuously stirred therein at the rate of 1,060 r.p.m.
for about 25 minutes. Thus, the interior of the mixer is ini-tially kept at said preheating temperature 75-80C, but as the blend with a lower temperature than such preheatin~
~ - 12 -temperature is supplied into the mixer, the temperature therein drops temporarily. However, since the blend is stirred at high speed in the mixer, the tempera,ure in the mixer begins to rise 5 minutes after the start of stirring owing to frictional heat which is generated by mixing of the blend materials. Such rise of temperature takes place slowly until moisture in the waste-paper in the blend is driven off to effect sufficient drying thereof. When drying of the wastepaper in the blend is sub-stantially completed, there takes place more sharp rise of intra-mixer temperature by dint of frictional heat, and when the tem-perature in the mixer reaches 162C, the thermoplastic sub-stances in the blend begin to melt. 20 minutes was required until such melting began from start of stirring. Melting of the thermoplastic substances causes sharp increase of the blend viscosity, so that frictional heat is generated succes-sively by the continued agitation to effect perfect melting of the thermoplastic substances. As the thermoplastic substances are thus melted, the wastepaper is beating into the melt phase.
In this condition, the beaten wastepaper and molten thermo-plastic substances (which rope) are kneaded while further pro-moting beating of the wastepaper and causing impregnation of the theremoplastic substances in the beaten wastepaper. If stir-ring isfurther continued for a long time, the temperaturein the mixer excessively rises to give rise to an unfavorable situation such as carbonatization of the wastepaper component in the blend, so that this kneading step was switched to the next nucleation step upon passage of about 25 minutes after start of stirring in the mixer. In the above-described process, the load current of the mixer motor is a~ound 200 A at the ` B~ stage where mixing and ~ 9 of the blend has been completed, but said load current ~egins to inrease with start of melting of the thermoplastic substances in the blend and the viscosity of the blend ri~o~ u~ in accordance ~ith advancement of melting, causing further increase of the load current of the mixer motor. When the load current of saia mixer motor has reached about 250 A, control of proceeding to the next nucleation step was performed. The blend temperature at the time of proceeding to the nucleation step was 180-190C. In the next nucleation step, additional stirring was'carried out for 6-7 minutes by dropping the stirring rate to 530 r.p.m. This has initiated ~ormation of clusters of small particles oi the kneaded blend (early phase of granulation). The blend tempera-ture upon completion of this nucleation step was 225C.
After completion of this nucleation step, the blend was transferred into another mixer which had been water-cooled to about 20C, and further subjected to additional 15-minute stirring at the rate of 100 r.p.m., whereby the blend wa~
formed into particles with diameter of approximately 2-3 mm, with temperature thereof being down to 70C. The thus granulated blend may be molded into a desired form of use by a vented l'l~i injection molding machine in the same way as molding of an ordinary synthetic resin.
'rhe moldings obtained from the above-described composite material compositions according to this invention had the properties shown in the following table. In Example 1, a composite material composition was prepared according to the above-described method by using 42.5 kg of wastepaper, 34 kg of ethylene-propylene copolymer resin, 4.25 kg of high-density polyethylene resin, 4.25 kg of ethylene-propylene rubber and 0.04 kg of ~H~, and a molding was formed from such composition.
In Example 2, a similar composition was prepared in the similar way by using 25.5 kg of wastepaper, 40.8 kg of ethylene-polypropylene copolymer resin, 5.1 kg of high-density polyethylene resin, 5.1 kg of ethylene-propylene rubber, 8.5 kg of calcium carbonate, 0.2 kg of stearic acid and 0.05 kg of BHT. In Comparative Example 1, a molding was formed from a blend consisting of 80 kg of ethylene-propylene copolymer resin, 10 kg of high-density polyethylene resin, 10 kg of ethylene-propylene rubber and 0.1 kg of BHT. The composition ~f Comparative Example 1 is same as that of Example 1 from which wastepaper was excluded. In Comparative Example 2, a composition was prepared by using 3 parts by weight of a thermoplastic resin and 2 parts by weight of talc. Thus, it shows the properties of a composition in which an înorganic filler is incorporated.
In Comparative Example 3, a composition was prepared according to Example 1 without using wastepaper but by using instead woodmeal crushed to the size of less than 30 meshes.
The ~n~g rate in the table was mea~red accord~g to the U.S. Federal Motor Vehicle Safety Standard~.
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Field of the Invention This invention relates to a composite material com-position using wastepaper obtained by first cutting wastepaper with no pretreatment and then mixing it with a thermoplastic resin, and a method of producing such composition.
Description of Prior Art Heretofore, synthetic resins either with or without an inorganic filler or woodmeal and compressed boards using regenerated wastepaper have been available as boarding material for interior parts of automobilesO
However, synthetic resin moldings are generally un-suited for use as interior parts of automobiles because of poor heat resistance and flame retardancy.
The woodmeal-incorporated synthetic resins have had problems in mechanical strength such as tensile strength, bending modulus of elasticity, bending strength and impact - strength.
In the case of synthetic resins provided with an inorganic filler such as talc or calcium carbonate, for improv-ing said defective properties of said synthetic resins alone or woodmeal-incorporated synthetic resins, although heat resistance and flame retardancy as well as mechanical strength are improved, linear shrinkage in molding such resins (0.8 - 1.5%) is not much different from that of the normal synthetic ~' _ ;~ _ 1~3~588 resins (1-2%), so that the molded parts therefrom, particularly those exceeding 1,000 mm in length such as for example front boards for automobiles, are elevated in dimensional tolerance to discommode mating or combined use of moldings.
s As for the compressed boards utilizing regenerated wastepaper, they are variable in water content as they absorb moisture from the air, and they are also subject to extention or shrinkage in accordance with the change of water content, resulting in irregular deformations such as warp or torsion.
~urther, such compressed boards, as compared with synthetic resins, have a certain limitation in bending or drawing work and are unsuitable for use to make the moldings with an in-tricate configuration.
Generally, such compressed boards have been produced by first beating wastepaper in water, subjecting the beaten wastepaper to a paper-making process, drying the thus processed wastepaper and then subjecting dried wastepaper to compression molding. According to this method, large equipment must be provided for performing such beating, paper processing and drying, and naturally high equipment costs result. Also, a large volume of industrial water is required for beating and paper processing of wastepaper, and this necessitates anti-pollution equipment for treating waste water released from said processes.
~ ~ 3 ~
1~3~88 SUMMARY OF THE INVENTION
This invention provides a composite material composition by utilizing wastepaper such as old newspaper, corrugated board, cardboard, and scrap paper, which usually are thown away in huge volumes every day, so as to contribute to saving of pulp resources as well as saving of petroleum resources by lessening the amount of use of petroleum-derived resins for said type of compositions.
The present invention principally provides a composite material composition using wastepaper which composition has the properties suited for use in the manufacture of automobile parts.
The present invention also provides a composite material composition using wastepaper which composition is free of the deficiencies of heat resistance and flame retardancy of synthetic resins, mechanical strength of woodmeal-blended synthetic resins and linear shrinkage in molding of inorganic filler-incorporated synthetic resins.
The present invention also provides a composite material composition using wastepaper which composition does not absorb moisture from the air as do compressed boards using regenerated wastepaper and hence is free from deformation such as warp or torsion after molding, and also has a same degree of moldability as normal synthetic resins.
3Q The composite material composition according to this invention comprises 3~
q~r ~ - 4 -~3~s~s adding about 70 to about 150 parts by weight of a thermo-plastic resin to 100 parts by weight of wastepaper. The composition may suitably also contain synthetic or natural rubber, an inorganic filler or there additives so as to provide the composition with the properties that are suitable for use as moldings.
The present invention also provides a method of producing a composite material composition using wastepaper which method avoids the steps of beating, paper processing and drying which require great volumes of industrial water.
The present invention further provides a method of producing a composite material composition using wastepaper in a short time and with high efficiency by using only a small amount of e~uipment for cutting the wastepaper and mixing and granulation of the blend.
According to this invention there is provided a method of producing a composite material composition using waste-paper which method comprises a wastepaper cutting step, a mixing and drying step in which cut wastepaper, a thermoplastic resin and/or other additives are mixed under stirring at high speed in a mixer while water contained in wastepaper is removed by frictional heat generated during the mixing to dry the mixture, a melting step în which high-speed stirring is further continued in the mixer to develop frictional heat thereby to melt the ,~
thermoplastic resin and additives, a kneading step in which high-speed stirring is still continued in the mixer to beat wastepaper in the melt phase so that wastepaper is impregnated with the melt, and a granulation step in which the kneaded composition is granulated. This method may further comprise preheating of the mixer for effecting the process in a shorter period of time with higher efficiency, incorporation of a nu-cleation step between the kneading and granulation steps, and employment of a controlling means.
The method of this invention can be applied for pro-ducing of a new composite material composition from a used one by pulverizing the scraps of the moldings from the composition of this invention and adding the pulverized material to the mix-ture of wastepaper, thermoplastic resin and/or additives.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The composite material composition according to this invention comprises 100 parts by weight of wastepaper and about70 to 150 parts by weight of a thermoplastic resin. The wastepaper used here is, for example, newspaper, corrugated board, cardboard and scraps thereof. Any sort of paper that is available in bulk at low cost may be used. Such wastepaper may be used with no such pretreatment as washing, tempering or drying. Therefore, the wastepaper, when used, may contain a size, filler, pigment, ink and other like substances.
It also contains moisture of usually about 10 to 15% when it is in an equilibrium state. Since large-sized wastepaper re-~uires a substantial time for mixing an~ milling with the ther-moplastic resin and other additives, wastepaper is usually cut-out small pieces with a size of less than 30 mm, preferablyabout 5 mm and then mixed and milled with the resin, etc.
The thermoplastic resin used in this invention may be of any type of thermoplastic polymer. Examples of such thermo-plastic resins are polyethylene, polypropylene, ethylene/propy-len~ copol~ymer, polybutene, polyvinyl chloride, polyvinyl ace-tate, polymethacrylic acid esters (particularly methyl esters), polyacrylic acid esters and polystyrene. These thermoplastic resins may be used singly, or they may be used in combination for imparting the properties that suit the intended use of the moldings. Also, the thermoplastic resin used in the process of this invention may be in the form of either pellets or powder.
The mixing ratio of the thermoplastic resin may be suitably selected within the range of about 70 to about 150 parts by weight per 100 parts by weight of wastepaper. If the amount of the thermoplastic resin mixed exceeds about 150 parts by weight, the properties of the resultantly produced composition appro-ximate to those of the thermoplastic resin per se, resulting in poor heat resistance and flame retardancy. On the other hand, if the amount of the thermoplastic resin mixed is less than about 75 parts ~.
1~,~8588 by weight~ mechanical strength, particularly impact strength, of the resultant composition is excessively lowered. For this reason, the most preferred mixing ratio of thermoplastic resin to wastepaer is 100:100 by weight part~
The composite material composition using wastepaper according to this invention may be blended with an additive or additives to provide the properties that are required of the moldings. ~enerally, if the mixing ratio of thermoplastic resin to wastepaper is lessened, mechanical strength (impact strength) of the moldings is deteriorated. In order to overcome such problem, æynthetic or natural rubber may be added in an amount of up to 20 parts by weight, together with about 70 to about 150 parts by weight of a thermoplastic resin, to 100 parts by weight of wastepaper. Addition of such rubber leads to a marked improvement of impact strength of the composition.
Synthetic rubber used for this purpose ~ay be suitably selected from the thermoplastic synthetic rubbers ~uch as styrene rubber, polybutadiene rubber, butyl rubber, nitrile rubber, ethylene/propylene rubber and ethylene/vinyl acetate rubber.
Such syntheti~ or natural rubber may be used in the form of either pellets or powder. Also, such rubber may be previously blended with a thermoplastic resin and used in the form of a comp~und.
In order to ~urther improve impact strength of the composition, an inorganic filler may be ~lended in an ~ 8 --113~S88 amount of up to 25 parts by weight to 100 parts by weight of wastepaper, about 50 to 150 parts by weight of a thermoplastic resin and up to 20 parts by weight of synthetic or natural rub-ber. Such înorganic filler may be calcium carbonate, talc, calcium sulfate, barium sulfate or the like.
It is also possible to blend stearic acid as lubri-cant so as to improve compatibility of wastepaper with thermo-plastic resin and/or other additives to facilitate mixing and kneading thereof and to thereby further improve the properties of the moldings.
rJe will now describe the method of producing the com-posite material composition using wastepaper that has been discussed above.
In the following description, the te~m "materials"
refers to wastepaper, thermoplastic resin and/or other addi-tives. Also, the term "thermoplastic substances" refers to thermoplastic resins and other thermoplastic materials in gen-eral, such as synthetic rubber among the additives.
First, wastepaper is cut into small pieces with size of less than 30 mm in the wastepaper cutting step for allowing efficient mlxingand kneading of the wastepaper, thermoplastic resin and/or other additive(s). Such cutting of wastepaper may be effected in various ways. For example, wastepa2er is first cut longitudinally and crosswise by a cutter and then the thus cut paper is crushed by a mill. This method is favorable as it allows obtention of cut pieces r ~1~
at high efficiency.
Then the cut peices of wastepaper are mixed with a thermoplastic resin and/or other additive(s) in a mixer. In this case, the thermoplastic resin, synthetic or natural rubber and an inorganic filler may be fed into the mixer independently in the form of pellets or powders, or all of these materials may be pre-compounded and then fed into the mixer. As the materials are thus supplied into the mixer, they are then agitated therein at high speed, whereby the materials are well mixed up and at the same time the water content of wastepaper is reduced to about 0.3 to 1.0~ by dint of frictional heat that is generated during said mixing, thus effecting drying of wastepaper.
As high-speed agitation of the materials in the mixer is further continued, the temperature in the mixer is raised by the frictional heat of mixing to a thermoplastic substance melting temperature, whereupon the thermoplastic substances be-gin to melt. Heating of the materials in the mixer is effected by said frictional heat until reaching the melt temperature, but since heating by such frictional heat alone takes a long time for raising the temperature from ambient to melt starting temperature, it is desirable to preheat the mixer by using a heating medium to a temperature suited for drying of wastepaper and then effect further drying of wastepaper and melting of the thermoplastic substances by ,.
~138S0 frictional heat of the materials. This can appreciably shorten the production time.
When high-speed stirring of the materials in the mixer is further continued, the wastepaper begins to beat into the melted thermoplastic substances to effect kneading of the wastepaper, thermoplastic resin and other additives. This kneading should not be continued for a long time because the material temperature in the mixer rises so high as to cause thermal decomposition of the wastepaper, etc., in the materials.
Also, too long time of beating and kneading excessively pro-motes beating of the wastepaper, resulting in reduced mechani-cal strength of the composition moldings.
.
Then the kneaded mass of materials is granulated by using a known granulator to form a composite material composi-tion. Molding of this composition into a form of use may be accomplished by using a known molding means. For example, said composition can be molded by a vented injection molding machine in the same was as molding of an ordinary thermoplastic resin.
In a preferred mode of practice of this invention, stirring in the mixer is decelerated to a medium speed for a short period of time upon completion of material kneading and then stirring of the materials is further continued to effect nucleation in the early stage of granulation. This can reduce the time required for the next granulation step.
No waste of material is suffered if the scraps of the ~r 11385~8 moldings from said composition are asain crushed into powder and mixed in the fresh feed of materials.
Now, the composite material composition using waste-paper according to this invention and the method of producing such composition are described in further detail by way of the embodiments thereof.
Described first is a preferred example of the compo-sition production method according to this invention.
First, old newspapers (wastepaper) are cut into square pieces with size of 7 cm x 7 cm, and the cut pieces of newspaper are further cut into smaller pieces by a turbo-mill.
Only those of the finely cut newspaper pieces which have pas-sed a 5 mm x 5 mm mesh screen are used as the ~astepaper ma-terial for the process. Used in the process of this example are 42.5 kg of the thus obtained newspaper cut pieces, 34 kg of ethylene-propylene copolymer resin as therr.~oplastic resin, 4.25 kg of high-density polyethylene resin, 4.25 kg of ethylene-propylene rubber and 0.04 kg of 2,6-di-t-butyl-4-methylphenol (BHT~ as antioxidant (these materials are hereinafter referred to as blend). This blend is supplied into a mixer which has been previously heated to 75-80C by a heating medium,and then is continuously stirred therein at the rate of 1,060 r.p.m.
for about 25 minutes. Thus, the interior of the mixer is ini-tially kept at said preheating temperature 75-80C, but as the blend with a lower temperature than such preheatin~
~ - 12 -temperature is supplied into the mixer, the temperature therein drops temporarily. However, since the blend is stirred at high speed in the mixer, the tempera,ure in the mixer begins to rise 5 minutes after the start of stirring owing to frictional heat which is generated by mixing of the blend materials. Such rise of temperature takes place slowly until moisture in the waste-paper in the blend is driven off to effect sufficient drying thereof. When drying of the wastepaper in the blend is sub-stantially completed, there takes place more sharp rise of intra-mixer temperature by dint of frictional heat, and when the tem-perature in the mixer reaches 162C, the thermoplastic sub-stances in the blend begin to melt. 20 minutes was required until such melting began from start of stirring. Melting of the thermoplastic substances causes sharp increase of the blend viscosity, so that frictional heat is generated succes-sively by the continued agitation to effect perfect melting of the thermoplastic substances. As the thermoplastic substances are thus melted, the wastepaper is beating into the melt phase.
In this condition, the beaten wastepaper and molten thermo-plastic substances (which rope) are kneaded while further pro-moting beating of the wastepaper and causing impregnation of the theremoplastic substances in the beaten wastepaper. If stir-ring isfurther continued for a long time, the temperaturein the mixer excessively rises to give rise to an unfavorable situation such as carbonatization of the wastepaper component in the blend, so that this kneading step was switched to the next nucleation step upon passage of about 25 minutes after start of stirring in the mixer. In the above-described process, the load current of the mixer motor is a~ound 200 A at the ` B~ stage where mixing and ~ 9 of the blend has been completed, but said load current ~egins to inrease with start of melting of the thermoplastic substances in the blend and the viscosity of the blend ri~o~ u~ in accordance ~ith advancement of melting, causing further increase of the load current of the mixer motor. When the load current of saia mixer motor has reached about 250 A, control of proceeding to the next nucleation step was performed. The blend temperature at the time of proceeding to the nucleation step was 180-190C. In the next nucleation step, additional stirring was'carried out for 6-7 minutes by dropping the stirring rate to 530 r.p.m. This has initiated ~ormation of clusters of small particles oi the kneaded blend (early phase of granulation). The blend tempera-ture upon completion of this nucleation step was 225C.
After completion of this nucleation step, the blend was transferred into another mixer which had been water-cooled to about 20C, and further subjected to additional 15-minute stirring at the rate of 100 r.p.m., whereby the blend wa~
formed into particles with diameter of approximately 2-3 mm, with temperature thereof being down to 70C. The thus granulated blend may be molded into a desired form of use by a vented l'l~i injection molding machine in the same way as molding of an ordinary synthetic resin.
'rhe moldings obtained from the above-described composite material compositions according to this invention had the properties shown in the following table. In Example 1, a composite material composition was prepared according to the above-described method by using 42.5 kg of wastepaper, 34 kg of ethylene-propylene copolymer resin, 4.25 kg of high-density polyethylene resin, 4.25 kg of ethylene-propylene rubber and 0.04 kg of ~H~, and a molding was formed from such composition.
In Example 2, a similar composition was prepared in the similar way by using 25.5 kg of wastepaper, 40.8 kg of ethylene-polypropylene copolymer resin, 5.1 kg of high-density polyethylene resin, 5.1 kg of ethylene-propylene rubber, 8.5 kg of calcium carbonate, 0.2 kg of stearic acid and 0.05 kg of BHT. In Comparative Example 1, a molding was formed from a blend consisting of 80 kg of ethylene-propylene copolymer resin, 10 kg of high-density polyethylene resin, 10 kg of ethylene-propylene rubber and 0.1 kg of BHT. The composition ~f Comparative Example 1 is same as that of Example 1 from which wastepaper was excluded. In Comparative Example 2, a composition was prepared by using 3 parts by weight of a thermoplastic resin and 2 parts by weight of talc. Thus, it shows the properties of a composition in which an înorganic filler is incorporated.
In Comparative Example 3, a composition was prepared according to Example 1 without using wastepaper but by using instead woodmeal crushed to the size of less than 30 meshes.
The ~n~g rate in the table was mea~red accord~g to the U.S. Federal Motor Vehicle Safety Standard~.
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~6
Claims (13)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A composition produced by mixing and beating 100 parts by weight of cut wastepaper pieces of a size less than 30 mm.
with a molten mixture consisting essentially of about 70 to 150 parts by weight of thermoplastic resin and upto about 20 parts by weight of rubber, the cut wastepaper being im-pregnated with the molten mixture.
with a molten mixture consisting essentially of about 70 to 150 parts by weight of thermoplastic resin and upto about 20 parts by weight of rubber, the cut wastepaper being im-pregnated with the molten mixture.
2. A composition of claim 1, further comprising upto about 25 parts by weight of an inorganic filler.
3. A composition according to claim 1 or 2, further comprising stearic acid as lubricant.
4. A composition according to claim 1 or 2, which contains about 20 parts by weight of rubber.
5. A method of producing a granular molding composition that provides substantially reduced linear shrinkage and excellent mechanical strength, comprising the steps of cutting wastepaper into pieces of a size less than 30 mm., stirring 100 parts by weight of the wastepaper at high speed in a mixer with about 70 to 150 parts by weight of the thermoplastic resin too drive off moisture from the wastepaper, and to melt the thermoplastic resin, continuing high speed stirring to beat and knead the cut wastepaper with the molten resin and thereby impregnate the cut wastepaper with the molten resin, and then granulating the composition.
6. A method of claim 5, wherein the wastepaper cutting step comprises cutting wastepaper with a cutter and then crushing the cut wastepaper in a mill.
7. A method of claim 5, wherein the mixer is preheated with a heating medium.
8. A method of claim 7, wherein before the kneading step is converted into the granulation step, the stirring rate of the mixer is reduced to a medium level for a short time after completion of the kneading step to nucleate the material, and the granulation step is then started.
9. A method of claim 8, wherein the kneading step is switched into the nucleation step before carbonization of the wastepaper occurs.
10. A method of claim 5, wherein scraps of moldings formed from a granular molding composite produced by the process of claim 5, are crushed into powder and mixed with the wastepaper and a thermoplastic resin or stirring.
11. A process as claimed in claim 5, 6 or 7, in which upto 20 parts by weight of rubber is admixed with the waste-paper resin.
12. A process as claimed in claim 5, 6 or 7, in which upto 25 parts by weight of an inorganic filler is added.
13. A process as claimed in claim 5, 6 or 7, in which stearic acid is added as lubricant.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000330990A CA1138588A (en) | 1979-07-03 | 1979-07-03 | Composite material compositions using wastepaper and method of producing same |
| JP4118080A JPS568454A (en) | 1979-07-03 | 1980-04-01 | Composite material composition utilizing wastepaper and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000330990A CA1138588A (en) | 1979-07-03 | 1979-07-03 | Composite material compositions using wastepaper and method of producing same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1138588A true CA1138588A (en) | 1982-12-28 |
Family
ID=4114599
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000330990A Expired CA1138588A (en) | 1979-07-03 | 1979-07-03 | Composite material compositions using wastepaper and method of producing same |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS568454A (en) |
| CA (1) | CA1138588A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2654943A4 (en) * | 2010-12-22 | 2017-01-25 | Kimberly-Clark Worldwide, Inc. | Oil absorbing material and processes of recycling absorbent articles to produce the same |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6038255B2 (en) * | 1981-12-21 | 1985-08-30 | 古河電気工業株式会社 | Method for producing polyolefin resin sheet containing paper material |
| EP1176167B1 (en) | 2000-07-26 | 2007-03-07 | Sumitomo Rubber Industries Ltd. | Rubber composition for tyre and pneumatic tyre |
| US8940205B2 (en) | 2010-02-26 | 2015-01-27 | Strandex Corporation | Production of useful articles from waste material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS528857B2 (en) * | 1971-11-01 | 1977-03-11 | ||
| JPS5654335B2 (en) * | 1972-07-11 | 1981-12-24 |
-
1979
- 1979-07-03 CA CA000330990A patent/CA1138588A/en not_active Expired
-
1980
- 1980-04-01 JP JP4118080A patent/JPS568454A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2654943A4 (en) * | 2010-12-22 | 2017-01-25 | Kimberly-Clark Worldwide, Inc. | Oil absorbing material and processes of recycling absorbent articles to produce the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5743575B2 (en) | 1982-09-16 |
| JPS568454A (en) | 1981-01-28 |
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