CN1060129A - With the bonding cellulose pulp of poly-hydroxy acid resin - Google Patents
With the bonding cellulose pulp of poly-hydroxy acid resin Download PDFInfo
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- CN1060129A CN1060129A CN 91109192 CN91109192A CN1060129A CN 1060129 A CN1060129 A CN 1060129A CN 91109192 CN91109192 CN 91109192 CN 91109192 A CN91109192 A CN 91109192A CN 1060129 A CN1060129 A CN 1060129A
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/53—Polyethers; Polyesters
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/26—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
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Abstract
With a kind of resin-bonding that contains polyhydroxy acid, improved cellulose pulp product of wet strength and dry strength and preparation method thereof.
Description
The present invention relates to bonding with new type resin, improved dry strength and wet strength and degradable cellulose pulp product and preparation method thereof.
Most of common paper are when wet the time, and its original dry tensile strength can lose and reach 95% or more.In order to improve the wet and/or dry strength of paper, technical known, can during paper-making process, add some water-soluble resin and/or thermoplastic polymer in the paper to usually.Have a lot of technical known resins can invest the long-time wet strength that continues, other resin can only invest of short duration wet strength.Espy is at United States Patent (USP) 4,035, the latter discussed in 229, thinks that temporary wet strength is useful for tissue paper and some other purposes.The temporary wet strength polymer produces people's United States Patent (USP)s 3,556,932 such as () Coscia by the reaction of glyoxal and vinyl amide polymer.
These resins are when being stored in the aqueous solution with the concentration that can be used for commercial paper technology, and Acceptable life is short.Espy(4,035,229) importance of the Acceptable life of high solid concentration and length for commercial purposes is disclosed, and propose to adopt a kind of resin based on branched water-soluble poly-beta-alanine and glyoxal reaction generation.
The commercial resin that can be used to invest dry strength and the long-time wet strength that continues is cationic, water soluble polyamide-chloropropylene oxide (PAE) resinous type.A lot of PAE resins are known technically.See United States Patent (USP) 3,332 for details, 901(Keim).
A kind of PAE preferably is by dimethyl glutarate and diethylenetriamines condensation polymerization.Make with chloropropylene oxide reaction then.The details of this polymerization sees Chan United States Patent (USP) 3,887 for details, and 510(belongs to Borden, Inc.).
PAE type resin has a lot of shortcomings.At first, PAE makes the toxic byproduct that produces and still is present in this product, and further processing is so that its concentration is minimized.These toxic byproducts comprise residual chloropropylene oxide, promptly a kind of suspect carcinogen; 1-chloro-2, ammediol, it changes into chloropropylene oxide again under the alkali condition of heat; And last, cyclopentanone stains, and this can detect in the PAE resin based on adipic acid.Second shortcoming is that the PAE resin is in the solution for continuous hydrolysis, and Acceptable life is limited.Another shortcoming is, most of PAE resins that can buy from the market at present, because limiting factors such as commodity processing and service lifes, maximum solids content is 30～35%.This has limited the commercial distance of freight carried of these aqueous solution.The PAE resin that adds on the paper products green end all is not trapped on the fiber.The efficient of PAE resin in papermaking is confined near neutral to alkaline pH, and is subjected to the strong influence of the existence of COOH group in the cellulose paper matrix.
People know that for a long time thermoplastic poly olefine particle or fiber can make the cellulose fibre heat bonding.These polymer provide much higher dry strength and wet strength, and this depends on the quantity of polymer in cellulosic matrix.
People's such as Aroi day disclosure special permission 7425,226(1974 March 6) a kind of technology of producing 10～50 micron diameters * 1～10 millimeter fiber (I) from polyethylene from high pressure process (PE) solution is described.These fibers obtain a kind of paper pulp shape mixture with the water making beating that contains low quantity of surfactant.(I) 50: 50 admixtures of paper pulp and native cellulose paper pulp are made into a kind of uniform paper with good wet strength.
In Espy United States Patent (USP) 4,458,042, disclose and the bonding absorbent wood suede cellulose paper pulp material of polyalkenes hydrocarbon paper pulp that handle, that be sprayed into the fibrillation shape with wetting agent.These products have good absorbing power, but they are not easy degraded when being dropped.
Badrian Deutsche Bundespatent 2,063,933(1971 July 1) use of the 10 dawn synthetic fiber of making from the polypropylene (PP) of having filled calcium carbonate has been described.Long filament is cut into staple fiber, and mixes, to improve the wet strength of paper with paper pulp.The PP silk of having filled inorganic matter mixes with paper pulp than virgin pp fiber is easier.
Barton and Matsuda(Proc IUPAC/EULEPA, in June, 1972: 133.50) described useful paper product based on polypropylene and polythene thermoplastic plastics (have or do not have wood pulp admixture).The advantage of being announced comprises resistance to water, DIMENSIONAL STABILITY, and wet strength is beautified effect and specific function.
Bogomol and Luchinkina(Bumazh, Prom(1): 10-11(1975); Report that Russian) making beating of wood pulp has increased specific area (s) and length/diameter (l/d) ratio.The increase of s and l/d has also improved bonding between the acrylic fiber.
The nylon of hydrolysis (FMC BP on April 28th, 1,229,806,1971) also has been used to improve wet strength.
Although alkene polymers provides excellent wet strength and dry strength by heat bonding, they are to be not easy biodegradablely, and are non-hydrolysables.Therefore, their disposal has caused problem.
Bohmer(Norsk Skogind, 28(11): 301～2) (in November, 1974) discussed about based on the result of study of paper the natural decomposition speed of the material of plastics.Photochemical degradating at first takes place in paper and plastic refuse, and relatively slow biodegradation takes place then.The existence of wet-strength resins has delayed the degraded of paper.Cellophane solves relative fast with polyethylene (PE) than polystyrene (PS) and polyvinyl chloride (PVC) branch.After exposing 15 months to the open air, paper and poly structure may still be kept intact, but strength character will approach zero.
Gottsching thinks that according to the degradation resistant performance be remote the future of synthetic paper-pulp.(future of the synthetic paper that Future of Synthetic Paper from Plastic Films(plastic sheeting is made), Papier 26(10A): 720-32(1972 October); German; ABIPC 43:A10360).The author has commented the cost development of raw material and synthetic paper, and asserts that no matter some specific use of aunt's dawn, such synthetic pulp paper did not have any breakthrough in 15～20 years from now on.
Most of common wet-strength resins rely on chemical bonding, promptly with the surface reaction of paper fiber carboxylic acid ester, provide and do and wet strength.When papermaker was used the chemistry of bleaching-Re mechanical pulp (BCTMP), these bonding mechanisms were ineffective especially.Sulfate pulp with bleaching is compared, and the bonding part bits number of most of such mechanical pulps has reduced.This is because inactive lignin sheath is arranged on the surface of BCTMP fiber.Paper the producer report, they are ready to use not too expensive BCTMP fiber more, but they are ready to improve the adhesive power of fiber in the scraps of paper.In addition, the rigidity of BCTMP paper pulp fiber provides limited contact for interfibrous chemical bonding.
Prior art disclose can with the cellulose surface chemical bonding, continue and the use of temporary transient cellulose bonding resin for a long time.Otherwise paper product of the present invention is to use a kind of degradable poly carboxylic acid (PHA) resin that utilizes the thermoplastic materials bonding mechanism to make.This PHA has nothing to do to the bonding of cellulose and inorganic matrix and the chemical activity of this matrix.
Prior art also discloses can be by bonding cellulose and the bonding useful polyacrylic adhesive of inorganic matrix of making of thermoplastic materials.These adhesives can not be degraded into the accessory substance (CO of breathing fully by microorganism
2, H
2And can not hydrolysis O etc.).In addition, these thermoplastic adhesives can not separate with cellulose matrix under common slurrying condition again.
According to the present invention, provide under common slurrying condition again slurrying fully again, with the bonding cellulose pulp product of fluoropolymer resin.Under some controlled slurrying condition again, this resin also can be used as a kind of can being retained in this paper pulp with resin binder again.In addition, under the selection of other condition and resin property, this resin can remove from cellulose pulp during the slurrying more fully.
Specifically, have been found that some degradable polyhydroxy acid (PHA) resin is the effective dry strength and the wet-strength resins of paper.These resins are stable in the aqueous solution under Papermaking Conditions.The advantage of PHA polymer is not expensive comparatively speaking, and can provide with 100% solid form with long life.
The present invention relates to high wet strength paper and other pulp product, and their preparation.Product of the present invention can be the form of even sheet material (hard with soft), laminated product or formed article.By suitable selection to resin property, can make suitable container and be used to hold hot liquid, for example the paper coffee cup also can be used for holding alkalescent or faintly acid material.Also can make the hydrophily flocculence material that can absorb liquid, for example be used to have disposable infant diaper, sanitary napkin and the medical liner of high absorbent capacity.The PHA silk also can be admixed in the cellulose fibre of nonwoven or the paper pulp and make disposable garment.
Composition of the present invention has diversified purposes, and this is because fluoropolymer resin can make chemically dissimilar surface such as BCTMP, the L/C sulfate paper pulp fibres of bleaching, synthetic organic fiber or inorfil and particle generation heat bonding under wide pH scope.Major advantage is that fluoropolymer resin of the present invention provides excellent heat bonding, keeps slurrying again, recirculation, hydrolysis and biodegradable ability simultaneously.
Product of the present invention comprises with the bonding cellulosic pulp fibers of some degradable poly carboxylic acid resin binder.5～50% of this this product weight of binder constitutes.If paper pulp fiber and PHA resin are wet fusion, better be to use a kind of wetting agent to be beneficial to fusion.Wetting agent better also becomes the product that is used for absorbing water such as a kind of composition in towel and the baby diaper.Better be that this wetting agent is a kind of molecular weight less than 10000 anionic or nonionic wetting agent.
Polyhydroxy acid as resin binder or polymer contains at least a carboxylic acid unit of selecting from following in the present invention:
（ⅰ）（OCR′R″COOCR′R″CO）q
（ⅱ）[O（CR′R″）nCO]p
（ⅲ）（OCR′R″CR′R″OCR′R″CO）r
（ⅳ）（OCR′R″CR′R″ZCR′R″CR′R″CO）s
(ⅴ) copolymer of (ⅰ)～(ⅳ) and non-hydroxyl acid comonomer
N is 2,4 or 5 in the formula; P, q, r and s are integers, and their summation scope can be from about 350～5,000; R ' and R " are hydrogen, contain the alkyl of 1～12 carbon atom or contain the alkyl of the replacement of 1～12 carbon atom; And Z is O, S, NH or PH.
Non-hydroxyl acid comonomer that is suitable for and example comprise those can with the monomer of lactide or lactic acid condensation polymerization, i.e. lactone, as 6-caprolactone, β-Bing Chunsuanneizhi, α, alpha-alpha-dimethyl-β-Bing Chunsuanneizhi and dodecanol acid lactone; Lactam; Other carboxylic acid such as glycollic acid; And amino acid.More complete list sees also United States Patent (USP) 4,800,219 the 9th hurdles the 27th row.The numerical value of p, q, r and s is selected as to invest degree of crystallinity and the crystallization rate that is suitable for orientation film production.PHA is a PLA preferably, perhaps is homopolymer form, perhaps is a kind of lactide unit more than 50%, better copolymer form more than 70% of containing.For some purposes, especially for food containers, the lactide of L shaped formula is preferably, because its natural human body that is present in neutralizes in some food such as the milk.
Polyhydroxy acid can be directly synthetic from hydroxy acid precursor by polymerization, perhaps synthesizes by the cyclic monomer of hydroxy acid precursor or the polymerization of cyclic dimer lactone.When lactone is produced, will depend on the carboxylic acid type as the cyclic monomer species of polymerization single polymerization monomer or the selection of cyclic dimer species.For production high molecular polyhydroxy acid, better be from the annular lactone polymerization, because the direct molecular weight from the polymer of carboxylic acid production is had practical limit with the balanced reaction of intermediate, cyclic dimer and low-molecular-weight species.
The molecular weight of carboxylic acid of the present invention is high enough to provide the intensity of sufficient viscosity at least, when using the such shaped structure of film and fiber with box lunch, can form lasting film and fiber from this polymer melt.Mean molecule quantity be about 50,000～about 600,000, to be preferably about 150,000～about 450,000 be effective in these forms of the present invention.If molecular weight is too high, then in the required temperature of these compositions of melt-processed too much degraded can take place.When this polymer is introduced in the paper pulp that is the particle form, also can use the polymer of lower molecular weight, comprise that those contain the polymer of a small amount of unreacted monomer and oligomer.Yet polymer must be by fully polymerization, so that be unhydrolyzed basically in manufacturing, storage and the use of paper, and it must not soften and adhere on the dryer drums.
The PHA resin will be used alone as binder resin usually.Yet, in order to strengthen some performance of some products,, better be to make the another kind of material of PHA fusion, as PAE, polyalkenes hydrocarbon, polyvinyl alcohol, starch, yuban and other as wet or dry strength, impact strength or tearing strength.If a kind of non-conforming polymer will with the PHA fusion, then will comprise a kind of compatibility agent, so that produce on a kind of microcosmic admixture uniformly.Better be that the PHA content of this binder resin is 50% at least.
" degradable " this term that this paper uses for polyhydroxy acid, the polyhydroxy acid that means this degradation material partly is biodegradable, and the more important thing is and can pass through hydrolytic degradation.Degradation speed is consistent with its desired use, that is, and the not significantly degraded of this product in normal storage with in using, but after abandoning, can degrade through one period reasonable time.For hydrolytic degradation, better can use subacidity or alkali condition.The speed of hydrolytic degradation is subjected to the influence of polymer crystallization degree and water exposure.By hydrolytic degradation, the words that monomeric unit such as hope change into useful polyhydroxy acid again can be reclaimed, and also can be used as the optimum waste material of a kind of environment and are abandoned.
When papermaking, mixing in the PHA resin paper chemical addition agent of mechanical entrapment in the paper substrate body to be useful.Such chemical addition agent comprises dyestuff, fluorescent whitening agent, organic and inorganic filler, the conduction chemicals, biocide, fungicide, sizing agent is made the crepe paper agent, defoamer, retention agent, drainage aids, crosslinking agent, anti-stick isolating agent, anticorrosive chemicals, deinking solvent, hydrophilic or oleophobic chemicals, and chelating agent.
In the manufacturing of product of the present invention, the PHA resin is the form with any hope, as the fiber or the sheet material of particle, fiber, ejection, directly introduces in this paper pulp.Fiber can be short length silk or continuous yarn, and can be fibrillation.Sheet material can be form of film, or spins or nonwoven sheet.Resin can be by do to mix or introduce in this paper pulp in any one stage of the wet processing of paper pulp, for example, is introduced on the screen cloth or directly and is introduced in the beater.Better be to be introduced in the beater, because paper pulp and resin are fully mixed.Prepare paper with routine techniques then.
If use a kind of wetting agent, it can be introduced in the dry cellulosic paper pulp, during paper pulp and PHA resin dry are mixed, add, or during wet procedure of processing, add.
For intensity and other perfect performance that reaches product of the present invention, be necessary to make PLA (PLA) polymer thermal softening with the binder fiber cellulose fiber, or make this polymer melt with dipping be coated with this cellulosic pulp fibers.Therefore, the preparation of these products is included in the step that is higher than the above heat-treated of polymer softening point.
The major advantage of the cellulose pulp product that these are bonding is that they not only have remarkable dry strength and wet strength, and slurrying and recirculation again; And resin is hydrolyzable and biodegradable.In addition, if resin is L-polylactide (it is present in a lot of food such as milk and other dairy products) basically, product then of the present invention has effective as wrapping material for food.
Example 1
The explanation of this example is a kind of to be contained the paper composition of polylactide silk and is used as doing and wet-strength resins of paper.
Part A
With 6 mil diameter medical grade polylactide silks as resin binder.
Part B
High yield bleached chemical-Re mechanical pulp (BCTMP) (northern softwood, TembecCompany, 4000 breaking length paper pulp) prepare according to the standard handmade paper step T-205 of US-built pulp and paper industry technological associations (TAPPI), different is, this paper pulp used a Tai Weilinshi blender high speed desintegrate 5 minutes, reached 670 milliliters canadian standard freeness (CSF).The preparation write by hand scraps of paper make it air-dry 24 hours 50% relative humidity, 73.Scraps of paper brightness is 79GE, and thickness is 0.006 inch.
Portion C
On BCTMP write by hand scraps of paper, cut off 20 polylactide fibers (4 inches are long), be arranged in parallel on about 1 inch * 4 inches areas in this write by hand scraps of paper center at a distance of 1mm between the fiber.With 3M Scotch board belt this fiber alignment is fixed.Place another BCTMP write by hand scraps of paper on these basic scraps of paper, thereby make the polylactide fiber clamp between the two pieces of paper sheet, this just is called a composite paper.
This composite paper is placed on the heating plate, and there is a retaining screen top.Composite paper is heated to 250 ℃ rapidly, guarantees the complete fusion of polylactide fiber of this interlayer inside.This heat of thermocouple measurement rises, and need just can reach 250 ℃ of temperature in 1.5 minutes.Composite paper after the heat bonding be 0.014 inch thick, and take from this composite in interlayer, do not contain polylactide another section be 0.12 inch to thickness in the same old way.
Part D
So that the polylactide fiber is orientated a kind of like this mode along tension direction, this composite paper is cut into 1 inch wide, 4 inches long stretching sample.In one 50% relative humidity, 73 air-conditioned rooms,, test with the crossing grip holder speed of 5 inch per minute clocks, 1/4 inch stroke with an Instron Co.1011 type tensile testing machine.Allowing specimen after in distilled water, soaking 5 minutes under the room temperature, carry out the wet strength test.
Polylactide silk described in this example part A is to use step described in the example 1, estimates as dried and wet-strength resins.The results are shown in table 1.
Table 1
The polylactide dry tensile strength wet tensile strength that adds
Percentage is described, with paper pulp (pound/1 inch wide) (pound/1 inch wide)
(butt) is benchmark
2 BCTMP scraps of paper 0 11.4 0
Be heated to 250 ℃
After 2 BCTMP 0 18.4 11.9
The scraps of paper
Be heated to 250 ℃ 22.0 26.4 20.1
Composite paper
1
1. between 2 BCTMP scraps of paper, accompany polylactide.
Table 1 shows that the wet and dry strength that invests these BCTMP joint products that contain polylactide has improved.
Embodiment 2
This example explanation is a kind of to be contained the paper composition that is sandwiched in 2 polylactide films between the BCTMP paper and does and the use of wet-strength resins as paper a kind of.
Part A
Make and contain 15% acetate dipropylene glycol methyl ether ester plasticiser and the 2%TiO that have an appointment
2The polylactic acid polymer mixing of pigment, and make it the double-screw extrusion machine that 6 inches wide moulds that remain on 140～150 ℃ arranged by one.Make film annealing then.Final film is 3 mil thick.The BCTMP write by hand scraps of paper are to prepare with the step described in the example 1 part B.
Part B
The polylactide film is inserted between two TAPPI standard BCTMP write by hand scraps of paper, and in the different temperatures heating, so that make this polymer melt on the surface of BCTMP fiber.The contrast scraps of paper do not have polylactide to be sandwiched in therebetween, and be with have the polylactide film to be sandwiched in the same temperature of therebetween the BCTMP scraps of paper to heat-treat.
Table 2 shows, the BCTMP(that polylactide arranged therebetween is that benchmark calculates 33% polylactide with the paper pulp of oven drying) dry strength depend on laminating temperature.Real laminating temperature is mostly 100～150 ℃ of scopes, yet the polylactide melting characteristic can be adjusted to paper plant's temperature operation scope.When heat treated to 200 ℃ made the polylactide fusion, dry strength doubled.
Table 3 explanation, the wet tensile strength of the contrast BCTMP scraps of paper raise with temperature and increase, and that the bonding lignin of fiber is had is to a certain degree bonding because of it contains oneself to show BCTMP.At room temperature, the polylactide film is not adhered on the BCTMP scraps of paper, and TENSILE STRENGTH is because the intensity of polylactide film just has.Along with temperature raises, polylactide 100 ℃ bonding, and wet strength is improved.Along with temperature raises, in figure GRE-2, still show further improvement.When temperature was higher than 200 ℃, remarkable variable color took place in BCTMP paper pulp.
Portion C
The tension test step sees example 1 part D for details.
Table 2 is sandwiched in the influence of the heat treatment of two polylactide films between the BCTMP write by hand scraps of paper to dry tensile strength
Table 2
Dry tensile strength (pound/inch is wide)
Heat treatment temperature (℃) contrast polylactide composite sheet
(two BCTMP scraps of paper)
100 22.5 39.5
150 22.5 43.1
200 23.5 48.7
Table 3 is sandwiched in the influence of the heat treatment of two polylactide films between the BCTMP write by hand scraps of paper to wet tensile strength
Table 3
Wet tensile strength (pound/inch is wide)
Heat treatment temperature (℃) contrast polylactide composite sheet
(℃) (two BCTMP scraps of paper)
100 0 6.2
150 1.3 7.2
200 6.1 12.2
Example 3
Part A
The effect of the polylactide silk (molecular weight 200,000,13 microns of diameters) of next example confirmation and bleached sulfate pulp fusion.
Part B
Use TAPPI standard 205 steps preparation 3 covers to contain 0% synthetic fiber, 20%(weight) polylactide silk and 20%(weight) polyethylene pulp (Du Pont Company Pulplus
TMQP 3800) the bleached sulfate pulp write by hand scraps of paper.
The extruded polylactide silk of 1/4th inchages (20%(weight), paper pulp with oven drying is benchmark) and bleached sulfate pulp (the northern hardwood of 70% northern softwood/30%) (345 milliliters of canadian standard freeness) fusion, TAPPI standard handmade paper made.Use the Du Pont Pulplus of equivalent amount
TMQP 3800
TM(now claim Plexafil
TM) polyethylene pulp, carry out the comparison of TAPPI write by hand scraps of paper tension test.Control sample is the bleached sulfate pulp that does not contain synthetic fiber.
Table 4.20%(weight is benchmark with the paper pulp of oven drying) heat treatment temperature that contains polyethylene and polylactide bleached sulfate pulp composite sheet of polyethylene and polylactide is to the influence of dry strength
Table 4
Dry tensile strength (pound/inch is wide)
Heat treatment temperature contrast polyethylene composite sheet polylactide composite sheet
（℃）
100 31.0 19.2 20.4
150 31.3 22.2 23.6
200 31.0 24.0 25.3
The heat treatment temperature of polyethylene that table 5 is same and polylactide-bleached sulfate pulp composite sheet is to the influence of wet strength
Table 5
Wet tensile strength (pound/inch is wide)
Heat treatment temperature contrast polyethylene composite sheet polylactide composite sheet
Room temperature 00 0.4
100 0 0 1.0
150 0 2.4 3.6
200 1.8 7.3 7.8
Table 4 explanation, polyethylene is compared with control group with the dry strength of polylactide-bleached sulfate pulp composite sheet and has been reduced.The composite sheet performance that contains the polylactide silk is better than the polyethylene filament composite sheet.By inference, these synthetic fiber have disturbed the hydrogen bond of cellulose fibre to form.The bleached sulfate pulp composite sheet is heat-treated at 100,150 and 200 ℃, so that synthetic fiber are thermally bonded on the cellulose.100～150 ℃ of these scopes are represented the true temperature scope of commercial paper technology.
Table 5 explanation, the paper that contains polylactide reaches the control group that does not contain synthetic fiber with the paper that contains polyethylene pulp and compares, and better wet strength is provided.Polylactide has Repulpable and this attendant advantages of fully biodegradable.
Contain in making before the write by hand scraps of paper of polylactide, the polylactide silk must be used 0.01%(weight) Zonyl
FSO(Du Pont Company) polyoxyethylene perfluoroalkyl ethanol surfactant-dispersed is in water, so that make these moistening and be dispersed in the write by hand scraps of paper.Polyethylene pulp is also used dispersant, to improve humidification and peptizaiton.
Example 4
A kind of flocculence product that contains cellulose fibre, wetting agent and PHA resin binder of this example explanation.
PHA ejection (fibrillation) fiber (binder resin) is to be sprayed onto with conventional method to contain 0.01% Zonyl
Prepare in the water of FSO wetting agent.This PHA ejection fiber that contains wetting agent is analysed fine dried the mixing of starching by premix and bleached softwood sulfate process, then by a blender.Admixture contains 25%PHA ejection fiber and 75% sulfate process is analysed fine slurry.This dried admixture with the wind deposition, forms a kind of floccule then, is heated to 175 ℃ and carries out bonding.Final floccule is used for making the baby diaper lining.These baby diapers have excellent absorbability.When abandoning landfill, this flocculence material is easy to degraded.Also just because of its biodegradable, it can be washed into septic tank system and abandoned by toilet.
Embodiment 5
This example illustrates the bonding paper of the PHA ability of slurrying again.The polylactide film is laminated between two TAPPI standard BCTMP scraps of paper at 100 ℃.The composite sheet of lamination is cut into 9 one inch wide stretching sample, is immersed in 60 ℃ the water, every 10 minutes test tensile strength, carries out altogether 90 minutes.In period, the TENSILE STRENGTH of this composite sheet does not have significant change at this section.
Otherwise, composite sheet stretching sample is immersed in 2% sodium hydroxide solution, cause the violent reduction and the good Repulpable of this composite sheet wet tensile strength.It is that the degraded of decision polylactide BCTMP matrix and of Repulpable measure that TENSILE STRENGTH reduces.After 60 ℃ were soaked 20 fens clock times, polylactide began and the delamination of the BCTMP write by hand scraps of paper.Soak after 30 minutes, this film extends before fracture, but after soaking 40 minutes, film comes off immediately when applying tension force.
Through (the great majority slurrying condition again that runs in for paper industry, this time is very enough) after 60 fens clock times, this laminate does not have remarkable wet strength, and can be easy to slurrying again.
Lamination composite sheet sample soaked 40 minutes in 60 ℃ 2% caustic solution, put into Wei Lin Shi blender high speed processing then 1 minute.Can see polylactide film and some very little film particles things of separating from the BCTMP scraps of paper after the fusion.In 2% caustic solution, after 40 minutes, handled 1 minute, do not see the film particles thing in Wei Lin Shi blender high speed in 90 ℃ of immersions.
Polylactide separates this fact and shows that the polylactide fiber can be back in the papermaking operation with BCTMP when handling with caustic solution, and this is impossible to other wet-strength resins.
The influence that table 6 description time, temperature and water and 2% caustic-alkali aqueous solution are degenerated to polylactide film wet tensile strength.The polylactide film is pressed the preparation of example 2 part A, is sandwiched between two Tembec, the 4000 BL BCTMP TAPPI standard T-205 handmade papers.
Table 6
In the soak time water in wet 2% caustic solution that stretches
(branch) (pound/inch is wide) wet stretch (pound/inch is wide)
10 6.9 1.7
20 10.2 0
30 7.8 0
40 8.6 0
50 7.1 0
60 10.2 0
70 10.2 4.9
80 13.3 2.0
90 7.7 0
Claims (14)
1, a kind of paper product that contains by the bonding cellulose fibre of the fluoropolymer resin that contains polymer, described polymer contain from by the carboxylic acid unit of selecting following a group of forming:
(i)(OCR′R″COOCR′R″CO)q
(ii)[O(CR′R″)nCO]p
(iii)(OCR′R″CR′R″OCR′R″CO)r
(iv)(OCR′R″CR′R″ZCR′R″CR′R″CO)s
(the v) copolymer of (i)～(iv) and non-hydroxyl acid comonomer
Wherein n is 2,4 or 5; P, q, r and s are integers, its summation is about 350～5,000; R ' and R " are selected from hydrogen, contain the alkyl of 1～12 carbon atom and contain the alkyl of the replacement of 1～12 carbon atom; Z is selected from O, S, NH or PH.
2, the product of claim 1, wherein this polymer contains at least 50% PLA.
3, the product of claim 1, wherein this polymer contains at least 70% PLA.
4, claim 2 and 3 product, wherein this polymer contains at least 50% and accounts for preferred PLA with the L-lactic acid units.
5, the product of claim 1, wherein this fluoropolymer resin contains at least 50% described polymer.
6, claim 1～5 contains the product of 5～50% fluoropolymer resins.
7, the product of claim 1～6, wherein cellulose fibre is a sulfate pulp.
8, the product of claim 1～6, wherein cellulose fibre is a BCTMP paper pulp.
9, claim 1～8 contains the product of wetting agent.
10, the product of claim 1～9, wherein fluoropolymer resin is the admixture that contains another kind of polymer.
11, claim 1～10 product in the form of a sheet.
12, claim 1～10 is the product of food containers form.
13, claim 9 is a kind of product that can absorb the hydrophilic cotton-shaped material forms of liquid.
14, the preparation technology of the plain pulp product of a kind of binder fiber comprises cellulosic pulp fibers is mixed with a kind of fluoropolymer resin that contains polymer, and described polymer contains and comprises from by the carboxylic acid unit of selecting following a group of forming:
（ⅰ）（OCR′R″COOCR′R″CO）q
（ⅱ）[O（CR′R″）nCO]p
（ⅲ）（OCR′R″CR′R″OCR′R″CO）r
（ⅳ）（OCR′R″CR′R″ZCR′R″CR′R″CO）s
(ⅴ) copolymer of (ⅰ)～(ⅳ) and non-hydroxyl acid comonomer
N is 2,4 or 5 in the formula; P, q, r and s are integers, its summation is from about 350～5,000; R ' and R " are selected from hydrogen, contain the alkyl of 1～12 carbon atom, and contain the alkyl of the replacement of 1～12 carbon atom; And Z is selected from O, S, NH or PH;
The mixture of fiber and resin is shaped; And the mixture heated that will be in dry state, shaping arrives the above a certain temperature of this resin softening point.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US588,412 | 1984-03-12 | ||
| US58841290A | 1990-09-26 | 1990-09-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1060129A true CN1060129A (en) | 1992-04-08 |
Family
ID=24353739
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91109192 Pending CN1060129A (en) | 1990-09-26 | 1991-09-26 | With the bonding cellulose pulp of poly-hydroxy acid resin |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0550490A4 (en) |
| JP (1) | JPH06500603A (en) |
| CN (1) | CN1060129A (en) |
| AR (1) | AR245249A1 (en) |
| AU (1) | AU8517891A (en) |
| CA (1) | CA2090975A1 (en) |
| IE (1) | IE913364A1 (en) |
| MX (1) | MX9101238A (en) |
| PT (1) | PT99052A (en) |
| WO (1) | WO1992005311A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109208387A (en) * | 2018-10-10 | 2019-01-15 | 马鞍山市康辉纸箱纸品有限公司 | A kind of high-strength anti-flaming environmental protection package paper |
| CN112262082A (en) * | 2018-03-29 | 2021-01-22 | 普乐模塑纤维技术私人有限责任公司 | Biodegradable and compostable food packaging unit from moulded pulp material with cellulose-based laminate layer and method for manufacturing such food packaging unit |
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|---|---|---|---|---|
| US5444113A (en) * | 1988-08-08 | 1995-08-22 | Ecopol, Llc | End use applications of biodegradable polymers |
| US6323307B1 (en) | 1988-08-08 | 2001-11-27 | Cargill Dow Polymers, Llc | Degradation control of environmentally degradable disposable materials |
| US5502158A (en) * | 1988-08-08 | 1996-03-26 | Ecopol, Llc | Degradable polymer composition |
| JP2513091B2 (en) * | 1991-05-10 | 1996-07-03 | 株式会社島津製作所 | Biodegradable composite material and manufacturing method thereof |
| CA2068368A1 (en) * | 1991-05-13 | 1992-11-14 | Masanobu Ajioka | Degradable laminate composition |
| EP0533314A3 (en) * | 1991-09-17 | 1993-06-30 | Novacor Chemicals (International) S.A. | Biodegradable polyester compositions |
| US5142023A (en) * | 1992-01-24 | 1992-08-25 | Cargill, Incorporated | Continuous process for manufacture of lactide polymers with controlled optical purity |
| US6005067A (en) * | 1992-01-24 | 1999-12-21 | Cargill Incorporated | Continuous process for manufacture of lactide polymers with controlled optical purity |
| US5247059A (en) * | 1992-01-24 | 1993-09-21 | Cargill, Incorporated | Continuous process for the manufacture of a purified lactide from esters of lactic acid |
| US6326458B1 (en) | 1992-01-24 | 2001-12-04 | Cargill, Inc. | Continuous process for the manufacture of lactide and lactide polymers |
| US5258488A (en) * | 1992-01-24 | 1993-11-02 | Cargill, Incorporated | Continuous process for manufacture of lactide polymers with controlled optical purity |
| US5247058A (en) * | 1992-01-24 | 1993-09-21 | Cargill, Incorporated | Continuous process for manufacture of lactide polymers with controlled optical purity |
| US6005068A (en) | 1992-10-02 | 1999-12-21 | Cargill Incorporated | Melt-stable amorphous lactide polymer film and process for manufacture thereof |
| US5338822A (en) * | 1992-10-02 | 1994-08-16 | Cargill, Incorporated | Melt-stable lactide polymer composition and process for manufacture thereof |
| AU5294893A (en) | 1992-10-02 | 1994-04-26 | Cargill Incorporated | A melt-stable lactide polymer fabric and process for manufacture thereof |
| JP3375369B2 (en) * | 1993-04-13 | 2003-02-10 | 三井化学株式会社 | Disposable food containers |
| US5905046A (en) * | 1995-10-13 | 1999-05-18 | Uni-Charm Corporation | Biodegradable and hydrolyzable sheet |
| DE19543635A1 (en) * | 1995-11-23 | 1997-05-28 | Hp Chemie Pelzer Res & Dev | Composite materials made from polyhydroxy fatty acids and fiber materials |
| JP2001212920A (en) * | 2000-01-31 | 2001-08-07 | Toppan Printing Co Ltd | Packing material, packaging bag, packaging container lid and packaging container |
| DE60334183D1 (en) * | 2002-09-18 | 2010-10-28 | Toray Industries | Fiberboard and process for its production |
| WO2011087438A1 (en) * | 2010-01-12 | 2011-07-21 | Innventia Ab | Mouldable material |
| EP2617896A1 (en) | 2012-01-20 | 2013-07-24 | ABB Technology Ltd | Cellulose based electrically insulating material |
| WO2013169203A1 (en) * | 2012-05-11 | 2013-11-14 | Södra Cell Ab | Process for manufacturing a composition comprising cellulose pulp fibers and thermoplastic fibers |
| AU2016393671A1 (en) | 2016-02-16 | 2018-09-13 | Kemira Oyj | Method for producing paper |
| US10435843B2 (en) | 2016-02-16 | 2019-10-08 | Kemira Oyj | Method for producing paper |
| NL2017421B1 (en) * | 2016-07-25 | 2018-01-31 | Huhtamaki Molded Fiber Tech Bv | Bottle divider from a moulded pulp material with reduced surface roughness, and method for manufacturing such bottle divider |
| WO2018021911A2 (en) * | 2016-07-25 | 2018-02-01 | Huhtamaki Molded Fiber Technology B.V. | Bottle divider from a moulded pulp material with reduced surface roughness, nd method for manufacturing such bottle divider |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3844987A (en) * | 1972-07-28 | 1974-10-29 | Union Carbide Corp | Contour adapted passenger loading ramp biodegradable transplanter containers |
| US4057537A (en) * | 1975-01-28 | 1977-11-08 | Gulf Oil Corporation | Copolymers of L-(-)-lactide and epsilon caprolactone |
| GB8910095D0 (en) * | 1989-05-03 | 1989-06-21 | Smith Ernest | Bags |
| GB2243327A (en) * | 1990-02-16 | 1991-10-30 | Procter & Gamble | Biodegradable, liquid-impervious sheet laminate |
| WO1991013207A1 (en) * | 1990-02-21 | 1991-09-05 | Pulp And Paper Research Institute Of Canada | POLY-β-HYDROXYALKANOATES FOR USE IN FIBRE CONSTRUCTS AND FILMS |
-
1991
- 1991-09-13 CA CA 2090975 patent/CA2090975A1/en not_active Abandoned
- 1991-09-13 EP EP19910916153 patent/EP0550490A4/en not_active Withdrawn
- 1991-09-13 AU AU85178/91A patent/AU8517891A/en not_active Abandoned
- 1991-09-13 WO PCT/US1991/006481 patent/WO1992005311A1/en not_active Application Discontinuation
- 1991-09-13 JP JP51517591A patent/JPH06500603A/en active Pending
- 1991-09-24 MX MX9101238A patent/MX9101238A/en unknown
- 1991-09-25 IE IE336491A patent/IE913364A1/en unknown
- 1991-09-25 PT PT9905291A patent/PT99052A/en not_active Application Discontinuation
- 1991-09-25 AR AR32074891A patent/AR245249A1/en active
- 1991-09-26 CN CN 91109192 patent/CN1060129A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112262082A (en) * | 2018-03-29 | 2021-01-22 | 普乐模塑纤维技术私人有限责任公司 | Biodegradable and compostable food packaging unit from moulded pulp material with cellulose-based laminate layer and method for manufacturing such food packaging unit |
| CN109208387A (en) * | 2018-10-10 | 2019-01-15 | 马鞍山市康辉纸箱纸品有限公司 | A kind of high-strength anti-flaming environmental protection package paper |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1992005311A1 (en) | 1992-04-02 |
| IE913364A1 (en) | 1992-04-08 |
| AU8517891A (en) | 1992-04-15 |
| PT99052A (en) | 1992-08-31 |
| MX9101238A (en) | 1992-05-04 |
| EP0550490A4 (en) | 1994-03-16 |
| EP0550490A1 (en) | 1993-07-14 |
| CA2090975A1 (en) | 1992-03-27 |
| JPH06500603A (en) | 1994-01-20 |
| AR245249A1 (en) | 1993-12-30 |
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