CN106149479B - Strength Compositions are used to improve the purposes of the wet dimensional stability of paper pulp moulded articles - Google Patents
Strength Compositions are used to improve the purposes of the wet dimensional stability of paper pulp moulded articles Download PDFInfo
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Abstract
It is used to improve the purposes of the wet dimensional stability of paper pulp moulded articles the present invention relates to Strength Compositions.The paper pulp moulded articles pass through the method included the following steps and produce: obtaining fibre stuff, and it is given to the forming tank for expecting molding device；Paper pulp moulded articles are formed by the fibre stuff；And the dry paper pulp moulded articles.The Strength Compositions include at least one permanent wet strength resins, and the Strength Compositions are added to the fibre stuff before forming the paper pulp moulded articles.
Description
Technical field
It is used to improve the purposes of the wet dimensional stability of paper pulp moulded articles the present invention relates to Strength Compositions.
Background technique
By preparing fibre stuff (usually being prepared by recycled fibrous material), and the slurry is put into mold and is manufactured
Paper pulp moulded articles.Mold generally includes perforation and/or mesh, and using suction and/or vacuum, to generate slurry in a mold
Uniform coating.Hereafter, drying be formed by mechanograph, such as in individual dryer or pass through heating mould itself.
Paper pulp moulded articles are widely used for various purposes, for example, packaging material, egg carton, food service tray,
Drinks carrier (beverage carrier), clamshell container, plate and bowl.Recently, having proposed can be by paper pulp moulded articles
Even for making mold used in the casting of concrete structure and/or product.Obviously, such use needs paper pulp moulded articles
Dimensional stability and physical strength (or even when they are wetted).Therefore, there is an urgent need to improve paper pulp moulded articles especially
Wet dimensional stability in strong basicity environment.
Summary of the invention
It is an object of the invention to minimize or may even be eliminated disadvantage existing in the prior art.
It is a further object to provide a kind of cost-efficient methods, are used to improve paper pulp moulded articles special
It is wet dimensional stability and/or physical strength in strong alkali environment.
In the typical use of wet dimensional stability that Strength Compositions according to the present invention are used to improve paper pulp moulded articles,
The paper pulp moulded articles are produced by the method included the following steps:
Fibre stuff is obtained, and it is given to the forming tank for expecting molding device,
Paper pulp moulded articles are formed by the fibre stuff,
The dry paper pulp moulded articles,
Wherein the Strength Compositions include at least one permanent wet strength resins (permanent wet strength
Resin), and before forming the paper pulp moulded articles by the Strength Compositions it is added to the fibre stuff.
It has now unexpectedly been found that when before forming mechanograph by the permanent wet strength comprising at least one synthesis
When the Strength Compositions of resin are added to fibre stuff, it is especially wet in strong alkali environment that paper pulp moulded articles are improved significantly
Dimensional stability and physical strength.It is not wishing to be bound by theory, it is assumed that Strength Compositions are added in the slurry and provide
Interaction so strong during forming mechanograph between intensity resin and fiber, so that even in such as highly basic property
The stability and intensity of raising are also provided in harsh environment.
Further it has been observed that especially improving the long-term wet dimensional stability and physical strength of mechanograph.Therefore, i.e.,
The mechanograph is set to be exposed to strong alkali environment, which is also able to maintain physical strength and physical size in extended period
It is constant or almost unchanged in (such as a few houres, preferably several days, sometimes even some months).An embodiment party according to the present invention
Formula can have > 2Nm/g by the paper pulp moulded articles that method of the invention produces, and preferably > 4Nm/g, more preferably > 10Nm/g are wet
Tensile strength coefficient.
In the context of the present invention, term " strong basicity environment " indicates that environment pH is 10~14, typically 11~14,
It is more typically 12~14.
Fibre stuff can be obtained and in water rupturing fibrous material.Fibre stuff may include from recycled writing paper
And/or the fibrous material of Regenerated plate, such as old corrugated carton (OCC).Preferably, fibrous material OCC.It is preferred according to one
Embodiment, fibrous material include at least 70wt%, preferably at least 80wt% from recycled writing paper and/or Regenerated plate (such as
OCC fibrous material).In some preferred embodiments, fibrous raw material (stock) may include even > 90wt%, preferably
The fibrous material from recycled writing paper and/or Regenerated plate (such as OCC) of even 100wt%.Fibre stuff is given and expects molding dress
The forming tank set.
Permanent wet strength resins can be the resin of crosslinking.Preferably, permanent wet strength resins can be selected from polyamides
Amino amine-epoxy halopropane resin or poly- diisocyanate resin.Especially it has been observed that polyamidoamines amine-epoxy halopropane
Resin and poly- diisocyanate resin provide improved property in strong alkali environment.
According to a preferred embodiment of the present invention, permanent wet strength resins are polyamidoamines amine-ring of self-crosslinking
Oxygen halopropane resin.Polyamidoamines amine-epoxy halopropane resin is based on polyamidoamines amine main chain, which is that adipic acid and two are sub-
The result of condensation reaction between ethyl triamine.Then with epoxyhalopropane react generate crosslinking fluoropolymer resin structure,
The middle main chain along polymer forms azetidine (azetidinium) group of high response.According to one embodiment,
Polyamidoamines amine-epoxy halopropane resin can have < 80%, preferably < 70%, more preferably < 60%, and even more preferably < 50%,
Sometimes azetidinium content even < 40%.According to one embodiment, polyamidoamines amine-epoxy halopropane resin can
To have 0.01~80%, preferably 0.01~70%, more preferable 0.01~60%, even more preferably 0.01~50%, sometimes very
To 0.01~40% azetidinium content.
The amount of azetidine group can be controlled by being carefully chosen such as epoxyhalopropane/amine ratio.Root
According to an illustrative embodiment, polyamides alkylamine-epichlorohydrin resins are with < 0.8, preferably < 0.5, more preferably <
0.45, even more preferably < 0.4, epoxyhalopropane even < 0.3/amine ratio sometimes.Epoxyhalopropane/amine ratio lower limit can
Think 0.1, preferably 0.01.According to one embodiment, resin can have 0.01~0.8, preferably 0.01~0.5, more preferably
0.01~0.45, even more preferably 0.01~0.4, sometimes even 0.01~0.3 epoxyhalopropane/amine ratio.Epoxy halogen third
Alkane/amine ratio can be calculated as the molar ratio of epoxyhalopropane and amine.
Suitable polyamidoamines amine-epoxy halopropane resin can have 80 000~250 000g/mol, preferably 150
The weight average molecular weight of 000~250 000g/mol.Molecular weight is determined by size exclusion chromatography, uses poly- (2- vinylpyridine
Pyridine) it is used as calibration standard.
As described above, polyamidoamines amine-epoxy halopropane resin has the reactive nitrogen azetidinyl of significant quantity
Group, the group provide high cationic charge for resin, this improves holding of the resin on fiber, and provides certainly for resin
Crosslinking ability.Preferably, it is measured by being titrated in pH 7 with polyvinyl sulfuric acid sylvite, polyamidoamines amine-epoxy halopropane tree
Rouge has 1.5~4.5meq/g, preferably 2.0~4.0meq/g, the charge density of more preferable 2.1~3.0meq/g.When retained
When in paper pulp moulded articles, polyamidoamines amine-epoxy halopropane resin self cross-links, and formed around Fiber-Fiber bonding
Strong protection, and prevent bonding hydrolyzed.Preferably, permanent wet strength resins are polyamidoamines amine-epoxy chloropropane.
According to a preferred embodiment of the present invention, permanent wet strength resins are poly- diisocyanate resin.It is preferred that
Poly- diisocyanate resin is used in the form of aqueous emulsion, is uniformly distributed with providing resin to fibre stuff.Poly- two is different
Cyanate ester resin may include aliphatic, alicyclic or fragrant adoption diisocyanate or their mixture.Suitable poly- two is different
Cyanate can preferably include more than two isocyanate groups, such as 2~5 isocyanate groups.Poly- diisocyanate tree
The preferred example of rouge is based on '-diphenylmethane diisocyanate, toluene di-isocyanate(TDI), hexamethylene diisocyanate and different Buddhist
That ketone diisocyanate chemicals.The amount of reactive isocyanate group, i.e. NCO content, can 5~50%, typically 7~
Change in the range of 25%.
According to a preferred embodiment, Strength Compositions include polyamidoamines amine epichlorohydrin resins and anion
Both type polyacrylamides.Anion-polyacrylamide can improve reservation of the permanent wet strength resins on fiber.Yin
The ratio of Ionomer and polyamidoamines amine epichlorohydrin resins can be about 0.05 to 1.
Before forming paper pulp moulded articles, such as during the manufacture of pulp, storage or transport, by intensity groups
Object is closed to be added in pulp.Strength Compositions can be added to the forming tank of pulper, pulp storage tank or molding device
In.
According to a preferred embodiment of the present invention, the additive amount of Strength Compositions is so that fibre stuff is strong in addition
Zeta-potential after degree composition remains < -2.0mV.When Zeta-potential is too close to neutral value, may have and generate asking for foam
Topic.It is therefore preferable that the additive amount of Strength Compositions be so that Zeta-potential of the fibre stuff after adding Strength Compositions be <-
3.0mV, more preferably < -5mV, even more preferably < -10mV.The additive amount of Strength Compositions can be for 1.3~26kg of generation forever
Long property wet-strength resins/ton dry fibers slurry, permanent wet strength resins/ton dry fibers slurry of preferably 2.6~18.2kg, more
It is preferred that the permanent wet strength resins of 5.2~13kg/ton dry fibers slurry, calculated with dry permanent wet strength resins.Meaning
Other places observes, in addition with the Strength Compositions of relatively low dosage can also obtain mechanograph wet dimensional stability and physics it is strong
The improvement of degree.This is favourable, not only due in this way can be to avoid the above-mentioned problem related with neutral Zeta-potential value, also as can
So that the chemicals cost minimization in technique.
According to embodiment of the present invention, defoaming agent can be added into fibre stuff.It can be in addition intensity groups
Defoaming agent is added before closing object.Defoaming agent can be selected from the defoaming agent based on silica and the defoaming agent based on fatty alcohol.It is logical
Often, the additive amount of defoaming agent be 200~500g/ tons of dry fibers slurries, preferably 200~300g/ tons of dry fibers slurry, more preferably
200~250g/ tons of dry fibers slurries.
According to a preferred embodiment, Strength Compositions further include hydrophobing agent.Hydrophobing agent can be alkyl alkene
Ketone dimer wax or paraffin, optimizing alkyl ketene dimer wax.Suitable alkyl ketene dimer wax can have 40~70 DEG C,
It is preferred that 44.5~64 DEG C, more preferable 44.5~49 DEG C of fusing point.
According to embodiment of the present invention, after paper pulp moulded articles molding, spontaneously dry it in atmosphere.Example
Such as, before thermoforming processing, make paper pulp moulded articles dry 10~24 hours, preferably 15~20 hours.It is spontaneously drying
Later, by hot press using 150 DEG C of temperature is higher than and make paper pulp moulded articles thermoforming.
According to a preferred embodiment of the present invention, the paper pulp moulded articles of production are used in concrete product and structure
In manufacture.Paper pulp moulded articles can be the casting mold for being used to form concrete product and/or structure or container (cast mould or
Pod), such as when being poured concrete floor, building basis or similar structure.
Specific embodiment
Some embodiments of the present invention are described in following non-limiting embodiment.
Embodiment 1
Business old corrugated carton (OCC) pulp of concentration 5wt% is used as recycled fiber sources.Use two kinds of differences
The wet-strength resins (Kemira Oyj, Finland) based on polyamidoamines amine-epoxy chloropropane (PAE) (be denoted as herein
Fiberbuilder A and Fiberbuilder B) Lai Tigao handmade paper (hand sheet) intensity.It is given in table 1 wet strong
Spend the property of resin.Alkyl ketene dimer wax (Kemira Oyj, Finland) is used in some implementations together with wet-strength resins
In example.
The performance of the wet-strength resins in embodiment of table 1.
| Chemicals | Solid content, % | PCD(meq/g) | pH |
| Fiberbuilder A | 26.32 | 2.52 | 3.88 |
| Fiberbuilder B | 26.60 | 2.93 | 3.72 |
The ability that fiber possesses wet-strength resins is assessed based on the Zeta-potential of fibre stuff, the Zeta-potential is by using M ü
Tek SZP-6 is measured.Influence of the intensity resin dosage to the Zeta-potential of fibre stuff is shown in Figure 1A and Figure 1B.From Figure 1A
And Figure 1B, the dosage of wet-strength resins increase, and improve the Zeta-potential of fibre stuff.
Under stiring with tap water by the concentration of the original OCC pulp dilution for being discongested (deflaked) to 1wt%.It will
Chemicals used is given in the pulp of OCC for expecting rupture.The dosage of wet-strength resins be 10kg/t, 30kg/t or
50kg/t, and the dosage of AKD is 0kg/t or 5kg/t.The pulp of preparation is stirred about 15 at about 500rpm first
Second, chemicals used is then fed with 15 seconds every time intervals.After feeding, continue mixed pulp slurry 15 seconds.In write by hand
Production has 100g/m in paper manufacturing machine2Base weight handmade paper.By page in the automatic drying chamber of handmade paper manufacturing machine
It is 6 minutes dry at 93 DEG C of temperature and the vacuum of 96kPa, quickly to remove moisture removal.
Before the intensity property (i.e. wet tensile index and dry tensile index) for testing handmade paper produced, according to ISO
Page is pre-processed 24 hours by 187 standards at 23 DEG C in 59% relative humidity.It gives in table 2 for measuring page
Performance device and standard.
2 sheet detecting apparatus of table and standard
Wet tensile index and dry tensile index under different wet-strength resins and AKD dosage are shown in Fig. 2 and Fig. 3
As a result.See from Fig. 2 and Fig. 3, obtains extraordinary wet tensile index result.The raising of dry tensile index is also observed.It is right
It is little with the difference between Fiberbuilder A or Fiberbuilder B result obtained in dry tensile index.However,
Observe that Fiberbuilder B ratio Fiberbuilder A produces better wet tensile index result.It is wet strong for both
Resin is spent, addition AKD provides additional enhancing.
Embodiment 2
Based on the laboratory test of embodiment 1, Fiberbuilder B is selected to be used for the factory in production paper pulp moulded articles
It is further tested with pilot-scale experiment.It is tested together with AKD or under without using AKD both of these case
Fiberbuilder B.Testing scheme is given in table 3.
The testing scheme of 3 pilot-scale of table experiment
| Test No. | Chemicals | Dosage kg/ton | Case number (CN) |
| 1 | AKD | 60 | 1,2,3 |
| 2 | Fiberbuilder B | 30 | B1,B2 |
| 3 | Fiberbuilder B+AKD | 30+5 | B3,B4 |
| 4 | Fiberbuilder B | 50 | B5,B6 |
| 5 | Fiberbuilder B+AKD | 50+5 | B7,B8 |
In test No. 1, AKD solution used has 13% solid content.For case 2, AKD is added into slurry, and
And for case 3, AKD is used as coating.
The production technology of paper pulp moulded articles is as follows:
1. preparing the regeneration corrugated sheet of about 5wt% fibre stuff in pulper, preparation spends about 5~6 minutes；
2. fibre stuff is transferred to 10m3Pulp storage tank in, wherein by pulp from the concentration dilution of 5wt% to
About 1wt%；
3. about 500 liters of pulp to be pumped into the forming tank of moulding press, be dehydrated and is molded into case (moulding of
box)；
4. drying in an atmosphere, thermoforming, and final product is manufactured with hot pressing, wherein temperature is about 180~190
℃。
In these tests, into the forming tank of moulding press add Strength Compositions/wet strength agent, and formed product it
Before, it stirs 5 minutes manually.Before thermoforming, spontaneously dries continue 16 hours in an atmosphere.
Table 4 lists the weight of each case before and after thermoforming processing.
Table 4 (weight in wet base) and weight of (dry weight) each case later before thermoforming processing.
| Case number (CN) | Weight in wet base (kg) | Dry weight (kg) | It handles time (minute) |
| 1 | - | 5.5 | - |
| 2 | - | 5.5 | - |
| 3 | - | 5.4 | - |
| B1 | 11.0 | 5.0 | 21 |
| B2 | 10.1 | 4.8 | 21 |
| B3 | 10.4 | 5.1 | 20 |
| B4 | 10.1 | 5.0 | 20 |
| B5 | 11.6 | 5.8 | 20 |
| B6 | 10.1 | 5.0 | 20 |
| B7 | 11.5 | 5.8 | 20 |
| B8 | 10.8 | 5.3 | 19.5 |
After the case of thermoforming is cooling, a series of performance tests are carried out, it is steady with physical strength and the size of testing each case
It is qualitative.Case 1,2,3, B2, B3, B6, B8 is selected to be used for a series of performance tests.
1. performance test 1
Whole casees is in line, and the weight of 80kg is put into the top about 10 seconds of each case.Whole casees
It is all stable.
2. performance test 2
Tap water is sprayed on case 15 minutes, then the weight of 80kg is put into the top about 10 seconds of each case.Entirely
The case in portion is all stable, but case 1 is apparently slightly softer than other casees.Hereafter, washer is placed on to the top of case, and by the weight of 80kg
Amount is placed on washer, to improve the intensity of pressure.Test the center and peripheral of the top surface of each case.Case 1 ruptures, but other
Case is still stable.
3. performance test 3
Continue for tap water to be sprayed on case 15 minutes, so that total spray time is 30 minutes.In spraying and then secondary general
The weight side of 80kg to the top about 10 seconds of each case.Whole casees are all stable.Then, washer is placed on to the top of case
Portion, and the weight of 80kg is placed on washer, to improve the intensity of pressure.Test the center and peripheral of the top surface of each case.Case 3
Rupture, but other casees are still stable.
4. performance test 4
By all remaining case plastic film wrappeds, to simulate moist environment, and kept for 2 hours.Then, by 80kg
Weight be placed on the top about 10 seconds of each case.In this stage, case 2 ruptures.Then, washer is placed on to the top of case, and
The weight of 80kg is placed on washer, the intensity of pressure is improved.In this stage, case B3 rupture.Case B2 is softer than case B6 and B8,
Still show satisfactory intensity property and dimensional stability.
It was therefore concluded that the Fiberbuider B of 50kg/ tons of dosages generates satisfactory wet strength performance
And dimensional stability.
Even if describing the present invention referring to apparently most viable and preferred embodiment at present, but it is to be understood that this
Invention is not limited to above embodiment, but the present invention also aims to the different modifications covered in the scope of the appended claims
And equivalent technical solution.
Claims (10)
1. a kind of Strength Compositions are used to improve the purposes of wet dimensional stability of the paper pulp moulded articles in strong alkali environment, wherein by force
The pH of alkali environment is 11~14, and the paper pulp moulded articles pass through the method included the following steps and produce:
Fibre stuff is obtained, and it is given to the forming tank for expecting molding device,
Paper pulp moulded articles are formed by the fibre stuff,
The dry paper pulp moulded articles,
It is characterized in that, the Strength Compositions include at least one permanent wet strength resins, the permanent wet strength tree
Rouge is selected from the polyamidoamines amine-epoxy halopropane resin of crosslinking, and by the intensity before forming the paper pulp moulded articles
Composition is added to the fibre stuff, and the additive amount of the Strength Compositions is the permanent wet strength for generating 1.3~26kg
Resin/ton dry fibers slurry, the Strength Compositions include hydrophobing agent, and the hydrophobing agent is selected from alkyl ketene dimer wax or stone
Wax.
2. purposes according to claim 1, which is characterized in that the additive amount of the Strength Compositions is so that the fiber
Zeta-potential of the slurry after adding the Strength Compositions remains < -2.0mV.
3. purposes according to claim 1 or 2, which is characterized in that the additive amount of the Strength Compositions be generate 2.6~
The permanent wet strength resins of 18.2kg/ton dry fibers slurry.
4. purposes according to claim 1 or 2, which is characterized in that the additive amount of the Strength Compositions be generate 5.2~
The permanent wet strength resins of 13kg/ton dry fibers slurry.
5. purposes according to claim 1 or 2, which is characterized in that the Strength Compositions are added to pulper, paper pulp
In the forming tank of storage tank or the molding device.
6. purposes according to claim 1 or 2, which is characterized in that the fibre stuff includes from recycled writing paper or plate
Fiber.
7. purposes according to claim 1 or 2, which is characterized in that the paper pulp moulded articles completed have > 2Nm/g it is wet
Tensile strength coefficient.
8. purposes according to claim 1 or 2, which is characterized in that the paper pulp moulded articles completed have > 4Nm/g it is wet
Tensile strength coefficient.
9. purposes according to claim 1 or 2, which is characterized in that the paper pulp moulded articles completed have > 10Nm/g it is wet
Tensile strength coefficient.
10. purposes according to claim 1 or 2, which is characterized in that the paper pulp moulded articles completed are to be used to form coagulation
The casting mold or container of native product and/or structure.
Priority Applications (13)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510190683.6A CN106149479B (en) | 2015-04-21 | 2015-04-21 | Strength Compositions are used to improve the purposes of the wet dimensional stability of paper pulp moulded articles |
| RU2017134974A RU2694755C2 (en) | 2015-04-21 | 2016-04-21 | Use of hardening composition for increasing dimensional stability in wet conditions of product from pressed fibrous mass |
| ES16723402T ES2743796T3 (en) | 2015-04-21 | 2016-04-21 | Use of a strength composition to increase the wet dimensional stability of a molded pulp article |
| US15/568,478 US20180148894A1 (en) | 2015-04-21 | 2016-04-21 | Use of a strength composition for increasing wet dimensional stability of a moulded pulp article |
| KR1020177025534A KR102403662B1 (en) | 2015-04-21 | 2016-04-21 | Use of a strength composition to increase the wet dimensional stability of molded pulp articles |
| PCT/FI2016/050261 WO2016170232A1 (en) | 2015-04-21 | 2016-04-21 | Use of a strength composition for increasing wet dimensional stability of a moulded pulp article |
| NZ735108A NZ735108A (en) | 2015-04-21 | 2016-04-21 | Use of a strength composition for increasing wet dimensional stability of a moulded pulp article |
| EP16723402.0A EP3286379B1 (en) | 2015-04-21 | 2016-04-21 | Use of a strength composition for increasing wet dimensional stability of a moulded pulp article |
| PL16723402T PL3286379T3 (en) | 2015-04-21 | 2016-04-21 | Use of a strength composition for increasing wet dimensional stability of a moulded pulp article |
| MYPI2017703954A MY185670A (en) | 2015-04-21 | 2016-04-21 | Use of a strength composition for increasing wet dimensional st ability of a moulded pulp article |
| JP2017554486A JP2018513285A (en) | 2015-04-21 | 2016-04-21 | Use of strength composition to enhance wet dimensional stability of pulp molding |
| AU2016252071A AU2016252071B2 (en) | 2015-04-21 | 2016-04-21 | Use of a strength composition for increasing wet dimensional stability of a moulded pulp article |
| CA2978243A CA2978243A1 (en) | 2015-04-21 | 2016-04-21 | Use of a strength composition for increasing wet dimensional stability of a moulded pulp article |
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|---|---|---|---|
| CN201510190683.6A CN106149479B (en) | 2015-04-21 | 2015-04-21 | Strength Compositions are used to improve the purposes of the wet dimensional stability of paper pulp moulded articles |
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| CN114269658B (en) * | 2019-04-04 | 2023-10-20 | 艾可产品公益公司 | Molded articles made from pulp compositions providing grease and water resistance |
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| US6429253B1 (en) * | 1997-02-14 | 2002-08-06 | Bayer Corporation | Papermaking methods and compositions |
| CN1209484A (en) * | 1997-08-21 | 1999-03-03 | 西安岳胜纸制食品容器有限公司 | Production process for disposable tableware |
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