CN105228657B - The modified cellulose of surface treatment and production and preparation method thereof from chemical kraft fibers - Google Patents

Abstract

The present invention provides a kind of Modified Kraft paper pulp fiber with unique properties.The modified fibre can be the almost indistinguishable modified bleached kraft fibers of counterpart with its routine, the difference is that it is with low polymerization degree (DP).The present invention also provides for manufacture the modified fibre method and the product being produced from it.The method can be the single step acidity that can merge into the single stage in multistage bleaching technique, iron catalysis peroxide cure process.The product can be chemical cellulose raw material, microcrystalline cellulose raw material, Time of Fluff Slurry and the product being produced from it.

Description

The modified cellulose of surface treatment from chemical kraft fibers and its manufacture and make Use method

Technical field

This disclosure relates to the chemical modification of cellulose fibre.More particularly, this disclosure relates to from a system is shown The chemically-modified cellulose fiber of the bleached kraft pulp of row unique property, by its performance improvement to surmounting from kraft pulp Standard fibers cellulose fiber and make it can be used for office so far to be also limited to expensive fiber (for example, cotton or high alpha content sulphite Paper pulp) application.In particular, the chemical modification bleached kraft fibers can express out one or more following beneficial spies Property, including but not limited to improved smell control, improved compressibility and/or increased whiteness (brightness).It is described Chemical modification bleached kraft fibers can express out these one or more beneficial characteristics, while also keep on-chemically modified bleaching One or more other characteristics of kraft fibers, for example, keeping fibre length and/or freedom.When with one or more work Property reagent processing fiber when, modified fibre benefit can be further enhanced.

The disclosure is further to from the bleached softwood and/or hardwood ox for showing low polymerization degree or ultra low polymerization degree The chemically-modified cellulose fiber of mulberry paper slurry, is adapted to the Time of Fluff Slurry as absorbent products, be used as include cellulose ether with Chemical cellulose raw material in the cellulose derivative production of ester and the consumer goods." degree of polymerization " used herein can be abbreviated as “DP”.The disclosure further relates to the fibre from the chemical modification kraft fibers with the equilibrium polymerization degree less than about 80 Dimension element.More particularly, chemical modification kraft fibers described herein show low polymerization degree or ultra low polymerization degree (herein In be known as " LDP " or " ULDP "), about 80 can be decreased below by acid or basic hydrolysis processing with further degree of being polymerized (such as decreasing below about 50), to be adapted to a variety of downstream applications.

The disclosure is directed to the method for manufacturing described modified fibre.A kind of use is provided on disclosure partial extent In the method for the carboxyl and aldehyde radical degree of functionality for increasing kraft fibers simultaneously.Described fiber undergoes catalytic oxidation treatment.One In a little embodiments, the fiber iron or copper are aoxidized, then further bleach has beneficial whiteness characteristic to provide Fiber, the beneficial whiteness be for example can be with the whiteness compared with standard bleached fiber.In addition, the present invention discloses at least one Technique can provide above-mentioned improved beneficial characteristics without introducing the increased step of cost for being post-processed to bleached fiber Suddenly.In the embodiment of this low cost, the fiber can be in the single of kraft process (such as brown paper bleaching process) It is handled in stage.Another embodiment is related to including D₀Five sectional bleaching sequences of E1D1E2D2 processes, wherein the 4th (E2) section Including catalytic oxidation treatment.

Finally, this disclosure relates to all consumer goods, the cellulose that are manufactured using described chemically-modified cellulose fiber Derivative (including cellulose ether and ester) and microcrystalline cellulose.

Background of invention

Cellulose fiber peacekeeping derivative is widely used in paper, absorbent products, food or food in relation to application, drug and work Industry application.The main source of cellulose fibre is wood pulp and cotton.Cellulose source and cellulose treatment conditions generally determine The characteristic of cellulose fibre, and therefore determine applicability of the fiber for certain intended applications.To processing cost phase There are demands for very extensive to relatively low but purposes and cellulose fibre to be used for a variety of applications.

Cellulose comprising the polymer chain of hundreds of to thousands of a glucose units usually to exist.Oxycellulose Various methods are known.In cellulose oxidation, the hydroxyl of the glucosides of cellulose chain can be converted to (for example) such as aldehyde radical Or the carbonyl of carboxyl.According to the method for oxidation and condition used, carbonyl modified type, degree and position may be different.It is known Certain oxidizing conditions can make cellulose chain itself degrade, such as by making the glucosides ring crack solution in cellulose chain lead to depolymerization.Greatly In most cases, not only viscosity reduces depolymerizing cellulose, but also fibre length is shorter compared with cellulosic material.Work as cellulose degradation When (such as by depolymerization and/or significantly decrease fibre length and/or fibre strength), be likely difficult to processing and/or may It is unsuitable for many downstream applications.The method of modified cellulose fibre for that can increase both carboxylic acid and aldehyde degree of functionality still has need to It asks, these methods will not make cellulose fibre widely degrade.The disclosure, which provides, solves one or more of these insufficient uniquenesses Method.

It has made various trials and has carried out oxycellulose to provide carboxyl and aldehyde degree of functionality without making cellulose to cellulose chain Fiber degradation.In traditional cellulose oxidation method, when there is aldehyde radical on cellulose, it may be difficult to which control or limitation are fine Tie up the degradation of element.The trial previously solved these problems includes using multistep oxidation technology, such as in one step with site Specificity pattern modifies certain carbonyls, and other hydroxyls are aoxidized in another step, and/or provides conditioning agent and/or guarantor Agent is protected, all steps all may come extra charge and by-product to cellulose oxidation process bands.Therefore, it is necessary to cost-effective And/or the method that cellulose is modified that can be carried out in single-step process (such as kraft process).

The disclosure provides novel method, and the middle method attempted provides huge improvement compared with prior art.In general, The oxidation of cellulose kraft fibers (in the prior art) is carried out after bleaching process.It was unexpected that human hair of the present invention The existing stage (especially the 4th sections of five sectional bleaching sequences) of bleaching process now can be used to carry out the oxidation of oxidized fibre cellulose fiber. In addition, it was unexpected that the inventors discovered that metallic catalyst (especially iron catalyst) can be used for completing this in bleaching process Kind oxidation without influence finished product, for example, because catalyst will not be kept in cellulose combination so that bleaching process terminal it The preceding at least some remaining iron of removing are more prone to than the expection based on ability domain knowledge.In addition, unexpectedly, the present inventor It was found that such method can be carried out and not make fiber degradation substantially.

Cellulose fibre (including kraft pulp) can use metal and peroxide and/or acid oxidase excessively known in the art 's.For example, cellulose available iron and peroxide (Fenton reagent (Fenton's reagent)) oxidation.Referring to Kishimoto Et al., Holzforschung, volume 52, the 2nd phase (1998), 180-184 pages.Metal and peroxide (such as Fenton reagent) are Relatively inexpensive oxidant makes them be suitable for the large-scale application of such as kraft process to a certain extent.With regard to Fenton reagent Speech, it is known that biodegradable fiber is plain in acid condition for this method for oxidation.Therefore, it does not expect natively in kraft process It is middle to use Fenton reagent without widely degradation of fibers, such as in acid condition with the loss of fibre length.In order to prevent The degradation of cellulose, Fenton reagent often uses under alkaline condition, but Fenton's reaction is significantly suppressed.However, in alkali Under the conditions of property other disadvantages are likely present using Fenton reagent.For example, cellulose still may degrade or fade.In ox-hide In pulp processing, cellulose fibre is usually bleached in multistage process, generally comprises highly acid and strong basicity blanching step, packet Include at least one basic step near bleaching process terminal or terminal.Therefore, with known in the art on the contrary, in ox-hide The fiber of the acid section iron oxidation of paper bleaching process can generate the fiber of the chemical property with enhancing, but not have mechanical degradation Or fade, this is quite surprising.

Therefore, it is necessary to one kind introducing aldehyde and carboxyl-functional to cellulose fibre (such as from the fiber of kraft pulp) It spends without widely degraded cellulose and/or so that cellulose is become unsuitable for many downstream applications low cost and/or single step oxygen Change.In addition, also oriented cellulose fibre introduces the demand of the carbonyl (such as carboxylic acid, ketone and aldehyde radical) of high-content.For example, it is desirable to Do not inhibit under conditions of oxidation reaction using oxidant (being different from for example using Fenton reagent in alkaline pH) to introduce high-content Carbonyl.In order to provide the method for meeting these demands, inventor overcomes many difficulties of the prior art.

Other than the difficulty in the chemical constitution of control fiber element oxidation product and the degradation of those products, it is known that Method for oxidation can influence the impurity in other properties, including chemical and physical features and/or finished product.For example, method for oxidation can shadow Ring the impurity content in crystallinity, hemicellulose level, color and/or finished product.Finally, method for oxidation can influence processing for work The ability of the cellulose products of industry or other application.

The purpose for usually carrying out wood pulp bleaching is the white or whiteness of selectively increase paper pulp (generally by removing wood Plain and other impurity), without negatively affecting physical property.Bleached chemical paper pulps (such as kraft pulp) usually require it is several not Same bleaching stage, to obtain the required whiteness with good selectivity.In general, bleaching process comes using with the pH ranges changed The stage of progress.This variation contributes to the product (for example) decomposed by dissolved lignin and is generated in bleaching process to remove Impurity.Therefore, generally, it is desirable to use a series of acidic phases (such as three acid ranks successively in bleaching process Section), the identical whiteness with alternate acidity/alkali stage (such as acidic-basic-acidity) will not be provided.For example, exemplary DEDED processes produce the product whiter than DEDAD process (wherein A refers to acidic treatment).Therefore, intermediate not have alkali stage But the process for producing the product with comparable whiteness is that the personnel of art technology are unexpected.

In general, although certain bleaching process in known kraft process may have advantage than other process, not The reason of fully understanding any advantage behind.For oxidation, researches show that oxygen in some moment of multistage process Any advantage changed, or show any understanding that can be influenced by rear oxidation stage/processing to fibre property.For example, existing skill The latter half oxidation is not disclosed in art has any advantage than previous stage oxidation.In some embodiments, the disclosure provides special It is beneficial in kraft process and generate tool in the method that moment (for example, later stage of bleaching process) carries out There is a series of fiber of unique physicals and chemical characteristic.

In addition, for the whiteness in brown paper bleaching process, it is known that metal (is especially naturally present in paper pulp raw material Transition metal) be unfavorable to the whiteness of product.Therefore, bleaching process be often intended to from finished product remove certain transition metal with Obtain target whiteness.For example, chelating agent can be used to remove naturally occurring metal from paper pulp.Therefore, because removing naturally occurring Metal in paper pulp is significant, so those skilled in the art will not usually add any metal into bleaching process, This obtains the difficulty of whiter product by increasing.

In addition, for iron, the material is added into paper pulp can cause significantly to change colour, and be deposited when similar to (for example) flaming paper Discoloration.Think that the discoloration (discoloration of similar flaming paper) is irreversible so far.Therefore, think that adding iron makes the wooden paper always After slurry discoloration, the paper pulp will be by the permanent loss of whiteness, this cannot be restored with additional bleaching.

Therefore, although known iron or copper and peroxide can oxycellulose at low cost, they are not yet so far It is given in association with pulp bleaching process in a manner of reaching with the comparable whiteness of standard sequence for the oxidation step for not using iron or copper To use.In general, avoiding using them in association with pulp bleaching process.It was unexpected that the present inventor overcomes these difficulties, and In some embodiments, provide it is a kind of in association with pulp bleaching process with the method for iron or copper oxycellulose at low cost. In some embodiments, the methods disclosed herein production product have make us it is very surprised and with based on the prior art Opposite characteristic is predicted in introduction.Therefore, disclosed method can provide better than prior art products product and its can be more Add and economically fabricates.

For example, being generally recognized in the art that metal (such as iron) and cellulose can good combinations and cannot be by normal Washing removes.In general, from cellulose except de-iron is difficult and cost is higher, and need additional processing step.It is known There are the iron of high-content residuals to have the shortcomings that in cellulose products, especially in paper pulp and papermaking application.For example, Iron can lead to the discoloration of finished product and/or may be unsuitable for and the application of the finished product of skin contact (such as diaper and wound dressing). Therefore, several disadvantages will be will produce using iron in brown paper bleaching process.

So far, the kraft fibers oxidation processes for increasing degree of functionality are often confined to carry out at oxidation after bleached fiber Reason.In addition, the already known processes for making fiber become more aldehyde also cause fibre whiteness or the concomitant loss of quality.In addition, The increased already known processes of aldehyde degree of functionality of fiber are caused also to lead to the loss of carboxyl functionality.Disclosed method avoids these One or more of disadvantage.

The kraft fibers manufactured by chemical kraft pulp method provide cheap cellulose fibre source, usually exist Its fibre length is kept in entire pulping process, and the finished product with good whiteness and strength characteristics is usually provided.Thus, It is widely used in paper application.However, due to the chemical constitution of standard brown kraft paper pulp and the made cellulose of bleaching, standard brown kraft Paper fiber has limited applicability in downstream application (such as cellulose derivative manufactures).In general, standard brown kraft paper Fiber contains too many remaining hemicellulose and may influence subsequent physically and/or chemically modified other natural of the fiber Existing material.In addition, standard brown kraft paper fiber has limited chemical functionality, and it is typically hard and can not highly press Contracting.

In the application (for example, diaper, amenities and tissue products) for needing to contact with application on human skin, kraft fibers are hard Hard and coarse property can need the laminated or different types of material (such as cotton) of addition.Thus, for example, in multi-layered product In, it may be desirable to provide the cellulose fibre with better flexibility and/or pliability uses the need of other materials to reduce It asks.

Be related to absorbing body excretions and/or liquid (for example, diaper, adult-incontinence articles, wound dressing, sanitary napkin and/ Or cotton wool) application cellulose fibre be often exposed to the ammonia for being present in body excretions and/or by being drained with body In object and/or the related bacteriogenic ammonia of liquid.In such application, it may be desirable to using not only provide bulk density and Absorbability but also with smell reduce and/or antibacterial properties (for example, the smell from nitrogenous compound, such as ammonia can be reduced Gas (NH₃)) cellulose fibre.So far, it is frequently accompanied by by oxidation modification kraft fibers with increasing its smell control ability Undesirable whiteness reduces.To showing good absorption characteristic and/or smell control ability while keeping good whiteness special There are demands for the low-cost modified kraft fibers of property.

In market now, consumer needs thinner absorbent products (for example, diaper, adult-incontinence articles and defending Raw towel).Ultrathin products designs needs lower fibre weight and if the too short product integrality that causes of the fiber used Loss.The chemical modification of kraft fibers can lead to the loss of fibre length, make it that can not be used in certain form of product (for example, ultrathin products).More particularly, be treated to increase aldehyde degree of functionality (with improved smell control in relation to) brown paper Fiber may be lost during chemical modification by fibre length, make them unsuitable for using in ultrathin products design.To table Reveal compressibility without losing fibre length to make it be specifically adapted to ultrathin design (that is, the product is maintained and is based on The good absorption of the amount of the fiber in smaller space is can be compressed into, while product integrality is kept with lower fibre weight) Inexpensive fiber there are demands.

Traditionally, the cellulose source suitable for the manufacture of absorbent products or paper handkerchief is not suitable for downstream fiber element derivative yet The manufacture of object (such as cellulose ether and cellulose esters).It is manufactured by high-viscosity cellulose raw material (such as standard brown kraft paper fiber) low Viscosity cellulose derivatives need additional manufacturing step, this will dramatically increase cost while introduce undesirable by-product simultaneously And reduce the cellulose derivative overall qualities.(it usually has height for velveteen and the sulfite pulp of high chemical cellulose content The degree of polymerization) commonly used in such as cellulose ether and ester cellulose derivative manufacture.However, due to raw material (for cotton) Cost；The high-energy of slurrying and bleaching, chemistry and Environmental costs (for sulfite pulp)；It is extensive pure with needs Chemical industry skill (is suitable for two kinds of situations), and it is expensive to manufacture velveteen and sulphite fiber with high polymerization degree and/or viscosity.It removes Except high cost, available sulfite pulp supply in the market is reduced.Therefore, these fibers are very expensive, and Have limited applicability (for example, the case where may need higher DP or viscosity higher paper pulp in paper pulp and paper application Under).For cellulose derivative manufacturers, these paper pulp constitute the pith of its total manufacturing cost.Therefore, to can be used for fibre There are demands for the inexpensive fiber (such as modified kraft fibers) of the plain derivative manufacture of dimension.

Inexpensive cellulosic material to can be used for microcrystalline cellulose manufacture also has demand.Microcrystalline cellulose is widely used in food Product, drug, cosmetics and commercial Application, and be the purified crystals form of the cellulose of part depolymerization.Kraft fibers are micro- Purposes (not adding extensive after bleaching processing step) in crystalline cellulose manufacture is limited so far.Microcrystalline cellulose manufacture is logical Highly purified cellulosic material is often needed, this raw material is by acidic hydrolysis to remove the amorphous segment of cellulose chain.Ginseng See the U.S. Patent No. 2,978,446 of Battista et al. and the U.S. Patent No. 5,346,589 of Braunstein et al.. The low polymerization degree for removing the chain after the amorphous segment of cellulose is known as " balance DP (level-off DP) ", is often crystallite The starting point of cellulose manufacture, and its numerical value depends primarily on the source of cellulose fibre and the processing of cellulose fibre.By In at least one following reason, the dissolving of the amorphous segment from standard brown kraft paper fiber usually makes fiber degradation to making its change It must be unsuitable for the degree of most of applications：1) residual impurity；2) lack sufficiently long crystalline segment；Or 3) it is generated with excessively high The cellulose fibre of the degree of polymerization (usually 200 to 400), to make it cannot be used for the manufacture of microcrystalline cellulose.For example, it is desired to Kraft fibers with good purity and/or lower balance DP values, because the kraft fibers are in microcrystalline cellulose Higher versatility can be provided in manufacture and application.

In the disclosure, there is the fiber of one or more described properties only can add drift via exemplary kraft pulp The improvement of white process manufactures.The fiber of the disclosure overcomes several limitations related with above-mentioned known modified kraft fibers.

Description of the drawings

Fig. 1 shows chart of the final 0.5% capillary CED viscosity as the function of the percentage peroxide of consumption.

Fig. 2 shows the charts of the wet strength of the function as wet-strength resins content and dry strength ratio.

Specific implementation mode

I. method

The disclosure provides the novel method for handling cellulose fibre.In some embodiments, the disclosure provides one The method that kind is modified cellulose fibre, including cellulose fiber peacekeeping oxycellulose fiber is provided.It is used herein " oxidation ", " catalysis oxidation ", " catalysis oxidation " and " oxidation " is all interpreted as interchangeable and refers to at least catalytic amount Iron or at least one of copper and at least one peroxide (such as hydrogen peroxide) handle cellulose fibre so that cellulose At least some hydroxyls of fiber are aoxidized.Phrase " iron or copper " and similar " iron (or copper) " expression " iron or copper or combinations thereof Object ".In some embodiments, oxidation includes while increasing the carboxylic acid of cellulose fibre and the content of aldehyde.

The cellulose fibre used in method described herein can derive from cork fibrous, hardwood fiber and its mixing Object.In some embodiments, the modified cellulose fibre derives from cork, such as Southern Pine.In some embodiments, The modified cellulose fibre derives from hardwood, such as eucalyptus.In some embodiments, the modified cellulose fibre source In the mixture of cork and hardwood.In yet another embodiment, the modified cellulose fibre is whole from experience in advance Or the cellulose fibre (that is, kraft fibers) of part kraft process.

" cellulose fibre " or " kraft fibers " referred in the disclosure be it is interchangeable, unless expressly indicated not Same or those of ordinary skill will be understood that as difference.

In at least one embodiment, the method includes providing cellulose fibre and oxidized fibre cellulose fiber simultaneously Generally keep the fibre length of cellulose fibre.

It is " fibre length " and " average when the property for describing fiber and when indicating length weighted average fiber length Fibre length " is interchangeably used.Thus, for example, the fiber with 2mm average fiber lengths is construed as indicating have The fiber of 2mm length weighted average fiber length.

In at least one embodiment, the method includes providing cellulose fibre, partly bleached cellulose fibres And oxidized fibre cellulose fiber.In some embodiments, the oxidation carries out in bleaching process.In some embodiments In, the oxidation carries out after bleaching process.

In at least one embodiment, the method includes provide cellulose fibre and oxidized fibre cellulose fiber to Reduce the degree of polymerization of cellulose fibre.

In at least one embodiment, the method includes providing cellulose fibre and aoxidize the cellulose fibre The Canadian Standard Freeness (" freedom (freeness) ") of the cellulose fibre is kept simultaneously.

In at least one embodiment, the method includes providing cellulose fibre, oxidized fibre cellulose fiber and make The whiteness of the oxidized fibre cellulose fiber increases to above the whiteness of standard fibers cellulose fiber.

As described above, according to the disclosure, the oxidation of cellulose fibre is related to using at least iron of catalytic amount or copper and peroxidating The hydrogen processing cellulose fibre.In at least one embodiment, the method includes with iron and hydrogen peroxide oxidation fiber Cellulose fiber.Source of iron can be any source appropriate (such as technical staff it is contemplated that), such as ferrous sulfate (such as sulfuric acid Ferrous heptahydrate), frerrous chloride, iron ammonium sulfate, iron chloride, ammonium ferric sulfate or ferric citrate.

In some embodiments, the method includes with copper and hydrogen peroxide oxidation cellulose fibre.Similarly, copper source Can be technical staff it is contemplated that any source appropriate.Finally, in some embodiments, the method includes with Cellulose fibre described in the combination of copper and iron and hydrogen peroxide oxidation.

In some embodiments, the disclosure provides a kind of method for handling cellulose fibre, including provides fiber Cellulose fiber makes cellulose fibre that slurry, bleached cellulose fibres and oxidized fibre cellulose fiber be made.

In some embodiments, the method further includes making cellulose fibre oxygen delignification.Oxygen delignification can lead to Any method known to a person of ordinary skill in the art is crossed to carry out.For example, oxygen delignification can be conventional two-stage oxygen delignification.It is known (for example) make cellulose fibre (such as kraft fibers) oxygen delignification can change during processing cellulose fibre carboxylic acid and/ Or aldehyde.In some embodiments, the method includes making the de- wood of cellulose fibre oxygen before bleached cellulose fibres Element.

In at least one embodiment, the method includes at least one kraft pulp step, oxygen delignification step With oxidized fibre cellulose fiber in brown paper blanching step.In a preferred embodiment, the method includes at least one Oxidized fibre cellulose fiber in brown paper blanching step.In at least one embodiment, the method includes at two or two Oxidized fibre cellulose fiber in the above brown paper blanching step.

When cellulose fibre aoxidizes in blanching step, cellulose fibre should not bleached during or after oxidation Significant alkaline condition is undergone in process.In some embodiments, the method includes in acid pH oxidized fibre cellulose fiber. In some embodiments, the method includes providing cellulose fibre, cellulose fibre is made to be acidified and then be aoxidized in acid pH Cellulose fibre.In some embodiments, pH is about 2 to about 6, for example, about 2 to about 5 or about 2 to about 4.

Any acid for adjusting pH appropriate that can consider of technical staff can be used, for example, sulfuric acid or hydrochloric acid or from floating The filtrate of the acidic bleaching stage (chlorine dioxide (D) section of such as multistage bleaching process) of white process.For example, cellulose fibre can It is acidified by the acid outside addition.The example of external acid is known in the art and includes but not limited to sulfuric acid, salt Acid and carbonic acid.In some embodiments, cellulose fibre is with the acid filtrate (such as waste water filtrate) from blanching step Acidification.In some embodiments, the acid filtrate from blanching step does not have high iron content.In at least one embodiment party In formula, cellulose fibre is acidified with the acid filtrate of the D sections from multistage bleaching process.

In some embodiments, the method includes the oxidized fibres in one or more stages of multistage bleaching process Cellulose fiber.In some embodiments, the method includes the oxidized fibre cellulose fibers in the single phase of multistage bleaching process. In some embodiments, the method includes the oxidized fibre cellulose fibers near the terminal or terminal of multistage bleaching process.One In a little embodiments, the method includes at least the 4th section of oxidized fibre cellulose fibers in five sectional bleaching sequences.

According to the disclosure, the multistage bleaching process can be after which step not comprising any of alkaline blanching step Bleaching process.In at least one embodiment, the multistage bleaching process is five sectional bleaching sequences.In some embodiments In, the bleaching process is DEDED processes.In some embodiments, the bleaching process is D₀E1D1E2D2 processes.One In a little embodiments, the bleaching process is D₀(EoP) D1E2D2 processes.In some embodiments, the bleaching process is D₀ (EO)D1E2D2。

The non-oxidative branch of multistage bleaching process may include a series of stages that are any conventional or finding later (in conventional strip Carried out under part), precondition is to be not available for alkaline blanching step after which step, in order to for manufacturing in the disclosure The modified fibre of description.

In some embodiments, the oxidation is merged into the 4th section of multistage bleaching process.In some embodiments In, the method is with D₀Implement in five sectional bleaching sequences of E1D1E2D2 processes, the 4th section (E2) is for aoxidizing ox Mulberry paper fiber.

In some embodiments, Kappa number (kappa number) increases after cellulose fibre oxidation.More specifically Ground is said, the reduction of expected material (such as lignin is reacted with permanganate agent) is based on, it will usually it is expected that this entire bleaching Kappa number in section reduces.However, in method described herein, the Kappa number of cellulose fibre may be because impurity (for example, Lignin) loss and reduce；However, Kappa number may be because the chemical modification of fiber and increase.It is not intended to be restricted by theory, according to The increase of letter modified cellulose degree of functionality provides the additional site that can be reacted with permanganate agent.Therefore, Modified Kraft The Kappa number of paper fiber increases relative to the Kappa number of standard brown kraft paper pulp fiber.

In at least one embodiment, the oxidation has been added in iron or copper and peroxide and provides one section of guarantor It holds and occurs in the single stage of bleaching process after the time.Holding appropriate is one be enough with iron or copper catalysis hydrogen peroxide Amount of time.The time can be readily determined by those of ordinary skill.

According to the disclosure, the oxidation is being enough to generate time and the temperature progress of desired reaction completeness.For example, institute It states temperature that oxidation can be at about 60 DEG C to about 80 DEG C and time at about 40 minutes to about 80 minutes carries out.The oxidation reaction institute The time and temperature needed can be readily determined by those skilled in the art.

Advantageously, cellulose fibre is cooked before bleaching to target Kappa number.For example, when the cellulose for wishing to aoxidize When for paper grade cellulose or fluff pulp fibers element, can by cellulose fibre before bleached cellulose in double tank hydraulic pressure boilings Lo-Solids is used in tank^TMCooking process boiling to about 30 to about 32 Kappa number and aoxidize the cellulose.Alternatively, if uncommon The cellulose of oxidation is hoped to apply (such as manufacture of cellulose ether) for cellulose derivative, it can be by cellulose fibre in bleaching Preceding boiling to about 20 to about 24 Kappa number and the cellulose is aoxidized according to disclosed method.In some embodiments In, cellulose fibre be bleach and oxidized fibre cellulose fiber before in traditional two-stage oxygen delignification step boiling and de- wood Element.Advantageously, when it is desirable that the cellulose aoxidized is used for cellulose derivative in application, delignification is to being reached about 6 to about 8 Target Kappa number, when it is desirable that the cellulose aoxidized for paper and/or villus in application, carrying out to of about 12 to about 14 Target Kappa number.

In some embodiments, the bleaching process is to reach about 88% to 90% final ISO whiteness (such as about 85% to about 95%, or 90%) about 88% to about carrying out under conditions of target.

The disclosure also provides a kind of method of processing cellulose fibre, and the method includes providing cellulose fibre, reduce The DP of cellulose fibre and the fibre length for keeping cellulose fibre.In some embodiments, cellulose fibre is ox-hide Paper fiber.In some embodiments, the DP of cellulose fibre is reduced in bleaching process.In some embodiments, fine The DP of cellulose fiber is reduced near the terminal or terminal of multistage bleaching process.In some embodiments, DP is in multistage At least the 4th section reduction of bleaching process.In some embodiments, DP is at the 4th section of multistage bleaching process or the 4th section It reduces later.

Alternately, multistage bleaching process can be changed to provide stronger bleaching before oxidized fibre cellulose fiber Condition.In some embodiments, the method includes stronger conditions of bleaching is provided before oxidation step.Stronger The degree of polymerization and/or viscosity of the permissible cellulose fibre of conditions of bleaching are in the oxygen with less amount of iron or copper and/or hydrogen peroxide Changing reduces in step.Therefore, it is possible to improve bleaching process condition so as to further control final cellulose products whiteness and/ Or viscosity.For example, reducing the amount of peroxide and metal, while stronger conditions of bleaching is provided before the oxidation, it is possible to provide Oxidation product than being generated with same oxidizing condition but less intense bleaching has lower viscosity and higher whiteness Product.It may be advantageous for such condition in some embodiments, especially in cellulose ether application.

In some embodiments, disclosed method further comprises the crystallinity for reducing cellulose fibre so that it compares The crystallinity of the cellulose fibre measured before oxidation stage is lower.For example, according to disclosed method, cellulose fibre Crystallinity index can reduce most 20% relative to the crystallization initiation degree index measured before oxidation stage.

In some embodiments, disclosed method further comprises being changed at least one causticity or alkaline matter for processing Property cellulose fibre.For example, at least one embodiment, a kind of method of processing cellulose fibre includes providing the disclosure Oxidation cellulose fibre, so that the cellulose fibre of oxidation is exposed to alkalinity or corrodent, then duse process (dry Laying) cellulose products.It is without being bound by theory, it is believed that at least one corrodent is added into modified cellulose can generate tool There is the cellulose fibre of very high functionality and nanofibres length.

The known cellulose comprising increased aldehyde radical has advantageous property in terms of the wet strength for improving cellulose fibre. See, e.g. the U.S. Patent No. 6,582,559 of the U.S. Patent No. 6,319,361 of Smith et al. and Thornton et al. Number.Such property may be beneficial in the application of (for example) absorbing material.In some embodiments, the disclosure provides a kind of Method for improving product wet strength, including the modified cellulose fibre of the disclosure and the modified fibre by the disclosure are provided Cellulose fiber is added in a kind of product (such as paper product).For example, the method can include oxidized fibre in bleaching process Cellulose fiber is further processed oxycellulose with acid or corrodent and the fiber of processing is added to cellulose products In.

According to the disclosure, by hydrogen peroxide to be enough to obtain the final fibre of desired oxidation and/or the degree of polymerization and/or viscosity The amount of the plain product of dimension is added to the cellulose fibre in acid medium.For example, peroxide can be based on pulp dry weight with about 0.1% to about 4% or about 1% to about 3% or about 1% to about 2% or about 2% to about 3% amount addition.

Iron or copper are at least to be added to the amount of the oxidation of cellulose with peroxide with being enough to be catalyzed.For example, iron can be with base It is added in the amount of about 25ppm to about 200ppm in kraft pulp dry weight.Those skilled in the art will easily optimize iron or The amount of copper is to obtain the final cellulose products of required horizontal or amount oxidation and/or the degree of polymerization and/or viscosity.

In some embodiments, the method adds steam further to before and after adding hydrogen peroxide.

In some embodiments, the final DP of paper pulp and/or viscosity can by the amount of iron or copper and hydrogen peroxide and The strength control of conditions of bleaching before oxidation step.Those skilled in the art are fine by the modified kraft that can take into account the disclosure Dimension other properties can be before by the amount and oxidation step of iron or copper and hydrogen peroxide conditions of bleaching intensity effect.Example Such as, the intensity of the amount and the conditions of bleaching before oxidation step of iron or copper and hydrogen peroxide is adjusted in those skilled in the art To reach or obtain desired finished product whiteness and/or the required degree of polymerization or viscosity.

In some embodiments, the disclosure provides a kind of method being modified to cellulose fibre, including provides fine Cellulose fiber, the degree of polymerization for reducing cellulose fibre and the fibre length for keeping cellulose fibre.

In some embodiments, the kraft fibers of the oxidation of the disclosure do not have defibrination.To the kraft fibers of oxidation Defibrination may have negative impact to its fibre length and integrality, such as fiber defibrination can cause fiber ruptures.

In some embodiments, each section of five sectional bleaching sequences includes an at least mixer, a reactor and a washing Device (such as known to those skilled in the art).

In some embodiments, kraft pulp is acidified on D1 sections of washers, and source of iron is also on D1 sections of washers It is added in kraft pulp, addition point of the peroxide after source of iron (or copper source) in mixer or pump is added, then Into E2 sections of towers, kraft pulp is reacted in E2 towers and is washed on E2 washers, is optionally existed before entering E2 towers Steam is added in steam mixer.

In some embodiments, until the terminal that iron (or copper) can be added to D1 sections, or can also start at E2 sections when, adds It is that paper pulp (that is, before adding iron) first is acidified at D1 sections to add iron (or copper), condition.Before or after peroxide adds Optionally add steam.

In an exemplary embodiment, the method for being used to prepare low viscosity modified cellulose fibre can relate in acidity In medium and in the presence of iron, using hydrogen peroxide treatment come the bleached kraft pulp in multistage bleaching process and in multistage The final stage (such as the 4th section of multistage bleaching process, such as the 4th section of 5 sectional bleaching sequences) of bleaching process nearby reduces paper The DP of slurry.For example, the final DP of paper pulp can be controlled by applying iron or copper and hydrogen peroxide appropriate, such as in embodiment part In further describe.In some embodiments, to be suitable for generating low DP fibers (that is, the DPw with about 1180 to about 1830 Or the fiber of the 0.5% capillary CED viscosity of about 7mPas to about 13mPas) amount and condition iron or copper and peroxide are provided Change hydrogen.It is to be suitable for generating ultralow DP fibers (that is, having about 700 to about 1180 in some illustrative embodiments The fiber of the 0.5% capillary CED viscosity of DPw or about 3.0mPas to about 7mPas) amount and condition iron or copper are provided And hydrogen peroxide.

For example, in some embodiments, in the acid medium with iron or copper with the processing of hydrogen peroxide can relate to by The pH of kraft pulp is adjusted to about 2 to about 5, source of iron is added into the paper pulp of acidification, and add hydrogen peroxide to kraft pulp.

In some embodiments, for example, the method for preparing the modified cellulose fibre within the scope of the disclosure can relate to Kraft pulp is acidified to the pH (such as using sulfuric acid) of about 2 to about 5, by source of iron (such as ferrous sulfate, such as ferrous sulfate seven Hydrate) it is mixed with the kraft pulp of acidification and hydrogen peroxide, wherein the applied amount of source of iron is about 1% to about 15% based on consistency The dry weight of kraft pulp be Fes of the about 25ppm to about 250ppm⁺², and hydrogen peroxide can be used as solution with about 1 weight % to about It the concentration of 50 weight % and is added with the amount of about 0.1% to about 1.5% based on kraft pulp dry weight.In some embodiments In, ferrous sulfate solution is mixed with the kraft pulp that consistency is about 7% to about 15%.In some embodiments, acid ox-hide Paper pulp is mixed with source of iron and the thermotonus with hydrogen peroxide at about 60 DEG C to about 80 DEG C, when reaction a length of about 40 minutes to about 80 minutes.

In some embodiments, the method for preparing the modified cellulose fibre within the scope of the disclosure is related to by used Hydrogen oxide handles kraft pulp to reduce DP, wherein the hydrogen peroxide of the acidity in acid medium in the presence of iron (or copper) It is integrated into multistage bleaching process with iron (or copper) processing.In some embodiments, with the processing of iron, acid and hydrogen peroxide It is integrated into the single stage of multistage bleaching process.In some embodiments, with the processing of iron (or copper), acid and hydrogen peroxide The single stage being integrated near multistage bleaching process terminal or terminal.In some embodiments, with iron (or copper), acid Processing with hydrogen peroxide is integrated into the 4th section in multistage bleaching process.For example, iron (or copper) and peroxide all After adding and some retention times being provided, can in the single stage (such as E2 sections) generation pulp processing.In some implementations In mode, each section of five sectional bleaching sequences includes an at least mixer, a reactor and a washer (as being people in the art Known to member), and kraft pulp can be acidified on D1 sections of washers, and source of iron also can be added to brown paper on D1 sections of washers In slurry, peroxide is made an addition in the addition point after source of iron (or copper source) in mixer or pump, subsequently into E2 sections of towers, ox Mulberry paper slurry can be reacted in E2 towers and be washed on E2 washers, before entering E2 towers optionally in steam mixer Add steam.In some embodiments, it for example, until the terminal that iron (or copper) can be added to D1 sections, or can also be opened at E2 sections Iron (or copper) is added when the beginning, condition is that paper pulp (that is, before iron addition) first is acidified at D1 sections, so that pH is fallen about if necessary The range of 3 to about 5 can add additional acid, and can add peroxide after iron (or copper).Before adding peroxide After can add steam.

For example, in one embodiment, tool can be generated with the above-mentioned five sectional bleachings sequence that softwood cellulose raw material carries out There is the modified cellulose fibre of one or more following properties：At least the average fiber length of 2.2mm, about 3.0mPas are to small It is severe in S10 caustic fusions degree, the S18 of about 14% to about 18% of viscosity, about 16% to about 20% within the scope of 13mPas Property alkali solubility, about 2meq/100g to the carboxyl-content of about 6meq/100g, about 1meq/100g to about 3meq/100g aldehyde contain Amount, about 1 to 4 carbonyl content, about 700mls to the freedom of about 760mls, the fibre strength of about 5km to about 8km and about 85 to The whiteness of about 95ISO.For example, in some embodiments, five sectional bleaching sequence of above-mentioned example can be generated with aforementioned each property The modified cellulose cork fibrous of matter.

According to another embodiment, wherein the cellulose fibre is cork fibrous, five sectional bleaching sequence of above-mentioned example The modified cellulose cork fibrous having the following properties that can be generated：At least 2.0mm (for example, about 2.0mm is to about 3.7mm, or about 2.2mm to about 3.7mm) average fiber length, be less than 13mPas (for example, about 3.0mPas to less than 13mPas or About 3.0mPas's to about 5.5mPas or about 3.0mPas to about 7mPas or about 7mPas to less than 13mPas Viscosity) viscosity and at least 85 (for example, about 85 to about 95) whiteness.

In some embodiments, the disclosure provides a kind of method for manufacturing Time of Fluff Slurry, including provides the disclosure Modified kraft fibers and then manufacture Time of Fluff Slurry.For example, the method includes the BK bleached kraft fibres in multistage bleaching process Dimension is aoxidized at least the 4th section or the 5th section iron or copper with hydrogen peroxide and catalytic amount under acid condition of multistage bleaching process The fiber, then forms Time of Fluff Slurry.In at least one embodiment, fiber after multistage bleaching process without defibrination.

In some embodiments, the fiber such as the manufacture can be handled with surface-active agents.Table for the present invention Face active agent can be solid or liquid.Surface-active agents can be any surface-active agents, including but not limited to softening agent, Degumming agent (debonder) and surfactant do not have significant quantity relative to fiber, i.e., the ratio of fiber will not be interfered to absorb Rate.Surface-active agents used herein relative to fiber " not having significant quantity " are shown as used PFI as described herein The specific absorption rate measured increases by 30% or lower.According to one embodiment, specific absorption rate increase by 25% or lower, such as 20% or lower, such as 15% or lower, such as 10% or lower.In the case where being not intended to be restricted by theory, surface is added Activating agent causes the competition to the same loci on the cellulose as test fluid.As a result, when surfactant is excessive, It is reacted in excessive site, to drop low-fiber absorbability.

PFI used herein is according to SCAN-C-33:80 testing standards, Scandinavian Pulp, Paper and Board Testing Committee are measured.This method is generally as follows.First, sample is prepared using PFI mat forming devices. It opens vacuum and feeds about 3.01g Time of Fluff Slurry into mat forming device entrance.Vacuum is closed, test block is taken out and is put In on balance with inspection pad quality.Villus quality is adjusted to 3.00 ± 0.01g, and is recorded as quality_{It is dry}.Villus is placed in test In cylinder.Cylinder containing villus is placed in the shallow perforation ware of absorption tester and opens water valve.When increasing test block cylinder Softly apply 500g loads and rapid started by press button to fluffy mat.Tester will operate 30 seconds, and display, which is read, later is 00.00.When display reading is 20 seconds, records and do padded degree, (the height in terms of immediate 0.5mm_{It is dry}).When display again When reading is 00.00, started by press button is so that pallet automatically increases water again, and then record time showing value is (when absorption Between, T).Tester will continue running 30 seconds.Water pond reduces automatically and the time will operate 30 seconds again.When display reading is 20 seconds When, wet padded degree is recorded, (the height in terms of immediate 0.5mm_{It is wet}).Sample holder is removed, wet pad is transferred to balance to survey Measure quality_{It is wet}And close water valve.Specific absorption rate (s/g) is T/ mass_{It is dry}.Specific capacity (g/g) is (quality_{It is wet}Quality_{It is dry})/quality_{It is dry}.It is wet Volume (cc/g) is [19.64cm²× height_{It is wet}/3]/10.Dry volume is [19.64cm²× height_{It is dry}/3]/10.For with through surface The reference standard that the fiber of activating agent processing compares is not add the identical fibre of surfactant.

It is generally acknowledged that softening agent and degumming agent usually only can be used as complex mixture and non-single compound is bought.Although with Lower discussion concentrates on main matter, it will be appreciated that in practice usually using commercial mixture.Suitable softening agent, degumming agent and Surfactant is apparent to a skilled reader and coverage is in document.

Suitable surfactant includes cationic surface active agent, the anion for not having significant quantity relative to fiber And nonionic surface active agent.According to one embodiment, surfactant is nonionic surface active agent.According to one Embodiment, surfactant are cationic surface active agent.According to one embodiment, surfactant is plant type table Face activating agent, such as plant-type fatty acids, such as plant-type fatty acids quaternary ammonium salt.These compounds include DB999 and DB1009, It is purchased from Cellulose Solutions.Other surfaces activating agent may include but be not limited to Berol 388, and one kind being purchased from Akzo The ethoxylated nonylphenol ether of Nobel.

Using biodegradable softening agent.Representative Biodegradable cationic type softening agent/degumming agent is disclosed in U.S. State's patent No. 5,312,522, No. 5,415,737, No. 5,262,007, No. 5,264,082 and No. 5,223,096 In, it is integrally incorporated herein by reference.These compounds are the diester of biodegradable season ammoniate, quaternary amine -ester And the biodegradable functionalized vegetable oil type ester of quaternary ammonium chloride and two mustard seed base dimethyl ammonium diester of chlorination, and be representative Property biodegradable softening agent.

The additive amount of surfactant is at most 8 lb/tons, the lb/ton of such as 2 lb/tons~7, the lb/ton of such as 4 lb/tons~7, Such as the lb/ton of 6 lb/ton~7.

Surface-active agents can be in any point addition before forming paper pulp volume, paper pulp bale packing or paper pulp thin slice.According to one A embodiment, surface-active agents are just before the head box of Paper pulp machine, especially in the entrance of the first detergent feed pump Addition.

According to one embodiment, when for adhering process, fiber of the invention is relative to being not added with surfactant Identical fibre have improved filterability (filterability).For example, the filtration of the viscose solution comprising fiber of the present invention Property lower than the viscose solution prepared under surfactant-free with identical fibre in the same manner at least 10%, for example, it is at least low 15%, such as at least low 30%, such as at least low 40%.The filterability of viscose solution measures by the following method.Solution is set It is put in nitrogen pressurization (27psi) container of bottom with 1 and 3/16 inch of filtering mouth, filter medium is from container external-to-internal As described below：Perforated metal disk, 20 mesh stainless steels sieve, agate appearance beautiful jade cotton, 54 filter paper of Whatman and villus side are upwardly toward appearance 2 layers of Ulrika Knape flannel of the content of device.Make solution through the media filtration 40 minutes, then refilters 140 at 40 minutes Minute (therefore in 40 minutes when t=0), measures the volume (weight) of the solution of filtering, using by the time as X-coordinate and filtering The weight of viscose glue is filterability value as the slope of this figure of Y coordinate-.It is recorded with 10 minutes intervals.For living with through surface Property agent processing the reference standard that compares of fiber be not add the identical fibre of surfactant.

According to embodiment of the present invention, the fiber of the invention handled through surfactant shows limited ratio Absorptivity increases (being, for example, less than 30%) and filterability reduces (for example, at least 10%) simultaneously.According to one embodiment, through table The fiber of face activating agent processing have the specific absorption rate less than 30% increase and at least 20%, such as at least 30%, such as at least 40% filterability reduces.According to another embodiment, there is the fiber handled through surfactant the ratio less than 25% to absorb Rate increases and at least 10%, such as at least about 20%, such as at least 30%, such as at least 40% filterability reduces.According to another One embodiment, through surfactant handle fiber have less than 20% specific absorption rate increase and at least 10%, such as extremely Few about 20%, such as at least 30%, such as at least 40% filterability reduces.According to another embodiment, through surfactant The fiber of processing have less than 15% specific absorption rate increase and at least 10%, such as at least about 20%, such as at least 30%, ratio Filterability such as at least 40% reduces.According to another embodiment, the fiber handled through surfactant has less than 10% Specific absorption rate increases and at least 10%, such as at least about 20%, such as at least 30%, such as at least 40% filterability reduces.

So far, to being considered as being unfavorable for fibre for producing the paper pulp of viscose to add cationic surface active agent Tie up glue production.The cationic surface active agent for being attached to the same loci that must be reacted with escharotic on cellulose starts to be disintegrated Cellulose fibre.Therefore, it has long been believed that the paper pulp that cationic materials are not used as the fiber for producing viscose is located in advance Reason.It is not intended to be restricted by theory, it is believed that since fiber produced by the invention is different in its form, characteristic and chemical composition In prior art fiber, thus cationic surface active agent not by with its it is identical to prior art fiber in a manner of combine. When being reacted with surfactant of the present invention, the fiber described in the disclosure is to improve the side of escharotic infiltration and filterability Formula detaches fiber.Therefore, according to one embodiment, the fiber of the disclosure can be than untreated fiber or prior art fiber It is used as the substitute of expensive cotton or sulphite fiber in the degree of bigger.

The performance for the fiber for being made into Time of Fluff Slurry is improved to the fiber addition surfactant of the present invention.Particularly, table Face active agent can reduce the knot that may be formed between the fibers, and therefore produce better air-laid (airlaid) or gas Stream molding (airformed) product.Surfactant also improves the structure of villus product.Since fiber has lower parent each other And power, therefore clumping (clumping) is reduced.In addition, the reduction of knot also leads to fibrosis and fluffing (fluffing) phase of paper pulp Between energy consumption it is lower.

The use of surfactant also influences the physical characteristic of the product produced by processed fiber.Including surface-active The fiber of agent or degumming agent will become apparent from the reduction of net rupture strength and emboss the improvement of ability.It is handled using surface-active agents It is the quantity that surfactant is likely to reduced hydrogen binding site by the shortcomings that fiber for absorbing product, and therefore reduces water suction Rate and whole volume.

The disclosure also provides a kind of method for reducing smell, smell such as from body excretions (such as from The smell of urine or blood).In some embodiments, the disclosure provides a kind of method for controlling smell, including provides root According to the modification bleached kraft fibers of the disclosure, and to bleached kraft fibers apply odorant so that with to equivalent mark The amount of odorant is compared in air after quasi- kraft pulp fiber application equivalent odorant, modified bleached kraft fibers The amount of odorant reduces in air.In some embodiments, the disclosure provides a kind of for controlling smell including inhibiting thin The method that bacterium smell generates.In some embodiments, the disclosure provides a kind of for controlling smell including by odorant (such as nitrogenous odorant) is absorbed into the method in modified kraft fibers.It should be by " nitrogenous odorant " used herein It is understood to mean that the odorant for including at least one nitrogen.

In at least one embodiment, a kind of method reducing smell includes the modified cellulose provided according to the disclosure Fiber, and apply odorant (such as nitrogenous compound, such as ammonia) to modified kraft fibers or can generate nitrogenous The organism of compound.In some embodiments, the method further includes being added with taste to modified kraft fibers Time of Fluff Slurry is formed by modified cellulose fibre before substance.In some embodiments, odorant includes that at least one can Generate the bacterium of nitrogenous compound.In some embodiments, odorant includes nitrogenous compound, such as ammonia.

In some embodiments, the method for reducing smell further comprises ammonia being absorbed into modified cellulose fibre In.In some embodiments, the method for reducing smell further comprises that bacterium ammonia is inhibited to generate.In some embodiments In, it includes inhibiting bacterial growth to inhibit the method that bacterium ammonia generates.In some embodiments, bacterium ammonia is inhibited to generate Method includes inhibiting bacterium urea synthesizing.

In some embodiments, it is a kind of reduce smell method include by modified cellulose fibre with it is at least one other Subtract taste agent (odor reductant) combination, then to applying odorant with subtracting in the modified cellulose fibre that taste agent is combined.

It is exemplary to subtract taste agent and be known in the art, and include such as smell palliative, odor masking agent, sterilization Agent, enzyme and urease inhibitor.For example, modified cellulose fibre can be combined with taste agent is subtracted selected from following at least one：Zeolite, Activated carbon, diatomite, cyclodextrin, clay, chelating agent (such as contain such as those of copper, silver or zinc ion metal ion), from Sub-exchange resin, antiseptic or antibacterial polymer and/or aromatic.

In some embodiments, modified cellulose fibre is combined at least one super absorbent polymer (SAP).One In a little embodiments, SAP can be to subtract taste agent.Example according to the available SAP of the disclosure includes but not limited to that BASF AG sells Hysorb^TM, Sumitomo companies sellIt is sold with Evonik companies

II. kraft fibers

" standard ", " routine " or " tradition " kraft fibers, brown paper bleached fiber, kraft pulp or ox-hide is mentioned above Paper bleached pulp.This fiber or paper pulp are passed through to be described frequently as reference point, for the improved property of the definition present invention.Herein Middle these terms used be it is interchangeable and refer to composition it is upper with do not undergo any oxidation and (individually or be followed by one or more A alkalinity or acidic treatment) (that is, being handled with standard or usual manner) target fibers or paper pulp it is identical and to be similar to State fiber or paper pulp that the mode of target fibers or paper pulp is handled.Term " modification " used herein, which refers to, has undergone oxidation processes The fiber of (individually or followed by one or more alkalinity or acidic treatment).

The physical property (for example, fibre length and viscosity) for the modified cellulose fibre mentioned in this specification is that basis exists The scheme provided in embodiment part measures.

The disclosure provides the kraft fibers with low viscosity and ultra-low viscosity.Unless otherwise mentioned, used herein " viscosity " refers to the 0.5% capillary CED viscosity measured according to the TAPPI T230-om99 of institute's reference in regulation.The present invention's Modified kraft fibers show unique characteristic, these characteristics are the characterizations for the chemical modification done to it.More particularly, The fiber of the present invention shows the characteristic (that is, length and freedom) of similar standard brown kraft paper fiber, but it is non-also to show some The characteristic of Chang Butong, these characteristics depend on the increased functional group's number being contained in modified fibre.When what is quoted When tappi test is to measure viscosity, which shows unique characteristic.Specifically, one as test method Point, the tappi test of reference handles fiber with escharotic.Modified fibre can be led to by applying escharotic to the modified fibre The hydrolysis different from standard brown kraft paper fiber, therefore the viscosity reported is usually lower than the viscosity of standard brown kraft paper fiber.Therefore, originally Field technology personnel will be understood that the viscosity of report can be influenced by Viscosity Measurement Methods.For purposes of the present invention, it reports herein The viscosity that the TAPPI methods by reference accused measure indicates the viscosity of the kraft fibers of the degree of polymerization for calculating fiber.

Unless otherwise mentioned, " DP " used herein refers to 0.5% capillary by being measured according to TAPPI T230-om99 The average degree of polymerization (DPw) by weight that CED viscosity is calculated.See, e.g., J.F.Cellucon Conference, The Chemistry and Processing of Wood and Plant Fibrous Materials, page 155, test is advised (Woodhead Publishing Ltd., Abington Hall, the Abinton Cambridge CBI 6AH of journey 8,1994 England, J.F.Kennedy et al. are edited)." low DP " indicates the DP or about 7mPas of about 1160 to about 1860 to about The viscosity of 13mPas.The viscosity of the DP or about 3mPas to about 7mPas of " ultralow DP " fibring about 350 to about 1160.

It is not wishing to be bound by theory, it is believed that when calculating DP according to the CED viscosity measured by TAPPI T230-om99 When, fibring of the invention goes out the false degree of polymerization.In particular, it is believed that not having to the catalytic oxidation treatment of the fiber of the present invention Make cellulose be corrupted to by measured DP instruction degree, but largely have open key and add substituent group from And cellulose is made to have more reactive effect, rather than cut staple element chain.It is also believed that for since adding caustic alkali CED viscosity tests (TAPPI T230-om99), have the effect of cut staple element chain, institute at new reactivity site The cellulosic polymer of generation is more much more than the number for the shorter section that finding has under fiber pretest condition.This is by cellulose The fact that length is not remarkably decreased in the fabrication process is confirmed.

In some embodiments, modified cellulose fibre has the DP of about 350 to about 1860.In some embodiments In, DP is about 710 to about 1860.In some embodiments, DP is about 350 to about 910.In some embodiments, DP is About 350 to about 1160.In some embodiments, DP is about 1160 to about 1860.In some embodiments, DP is less than 1860, it is less than 1550, is less than 1300, is less than 820 or less than 600.

In some embodiments, modified cellulose fibre has the viscosity of about 3.0mPas to about 13mPas.One In a little embodiments, viscosity is about 4.5mPas to about 13mPas.In some embodiments, viscosity be about 3.0mPas extremely About 5.5mPas.In some embodiments, viscosity is about 3.0mPas to about 7mPas.In some embodiments, it glues Degree is about 7mPas to about 13mPas.In some embodiments, viscosity be less than 13mPas, less than 10mPas, be less than 8mPas, it is less than 5mPas or is less than 4mPas.

In some embodiments, the modified kraft fibers of the disclosure keep its freedom during bleaching process. In some embodiments, modified cellulose fibre have at least about 690mls, such as at least about 700mls or about 710mls or " freedom " of about 720mls or about 730mls.

In some embodiments, the modified kraft fibers of the disclosure keep its fibre length during bleaching process.

In some embodiments, when modified cellulose fibre is cork fibrous, the modified cellulose fibre has The average fiber length (being measured according to testing scheme 12 (being described in following embodiment part)) of about 2mm or bigger.In some realities It applies in mode, average fiber length is not greater than about 3.7mm.In some embodiments, average fiber length is at least about 2.2mm, about 2.3mm, about 2.4mm, about 2.5mm, about 2.6mm, about 2.7mm, about 2.8mm, about 2.9mm, about 3.0mm, about 3.1mm, about 3.2mm, about 3.3mm, about 3.4mm, about 3.5mm, about 3.6mm or about 3.7mm.In some embodiments, average Fibre length is about 2mm to about 3.7mm, or about 2.2mm to about 3.7mm.

In some embodiments, when modified cellulose fibre is hardwood fiber, the modified cellulose fibre has The average fiber length of about 0.75mm to about 1.25mm.For example, average fiber length can be at least about 0.85mm, such as about 0.95mm, or about 1.05mm, or about 1.15mm.

In some embodiments, the modified kraft fibers of the disclosure have and kraft fibers standard brown kraft paper fiber Identical whiteness.In some embodiments, the modified cellulose fibre has at least 85,86,87,88,89 or 90ISO's Whiteness.In some embodiments, whiteness is not greater than about 92.In some embodiments, whiteness is about 85 to about 92, or about 86 To about 90, or about 87 to about 90, or about 88 to about 90.

In some embodiments, the modified cellulose fibre of the disclosure it is more compressible than standard brown kraft paper fiber and/or It can emboss (embossable).In some embodiments, modified cellulose fibre may be utilized in fabricating than with equivalent standard brown kraft The structure of paper fiber manufacture is thinner and/or has more highdensity structure.

In some embodiments, the modified cellulose fibre of the disclosure can be compressed at least about density of 0.21g/cc, For example, about 0.22g/cc, or about 0.23g/cc, or about 0.24g/cc.In some embodiments, the modified cellulose of the disclosure Fiber is compressible to about 0.21g/cc to the density of about 0.24g/cc.In at least one embodiment, the disclosure is modified fine Cellulose fiber (when 20psi gauge pressures are compressed) has the density in about 0.21g/cc to about 0.24g/cc.

In some embodiments, the modified cellulose fibre of the disclosure has (when the gauge pressure of about 5psi is compressed) In about 0.110g/cc to the density of about 0.114g/cc.For example, the disclosure modified cellulose fibre (about 5psi gauge pressure into When row compression) can have at least about 0.110g/cc, for example, at least about 0.112g/cc or about 0.113g/cc or about 0.114g/ The density of cc.

In some embodiments, modified cellulose fibre (when the gauge pressure of the about 10psi is compressed) tool of the disclosure There is the density to about 0.155g/cc in about 0.130g/cc.For example, the modified cellulose fibre of the disclosure is (in the table of about 10psi When being compressed) can have at least about density of 0.130g/cc, for example, at least about 0.135g/cc, or about 0.140g/cc, or About 0.145g/cc, or about 0.150g/cc.

In some embodiments, the modified cellulose fibre of the disclosure can be compressed to the density than standard brown kraft paper fiber Up at least about 8% density.In some embodiments, the modified cellulose fibre of the disclosure has than standard brown kraft paper fiber Density high about 8% to about 16% density, such as high about 10% to about 16% or high about 12% to about 16% or high about 13% to about 16% or high about 14% to about 16% or high about 15% to about 16%.

In some embodiments, the modified kraft fibers of the disclosure have increased relative to standard brown kraft paper fiber Carboxyl-content.

In some embodiments, carboxyl of the modified cellulose fibre with about 2meq/100g to about 9meq/100g contains Amount.In some embodiments, carboxyl-content is about 3meq/100g to about 8meq/100g.In some embodiments, carboxyl Content is about 4meq/100g.In some embodiments, carboxyl-content is at least about 2meq/100g, for example, at least about 2.5meq/100g, for example, at least about 3.0meq/100g, for example, at least about 3.5meq/100g, for example, at least about 4.0meq/ 100g, for example, at least about 4.5meq/100g, or for example, at least about 5.0meq/100g.

The modified kraft fibers of the disclosure have increased aldehyde relative to standard bleached kraft fibers.At some In embodiment, modified kraft fibers have the aldehyde of about 1meq/100g to about 9meq/100g.In some embodiments In, aldehyde is at least about 1.5meq/100g, about 2meq/100g, about 2.5meq/100g, about 3.0meq/100g, about 3.5meq/100g, about 4.0meq/100g, about 4.5meq/100g or about 5.0meq/100g, or at least about 6.5meq, or at least About 7.0meq.

In some embodiments, modified cellulose fibre has the ratio of greater than about 0.3 total aldehyde and carboxyl-content, all Such as larger than about 0.5, such as greater than about 1, such as greater than about 1.4.In some embodiments, aldehyde and carboxyl ratio be about 0.3 to About 1.5.In some embodiments, ratio is about 0.3 to about 0.5.In some embodiments, ratio is about 0.5 to about 1. In some embodiments, ratio is about 1 to about 1.5.

In some embodiments, modified kraft fibers have higher kink and curling than standard brown kraft paper fiber. Modified kraft fibers according to the present invention have the kink index of about 1.3 to about 2.3.For example, kink index can be about 1.5 to About 2.3, or about 1.7 to about 2.3 or about 1.8 to about 2.3, or about 2.0 to about 2.3.According to the modified kraft fibers of the disclosure It can be with the length weight crimp index of about 0.11 to about 0.23 (such as about 0.15 to about 0.2).

In some embodiments, crystallization of the crystallinity index of modified kraft fibers relative to standard brown kraft paper fiber Spending index reduces about 5% to about 20%, for example, about 10% to about 20%, or about 15% to about 20%.

In some embodiments, the R10 values in about 65% to about 85%, example are had according to the modified cellulose of the disclosure Such as from about 70% to about 85%, or about 75% to about 85%.In some embodiments, had according to the modified fibre of the disclosure The R18 values of about 75% to about 90%, for example, about 80% to about 90%, for example, about 80% to about 87%.R18 and R10 contents exist Described in TAPPI 235.R10 is indicated with the remaining undissolved material of residual of 10 weight % caustic solutions extraction paper pulp, R18 tables Show the residual quantity that remaining undissolved material after paper pulp is extracted with 18% caustic solution.In general, in 10% caustic solution In, the short chain cellulose of hemicellulose and chemical degradation is dissolved and removes in the solution.In contrast, usually only half fiber Dimension element is dissolved and is removed in 18% caustic solution.Therefore, the difference between R10 values and R18 values (R=R18-R10) expression is deposited It is the amount of the short chain cellulose of the chemical degradation in pulp sample.

Based on one or more above-mentioned property (kink and curling of such as fiber, increased degree of functionality and modified krafts The crystallinity of fiber), those skilled in the art will expect that the modified kraft fibers of the disclosure have standard brown kraft paper fine Tie up the certain characteristics not having.For example, it is believed that the kraft fibers comparable standard kraft fibers of the disclosure are more flexible, and can It elongates and/or bending and/or demonstrates flexibility and/or increase wicking.In addition, without being bound by theory, it is desirable to which modified kraft is fine Dimension can provide a kind of physical arrangement (such as in Time of Fluff Slurry), and fibre matting and fibre/fibre can be caused to combine or can incite somebody to action It is applied to the material winding of the paper pulp, so that these materials are maintained at the relatively-stationary interstitial site in paper pulp, blocks it Diffusion.In addition, at least due to crystallinity is reduced relative to standard brown kraft paper fiber, it is desirable to which the modified kraft fibers of the disclosure will Can be more soft than standard brown kraft paper fiber, enhance it in absorbent products application (for example, such as diaper and bandage application) Applicability.

In some embodiments, modified cellulose fibre has about 16% to about 30% or about 14% to about 16% S10 caustic fusion degree.In some embodiments, modified cellulose fibre have about 14% to about 22% or about 14% to About 16% S18 caustic fusion degree.In some embodiments, modified cellulose fibre has the Δ R of about 2.9 or bigger (difference between S10 and S18).Δ R is about 6.0 or bigger in some embodiments.

In some embodiments, modified cellulose fibre intensity (being measured by wet zero span breaking length) is about 4km to about 10km, for example, about 5km to about 8km.In some embodiments, fibre strength is at least about 4km, about 5km, about 6km, about 7km Or about 8km.In some embodiments, fibre strength in about 5km to about 7km, or about 6km to about 7km.

In some embodiments, modified kraft fibers have smell domination property.In some embodiments, modified Kraft fibers can mitigate the smell of body excretions, such as urine or menstruation.In some embodiments, modified kraft is fine Dimension absorbs ammonia.In some embodiments, modified kraft fibers inhibit bacterium smell to generate, for example, in some embodiment party In formula, modified kraft fibers inhibit bacterium ammonia to generate.

In at least one embodiment, modified kraft fibers can absorb odorant, such as nitrogenous odorant (such as ammonia).

Term " odorant " used herein is understood to mean that the chemical material with taste or smell, or can be with Olfactory receptor interacts, or indicates that the compound for generating taste or smell (such as generating the bacterium of urea) biology can be generated Body (such as bacterium).

In some embodiments, the air ammonia concentration that modified kraft fibers reduce is than standard bleached kraft fibers The air ammonia of reduction is more.For example, modified kraft fibers can be applied partially onto modified kraft fibers by absorbing Ammonia sample, or pass through inhibit bacterium ammonia generate reduce air ammonia.In at least one embodiment, modified kraft Fiber absorbs ammonia and bacterium ammonia is inhibited to generate.

In some embodiments, modified kraft fibers are more than the air ammonia concentration that standard brown kraft paper pulp fiber reduces At least 40%, for example, more than standard brown kraft paper fiber at least about 50% or more about 60% or more about 70% or more about 75% or More about 80% or more about 90% ammonia.

In some embodiments, the modified kraft fibers of the disclosure (apply to about 9 grams of modified celluloses 0.12g50% Ammonias and after 45 minutes soaking times) so that the air ammonia concentration in 1.6L volumes is dropped Down to less than 150ppm, for example, being less than about 125ppm, for example, less than about 100ppm, for example, being less than about 75ppm, for example, being less than About 50ppm.

In some embodiments, every gram of fiber of modified kraft fibers absorbs about 5ppm to about 10ppm ammonias.Example Such as, the every gram of Fibrillar absorbable about 6ppm to about 10ppm or about 7ppm to about 10ppm or about 8ppm of modified cellulose are to about 10ppm ammonias.

In some embodiments, compared with standard brown kraft paper fiber, modified kraft fibers have improved gas simultaneously Taste domination property and increased whiteness.In at least one embodiment, modified cellulose fibre with about 85 to about 92 it is white It spends and smell can be reduced.For example, modified cellulose can be with the whiteness of about 85 to about 92, and every gram of fiber absorbs about 5ppm is to about 10ppm ammonias.

In some embodiments, modified cellulose fibre has the MEM elution cytotoxicity examinations less than 2 in terms of 0 to 4 grade Test (ISO 10993-5) value.Such as cytotoxicity is smaller than about 1.5 or less than about 1.

The cellulose (especially including the cellulose of aldehyde and/or carboxyl) of known oxidation shows antiviral and/or anti-micro- It is biological.See, e.g., Song et al., Novel antiviral activity of dialdehyde starch, Electronic J.Biotech., volume 12, the 2nd phase, 2009；The U.S. Patent No. of Looney et al. 7,019,191.For example, Known aldehyde radical in dialdehyde starch provides antiviral activity, the regenerated cellulose of the cellulose of oxidation and oxidation (such as containing Carboxylic acid group) it is frequently used for wound care application, partially due to its sterilization and hemostatic properties.Therefore, in some embodiments In, the cellulose fibre of the disclosure can express out antiviral and/or antimicrobial acivity.In at least one embodiment, change Property cellulose fibre shows antibacterial activity.In some embodiments, modified cellulose fibre shows antiviral activity.

In some embodiments, the modified kraft fibers of the disclosure have less than 200, are such as less than about 100 or small In the about 80 or balance DP less than about 75 or less than about 50 or less than or equal to about 48.Balance DP can pass through side known in the art Method measures, such as passes through the Level-Off Degree of Polymerization, Division disclosed in Battista et al. of Cellulose Chemistry,Symposium on Degradation of Cellulose and Cellulose Derivatives,127^thMethod in Meeting, ACS, Cincinnati, Ohio (March nineteen fifty-five-April) measures.

In some embodiments, modified kraft fibers have the Kappa number less than about 2.For example, modified kraft is fine Dimension can have the Kappa number less than about 1.9.In some embodiments, modified kraft fibers have about 0.1 to about 1, such as About 0.1 to about 0.9, such as about 0.1 to about 0.8, for example, about 0.1 to about 0.7, for example, about 0.1 to about 0.6, such as about 0.1 to about 0.5 or about 0.2 to about 0.5 Kappa number.

In some embodiments, modified kraft fibers are the kraft fibers bleached in multistage technology, wherein oxygen Change step has at least one blanching step later.In such embodiment, the modification after at least one blanching step Fiber has " k values " (being measured according to TAPPI UM 251) about 0.2 to about 1.2.For example, k values can be about 0.4 to about 1.2, Or about 0.6 to about 1.2, or about 0.8 to about 1.2, or about 1.0 to about 1.2.

In some embodiments, modified cellulose fibre has greater than about 2 copper valence (copper number).One In a little embodiments, copper valence is more than 2.0.In some embodiments, copper valence is greater than about 2.5.For example, copper valence can be greater than about 3. In some embodiments, copper valence is about 2.5 to about 5.5, such as about 3 to about 5.5, for example, about 3 to about 5.2.

In at least one embodiment, the hemicellulose level of modified kraft fibers does not substantially bleach ox with standard Mulberry paper fiber it is identical.For example, the hemicellulose level of cork kraft paper fiber can be about 16% to about 18%.For example, hardwood The hemicellulose level of kraft fibers can be about 18% to about 25%.

III. it is further processed --- acidity/basic hydrolysis

In some embodiments, manufacture of the modified kraft fibers of the disclosure suitable for cellulose derivative, such as with In the manufacture of more low viscosity cellulose ether, cellulose esters and microcrystalline cellulose.In some embodiments, the modification of the disclosure Kraft fibers are the modified kraft fibers of hydrolysis." modified kraft fibers of hydrolysis " the used herein, " ox of hydrolysis Mulberry paper fiber " etc. is understood to mean that makes any acid of cellulose chain depolymerization or the fiber of alkali process by having notified.One In a little embodiments, it is further processed according to the kraft fibers of the disclosure to reduce its viscosity and/or the degree of polymerization.For example, According to the kraft fibers usable acid or alkali process of the disclosure.

In some embodiments, the disclosure provides a kind of method of processing kraft fibers, including bleaching is according to this public affairs Then the kraft fibers opened hydrolyze the kraft fibers of bleaching.Hydrolysis can pass through any method known to a person of ordinary skill in the art It carries out.In some embodiments, bleached kraft fibers are at least one sour water solution.In some embodiments, it bleaches Kraft fibers pass through the sour water solution selected from sulfuric acid, inorganic acid and hydrochloric acid.

The disclosure also provides a kind of method for manufacturing cellulose ether.In some embodiments, for manufacturing fiber The method of plain ether includes the kraft fibers bleached according to the disclosure, is handled and is floated at least one alkaline agent (such as sodium hydroxide) White kraft fibers, and fiber is made to be reacted at least one etherifying agent.

The disclosure also provides the method for manufacturing cellulose esters.In some embodiments, for manufacturing cellulose esters Method include the kraft fibers bleached according to the disclosure, with catalyst (such as sulfuric acid) handle bleached kraft fibers, so At least one of acetic anhydride or acetic acid is used to handle fiber afterwards.In an alternate embodiments, for manufacturing cellulose acetate The method of ester includes the kraft fibers bleached according to the disclosure, with sulphuric acid hydrolysis bleached kraft fibers, and uses acetic anhydride Or the kraft fibers of at least one of acetic acid processing hydrolysis.

The disclosure also provides the method for manufacturing microcrystalline cellulose.In some embodiments, for manufacturing crystallite fibre The method of dimension element includes the bleached kraft fibers provided according to the disclosure, straight at least one sour water solution bleached kraft fibers It reaches desired DP or hydrolyzes bleached kraft fibers under the conditions of reaching balance DP.In yet another embodiment, it hydrolyzes Bleached kraft fibers through mechanical treatment, such as by milling, grinding or shear.To machinery in microcrystalline cellulose manufacture The method that mode handles the kraft fibers of hydrolysis is known to those skilled in the art, and can provide desired grain size.For The other parameters and condition for manufacturing microcrystalline cellulose are known, and in such as U.S. Patent No. 2,978,446 and the 5th, Described in No. 346,589.

In some embodiments, alkaline agent or escharotic is further used to handle according to the modified kraft fibers of the disclosure To reduce its viscosity and/or the degree of polymerization.Basic treatment (about 9 or more pH) causes two aldehyde reactions and carries out beta-hydroxy elimination. The fiber being further modified handled with alkaline agent can also be used for paper handkerchief, towel and other absorbent products and cellulose The manufacture of derivative application.In more conventional paper technology, strength agents are often added into fiber pulp to improve finished product Physical property.The alkali modification fiber can be used to some or all the intensity adjustment agent for replacing manufacturing for paper handkerchief and towel.

As described above, there is three classes fiber product that can be prepared by technique described herein.The first kind is to have passed through catalysis The fiber of oxidation processes, the fiber and its conventional counterpart almost undistinguishable (physical property at least related to and papermaking For matter), however its degree of functionality with the relevant imparting following property of one or more：Its smell domination property can press Contracting, low DP and ultralow DP, and/or alkalinity or acidic hydrolysis conditions (such as manufacture cellulose derivative (for example, manufacture ether or Acetate) condition) under " original position " be converted to the ability of low DP/ low viscosities fiber.The physical characteristic of the fiber of the type and papermaking Property makes it suitable for using in general papermaking and absorbent products application.On the other hand, increased degree of functionality is (for example, aldehyde And carboxyl) and property related with degree of functionality so that the fiber is more catered to the need and more general than standard brown kraft paper fiber.

Second fiber is the fiber for having undergone catalysis oxidation and having used alkalinity or escharotic processing later.Alkaline agent draws Fiber is played to be broken via at the increased carbonyl functionality site of oxidation technology.The fiber and the fiber of only experience oxidation have not Same physics and Papermaking Properties, but same or similar DP levels are can express out, because for measuring viscosity and and then measurement DP Test make fiber undergo escharotic.For those skilled in the art, different alkaline agents and content can provide different DP levels It is obvious.

Third fiber is the fiber for having undergone catalysis oxidation and having been handled in acidic hydrolysis step later.Acidic hydrolysis Lead to fiber hydrolization, may decompose to and its level that balance DP consistent.

IV. the product manufactured by kraft fibers

The disclosure provides the product manufactured by modified kraft fibers described herein.In some embodiments, institute It is the product that those are usually manufactured by standard brown kraft paper fiber to state product.In other embodiments, the product is that those are logical The product often manufactured by velveteen or sulfite pulp.More particularly, modified fibre of the invention can be (without further changing Property) raw material is used and is used as in the preparation of chemical derivative (such as ether and ester) in absorbent products manufacture.So far, also Do not have available fiber for replace high alpha content cellulose (such as cotton and sulfite pulp) and traditional brown paper fibre The fiber of dimension.

It is such as " it can replace velveteen (or sulfite pulp) ... " and " can be with velveteen (or sulfite pulp) ... mutual Change " and " its can be used for replace velveteen (or sulfite pulp) ... " etc. phrase only indicate the fiber have be suitable for it is logical The property being often used in the final application of velveteen (or sulfite pulp) manufacture.The phrase, which is not intended to, indicates the fiber Must have and velveteen (or sulfite pulp) identical characteristic.

In some embodiments, the product is absorbent products, including but not limited to medical equipment (including wound shield Manage (such as bandage)), baby' diaper nursing pad, adult-incontinence articles, feminine hygiene articles (including for example, sanitary napkin and health Cotton), dustless nonwoven products, dustless composition, " desktop " rag, napkin, paper handkerchief, towel etc..According to the absorbability of the disclosure Product can be disposable.In those embodiments, modified fibre according to the present invention can be used as being commonly used in these products The bleached hardwood of manufacture or all or part of substitute of cork fibrous.

In some embodiments, modified cellulose fibre is Time of Fluff Slurry form and having makes modified cellulose fibre exist One or more properties more significantly more efficient than conventional Time of Fluff Slurry in absorbent products.More particularly, modified fibre of the invention Can have increased compressibility and increased smell controlling, both of which to be adapted for as current fluff pulp fibers Substitute.Since the compressibility of the fiber of the disclosure increases, it can be used for trying thinner, the overall compact absorbing structure of manufacture Embodiment in.After the compressible character for the fiber for understanding the disclosure, those skilled in the art, which are readily appreciated, to be made With the absorbent products of the fiber.In some embodiments, by way of example, the disclosure provides the Modified Kraft for including the disclosure The ultra-thin amenities of paper fiber.Ultra-thin villus core is commonly used in (for example) feminine hygiene articles or baby' diaper.This public affairs can be used The other products for the fiber manufacture opened can be any required absorbent cores or compress the article of absorbed layer.Upon compression, of the invention The absorbability of fiber does not show to lose or does not show significantly to lose, but shows flexible increase.

The modified fibre of the present invention can also be used for the manufacture of absorbent products without further modification, including but not limited to Paper handkerchief, towel, napkin and the other paper products formed on traditional papermaking machine.Traditional paper technology is related to preparing logical The fiber pulp aqueous solution being often stored on forming net removes water in forming net later.The modified cellulose fibre of the disclosure increases Degree of functionality improved product characteristic can be provided in the product including these modified fibres.It is of the invention due to the above reasons, Modified fibre can cause to show increased intensity with the product that this is manufactured, may be related with the increased degree of functionality of the fiber. The modified fibre of the present invention can also make product have increased pliability.

In some embodiments, the modified fibre of the disclosure can be used for cellulose without further modified In ether (such as carboxymethyl cellulose) and the manufacture of ester, the fiber as the high DP with about 2950 to about 3980 is (that is, have In the fiber for the viscosity of about 30mPas to about 60mPas measured by 0.5% capillary CED) and high cellulose percentage Than (such as 95% or higher) fiber (such as from velveteen and from being manufactured by acid accumulator sulfite pulping process Bleached softwood fiber) substitute.Do not undergo acidic hydrolysis the present invention modified fibre would generally manufacture cellulose ether or Receive this acidic hydrolysis processing in the production technology of ester.

As described above, the second class and third fiber are via making the technique of fiber derivatization or hydrolysis manufacture.These are fine The manufacture that dimension can also be used for absorbing articles, absorb paper product and the cellulose derivative including ether and ester.

V. acidity/alkaline hydrolysis products

In some embodiments, the disclosure provides a kind of modification ox can be used as velveteen or sulfite pulp substitute Mulberry paper fiber.In some embodiments, the disclosure provides a kind of modification can be used as velveteen or sulfite pulp substitute Kraft fibers, such as in the manufacture of cellulose ether, cellulose acetate and microcrystalline cellulose.

It is without being bound by theory, it is believed that be provided relative to the increased aldehyde of conventional kraft pulp and finished product is made for being etherified The additional active site of (carboxymethyl cellulose, methylcellulose, hydroxypropyl cellulose etc.) so that can be used for papermaking and fibre The fiber of the plain derivative of dimension is manufactured as possibility.

In some embodiments, modified kraft fibers have the chemical property for being adapted to cellulose ether manufacture.Cause This, the disclosure provides a kind of cellulose ether from described modified kraft fibers.In some embodiments, fiber Plain ether is selected from ethyl cellulose, methylcellulose, hydroxypropyl cellulose, carboxymethyl cellulose, hydroxypropyl methyl cellulose and hydroxyl Ethylmethylcellulose.It is believed that the cellulose ether of the disclosure can be used for any application of conventionally used cellulose ether.Such as (but It is not intended as limiting), the cellulose ether of the disclosure can be used for coating, ink, adhesive, controlled release drug tablet and film.

In some embodiments, modified kraft fibers have the chemical property for being adapted to cellulose esters manufacture.Cause This, the disclosure provides a kind of cellulose esters of the modified kraft fibers from the disclosure, such as cellulose acetate.At some In embodiment, the disclosure provides a kind of production of the cellulose acetate comprising the modified kraft fibers from the disclosure Product.For example, but without limitation, the cellulose esters of the disclosure can be used for household items, cigarette, ink, absorbent products, medical treatment Device and plastics (including for example, LCD and plasma panel and wind shield).

In some embodiments, modified kraft fibers have the chemical property for being adapted to microcrystalline cellulose manufacture. Microcrystalline cellulose manufacture needs relatively pure, highly purified cellulosic material.Thus, it is traditionally, main using expensive Sulfite pulp for its manufacture.The disclosure provides the microcrystalline cellulose of the modified kraft fibers from the disclosure. Therefore, the disclosure provides a kind of cost-effective cellulose source for microcrystalline cellulose manufacture.In some embodiments, micro- Crystalline cellulose derives from the modified kraft fibers with the DP for being less than about 100 (for example, less than about 75 or less than about 50).One In a little embodiments, microcrystalline cellulose derive from and have about 65% to about 85% (for example, about 70% to about 85%, or about 75% to About 85%) R10 values and about 75% to about 90% (for example, about 80% to about 90%, for example, about 80% to R18 values about 87%) Modified kraft fibers.

The modified cellulose of the disclosure can be used for any application of conventionally used microcrystalline cellulose.For example, but not making For limitation, the modified cellulose of the disclosure can be used for drug or health products application, food applications, cosmetic applications, paper application Or structural composites.For example, the modified cellulose of the disclosure can be adhesive, diluent, disintegrant, lubricant, tableting aid, Stabilizer, thickener, fat substitute, filler, anti-caking agent, foaming agent, emulsifier, thickening agent, release agent, gelling agent, Carrier material, opacifier or viscosity modifier.In some embodiments, microcrystalline cellulose is colloid.

VI. include the product of Acidic Hydrolysis Products

In some embodiments, the disclosure provides a kind of modified kraft fibers system comprising from the disclosure hydrolyzed The drug products for the microcrystalline cellulose made.The drug products can be any drug products of conventionally used microcrystalline cellulose. For example, but be not intended as limiting, the drug products can be selected from tablet and capsule.For example, the microcrystalline cellulose of the disclosure can be Diluent, disintegrant, adhesive, compression aid, coating and/or lubricant.In other embodiments, the disclosure provides a kind of Include the drug products of at least one modified derivatization disclosure kraft fibers (modified kraft fibers such as hydrolyzed).

In some embodiments, the disclosure provides a kind of food production of the bleached kraft fibers of the disclosure hydrolyzed Product.In some embodiments, the disclosure provides a kind of at least one including the bleached kraft fibers from the disclosure The food product of product.In other embodiments, it includes the kraft fibers from the disclosure that the disclosure, which provides a kind of, The food product of microcrystalline cellulose.In some embodiments, the food product includes the brown paper fibre from the disclosure The Colloidal microcrystalline cellulose of dimension.The food product can be any food product of conventionally used microcrystalline cellulose.It can be used The exemplary food product type of microcrystalline cellulose is known to those of ordinary skill, it is seen that in such as Codex Alimentarius (such as table 3).For example, the microcrystalline cellulose from the chemical modification kraft fibers of the disclosure can be anti-caking agent, filling Agent, emulsifier, foaming agent, stabilizer, thickening agent, gelling agent and/or suspending agent.

Including from according to the cellulose derivatives of the chemical modification kraft fibers of the disclosure and microcrystalline cellulose Other products can also be expected by those of ordinary skill.Such product is found in such as cosmetics and commercial Application.

Used herein " about " is changed in order to illustrate caused by experimental error.Unless expressly stated otherwise, will Whole measurement results are interpreted as being modified by " about ", in spite of clearly statement " about ".Thus, for example, " there is 2mm length Fiber " statement be considered as indicate " with about 2mm length fiber ".

The details of one or more non-limiting embodiments of the present invention illustrates in the examples below.The disclosure is discussed Later, other embodiments of the present invention should be obvious for those of ordinary skill.

Embodiment

A. test procedure

1. caustic fusion degree (R10, S10, R18, S18) is measured according to TAPPI T235-cm00.

2. carboxyl-content is measured according to TAPPI T237-cm98.

3. aldehyde is measured according to the program ESM 055B of Econotech Services LTD ownership.

4. bronze medal valence is measured according to TAPPI T430-cm99.

5. carbonyl content is to be calculated according to the following formula by copper valence：Carbonyl=(copper valence -0.07)/0.6, comes from Biomacromolecules 2002,3,969-975.

6. 0.5% capillary CED viscosity is measured according to TAPPI T230-om99.

7. inherent viscosity is measured according to ASTM D1795 (2007).

8.DP is according to the following formula by 0.5% capillary CED viscosity calculations：DPw=-449.6+598.4ln (0.5% capillarys Pipe CED)+118.02ln²(0.5% capillary CED), from publication in the The Chemistry of Cellucon meetings in 1994 And Processing Of Wood And Plant Fibrous Materials pages 155, Woodhead Publishing Ltd, Abington Hall, Abington, Cambridge CBI 6AH, England, J.F.Kennedy et al. editors.

9. carbohydrate is measured by Dionex ion chromatography analysis according to TAPPI T249-cm00.

10. content of cellulose is to be calculated according to the following formula by carbohydrate composition：(sweet dew is poly- for cellulose=glucan- Sugar/3), come from TAPPI Journal 65 (12):78-80,1982.

11. hemicellulose level is to subtract content of cellulose by the summation of sugar to calculate.

12. fibre length and roughness are according to the standardization program of manufacturer from OPTEST, Hawkesbury, The Fiber Quality Analyzer of Ontario^TMUpper measurement.

13. wet zero tensile (wet Zero Span Tensile) is measured according to TAPPI T273-pm99.

14. freedom is measured according to TAPPI T227-om99.

15. water retention value is measured according to TAPPI UM 256.

16.DCM (dichloromethane) extract is measured according to TAPPI T204-cm97.

17. iron content is measured by acidolysis and icp analysis.

18. ash content is measured according to TAPPI T211-om02.

19. peroxide residual is according to Interox program determinations.

20. whiteness is measured according to TAPPI T525-om02.

21. porosity is measured according to TAPPI 460-om02.

22. burst factor (burst factor) is measured according to TAPPI T403-om02.

23. tear factor is measured according to TAPPI T414-om98.

24. fracture length and extensibility are measured according to TAPPI T494-om01.

25. opacity is measured according to TAPPI T425-om01.

26.Frazier porositys are according to the program of manufacturer from Frazier Instruments, It is measured on the Frazier Low Air Permeability Instrument of Hagerstown, MD.

27. fibre length and form factor are according to the standardization program of manufacturer from Lorentzen＆Wettre, It is measured on the L＆W Fiber Tester of Kista, Sweden.

28. dust and fibre bundle (shive) are measured according to TAPPI T213-om01.

B. the illustrative methods of modified cellulose fibre are manufactured

Usable acid, iron and hydrogen peroxide treatment half bleaching or most of bleached kraft pulp, it is low-fiber viscous for dropping Degree or DP.The fiber can use sulfuric acid, hydrochloric acid, acetic acid or the filtrate from acid bleaching section (such as chlorine dioxide stage) washer PH is adjusted to about 2 to about 5 (if not yet within this range).Iron can be with Fe⁺²Form is added, such as iron can be used as ferrous sulfate Heptahydrate (FeSO₄·7H₂O it) adds.It can be soluble in water with the concentration of about 0.1g/L to about 48.5g/L by ferrous sulfate.Sulfuric acid Ferrous iron solution can be based on pulp dry weight in about 25ppm to the Fe of about 200ppm⁺²Application speed addition.It then can be by sulfuric acid Asia The paper pulp of ferrous solution and pH after the adjustment are using the consistency of about 1% to about 15% of the dry pulp content measurement as total wet pulp quality It is thoroughly mixed.Then can be used as solution addition has with H₂O₂The hydrogen peroxide of about 1% to about 50% concentration of weight meter in water (H₂O₂), dosage is based on the pulp dry weight about 0.1% to about 3%.The permissible pH mixed with ferrous sulfate and peroxide Paper pulp in about 2 to about 5 reacts about 40 minutes to about 80 minutes at about 60 DEG C to about 80 DEG C.Viscosity (or DP) reduction degree depends on In the amount of the peroxide consumed in the reaction, when which depends on the concentration of the peroxide applied and iron and measures and keep Between and temperature.

The processing can be with D₀It is completed in five sections of bleach plants of typical case of E1D1E2D2 standard procedures.Pass through the party Case does not need additional storage tank, pump, mixer, tower or washer.4th section or E2 sections is preferred for the processing.At D1 sections Fiber on washer can be on demand by adding acid or pH being adjusted to about 2 to about 5 from D2 sections of filtrate.Ferrous sulfate is molten Liquid can be added in paper pulp one of in the following manner：(1) it is washed at D1 sections via already present spray head or new nozzle It sprays on device pad, (2) are via the humidifier device addition in repulper, or (3) via in the 4th section of mixer or pump Addition point addition before.In solution form peroxide can then ferrous sulfate enter the 4th section of tower mixer or pump In before addition point addition.Also steam can be added in steam mixer on demand before entering the column.Then paper pulp can The retention time appropriate is reacted in the tower.Then can in the 4th section of washer washing chemistry modified paper in the normal fashion Slurry.Additional bleaching then can be completed optionally by the 5th section or D2 sections operated in the normal fashion in the processing.

Embodiment 1

The method for preparing the fiber of the disclosure

A. factory method A

Boiling Southern Pine cellulose and oxygen delignification is carried out in traditional two-stage oxygen delignification step to about 9 to about 10 Kappa number.By the paper pulp of delignification in five sections of bleach plants, pass through D₀(EO) D1E2D2 processes are bleached.At the 4th section or Before E2 sections, paper pulp pH is adjusted to about 2 to about 5 with the filtrate from the step D section.After adjusting pH, paper pulp will be based on The hydrogen peroxide of dry weight 0.2% and FeSO based on pulp dry weight₄·7H₂The 25ppm Fe of O forms⁺²It is added in E2 sections of towers Kraft fibers in, and reacted about 90 minutes at about 78 DEG C to about 82 DEG C.Then the fiber of reaction is washed at the 4th section It is washed on device, then in the 5th (D2) section ClO 2 bleaching.

B. factory method B

Fiber is prepared according to the description in factory method A, the difference is that with 0.6% peroxide and 75ppm Fe⁺²Processing The paper pulp.

C. factory method C

Fiber is prepared according to the description in factory method A, the difference is that with 1.4% peroxide and 100ppm Fe⁺²Processing The paper pulp.

The property of exemplary fiber

Then above-mentioned five sectional bleachings sequence collection is prepared according to factory method A (sample 2), B (sample 3) and C (sample 4) Fiber sample.These samples and standard villus grade fibre (GP Leaf River are measured according to said program Cellulose, New Augusta, MS；Sample 1) and commercial samples (PEACH^TM, Weyerhaeuser Co. sales；Sample 5) Properties.These results measured are reported in the following table 1.

Table 1

It is such as reported in table 1, does not measure the iron content of control fiber (sample 1).It is reported with sample 1 however, measuring Accuse the iron content of the four factories manufacture pulp sample handled under the same conditions.The iron content of these samples is averagely 2.6ppm.Therefore, for sample 1, it is contemplated that iron content be about 2.5ppm.

As seen from Table 1, (sample 1 and another commercially available oxidation are fine for modified fibre according to the present invention and two kinds of control fibers Tie up sample 5) total carbonyl content and carboxyl-content and aldehyde it is unexpectedly different.There is difference between total carbonyl and aldehyde radical In the case of other, other carbonyl functionalities may be in the form of other ketone.Data show the present inventor in relatively high aldehyde Carboxyl is kept while content and at the same time keeping the ratio of aldehyde and total carbonyl close to consistent (such as in table 1 as it can be seen that about 1.0 (0.95) to 1.6).In showing high whiteness and also relatively tough and absorptive fiber, this is more astonishing.

Such as in table 1 as it can be seen that the standard villus grade fibre (sample 1) with 3.13meq/100g carboxyl-content and The aldehyde of 0.97meq/100g.Use 0.2%H₂O₂With 25ppm Fe⁺²Low dosage processing (sample 2) or use 0.6%H₂O₂With 75ppm Fe⁺²The high dose of (sample 3) is handled, or uses 1.4%H₂O₂With 100ppm Fe⁺²Higher doses processing (sample 4) it Afterwards, fibre length and the content of cellulose of calculating are relatively unchanged, and by wet zero fibre strength away from method measurement, some are reduced, However carboxyl, carbonyl and aldehyde all increase, and show the cellulose through extensive oxidation.

In contrast, compared with the villus grade fibre reported as sample 1, pass through the oxidation ox-hide of alternative manufacture The commercial samples (sample 5) of paper cork Southern Pine fiber show that fibre length significantly reduces and by wet zero away from method measurement Fibre strength loss 70%.The aldehyde of sample 5 is actually unchanged compared with standard villus grade fibre, however passes through factory Fiber (sample 2-4) aldehyde height of the present invention prepared by method A-C increases, and is equivalent to the cellulose and always calculates carbonyl About the 70% to about 100% of content.In contrast,Aldehyde always calculates carbonyl content less than the cellulose 30%.The ratio of total carbonyl and aldehyde will be the good of wide applicability of the fiber with the modified fibre within the scope of the disclosure Mark, especially if the ratio is about 1 to about 2, sample 2-4 is such.With about 1.5 to less than 2.0 carbonyl/aldehyde The low viscosity fiber (such as sample 3 and 4) of ratio maintains fibre length, and those of comparative sample 5 does not have.

Compare freedom, density and the intensity of above-mentioned standard fiber (sample 1) and above-mentioned sample 3.The result of this analysis Described in table 2.

Paper pulp, paper and the fibre property of 2 standard of table and modified kraft fibers

As it can be seen that can be had according to the modified cellulose fibre of the disclosure and not passed through in bleaching process such as in upper table 2 Go through the comparable freedom of standard villus fiber of oxidation processes.

Embodiment 2

The 0.5% capillary CED viscosity with about 14.6mPas of D1 sections of OD (EOP) D (EP) D bleach plants will be come from Southern Pine pulp sample to 0.25% to 1.5% apply hydrogen peroxide and as FeSO₄·7H₂O addition 50 or 100ppm Fe⁺²It is handled under about 10% consistency.Fe⁺²It adds as aqueous solution and is thoroughly mixed with paper pulp.Then by 3% Aqueous hydrogen peroxide solution is mixed with paper pulp.Mixed paper pulp is kept for 1 hour at 78 DEG C in water-bath.After reaction time, by paper Slurry filters and measures the pH and residual peroxide of filtrate.Washing pulp and 0.5% capillary is measured according to TAPPI T230 Pipe CED viscosity.As a result it is shown in table 3.

Table 3

Embodiment 3

Other than the retention time became 80 minutes from 45 minutes, the bleach plant also described in leisure in future embodiment 2 D1 pulp samples (with 15.8mPas 0.5% capillary CED viscosity) (DPw 2101) with apply 0.75% peroxide Change hydrogen processing and adds 50ppm to 200ppm Fe in method same as Example 2⁺².As a result it shows in table 4.

Table 4

Embodiment 4

D1 pulp samples (0.5% capillary with 14.8mPas of bleach plant described in comfortable embodiment 2 in the future Pipe CED viscosity) (DPw 2020) with 0.75% hydrogen peroxide and 150ppm Fe⁺²With with the same procedure that describes in example 2 Processing, the difference is that processing time is 80 minutes.As a result it shows in table 5.

Table 5

Embodiment 5

OD will be come from₀(EO) Southern Pine pulp (0.5% capillary with 15.6mPas of the D1 sections of D1 (EP) D2 processes Pipe CED viscosity) (DPw 2085) use the hydrogen peroxide of based on pulp weight 0.25% or 0.5% application and as FeSO₄·7H₂O 25ppm, 50ppm or 100ppm Fe of addition⁺²It is handled under 10% consistency.Fe⁺²It is added as aqueous solution and thorough with paper pulp Mix to bottom.Hydrogen peroxide is then 3% aqueous solution mixes it with paper pulp, and mixed paper pulp keeps 1 at 78 DEG C in water-bath Hour.After reaction time, by paper pulp filtering and the pH and residual peroxide of filtrate are measured.Washing pulp and according to TAPPI T230 measure 0.5% capillary CED viscosity.As a result it is shown in table 6.

Table 6

Embodiment 6

Another D1 pulp sample (the 0.5% capillary CED viscosity with 15.2mPas) (DPw 2053) is used 0.10%, 0.25%, 0.50% or 0.65% hydrogen peroxide and 25ppm, 50ppm or 75ppm Fe⁺²With same as Example 5 Method processing.As a result it is shown in table 7.

Table 7

Embodiment 7

Delignification degree in increasing brown paper and oxygen section is to manufacture with lower DPw or 0.5% capillary After the paper pulp of CED viscosity, Southern Pine pulp is collected from the D1 sections of OD (EO) D (EP) D bleaching process.Originate 0.5% capillary CED viscosity is 12.7mPas (DPw 1834).By 0.50% or 1.0% hydrogen peroxide and 100ppm Fe⁺²Addition.Other places Manage bar part is 10% consistency, 78 DEG C and 1 hour processing time.As a result it is shown in table 8.

Table 8

Embodiment 8

The low viscosity sample that the D1 paper pulp of the D1 sections of OD (EO) D (EP) D processes will be come from (has 11.5mPas's 0.5% capillary CED viscosity (DPw 1716)) with 0.75% or 1.0% hydrogen peroxide and 75ppm or 150ppm Fe⁺²With similar It is handled in the method for embodiment 7, the difference is that processing time is 80 minutes.As a result it is shown in Table 9.

Table 9

Embodiment 9

Southern Pine pulp is collected from the D1 sections of OD (EO) D (EP) D processes.Originating 0.5% capillary CED viscosity is 11.6mPa·s(DPw 1726).By 1.0%, 1.5% or 2% hydrogen peroxide and 75ppm, 150ppm or 200ppm Fe⁺²Add Add.Other treatment conditions are 10% consistency, 78 DEG C and 1.5 hour processing time.As a result it is shown in Table 10.

Table 10

Embodiment 10

Southern Pine pulp is collected from the D1 sections of OD (EO) D (EP) D processes.Originating 0.5% capillary CED viscosity is 14.4mPa·s(DPw 1986).By 1.0%, 1.5% or 2% hydrogen peroxide and 75ppm, 150ppm or 200ppm Fe⁺²Add Add.Other treatment conditions are 10% consistency, 78 DEG C and 1.5 small the reaction times.As a result it is shown in Table 11.

Table 11

Embodiment 11

Southern Pine pulp is collected from the D1 sections of OD (EO) D (EP) D processes.Originating 0.5% capillary CED viscosity is 15.3mPa·s(DPw 2061).The hydrogen peroxide and 200ppm Fe of paper pulp 3% are pressed in addition⁺².Other treatment conditions are 10% thick Degree, 80 DEG C and 1.5 small the reaction times.As a result it is shown in table 12.

Table 12

Above example 2-11 is shown, 0.5% capillary may be implemented using the acidic catalyst peroxide treatment of the disclosure The significant decrease of pipe CED viscosity and/or the degree of polymerization.Final viscosity or DPw are likely to be dependent on by the peroxide of reaction consumption Amount, as shown in Figure 1, this is sought ways to return sb.'s kindness, conduct of the announcement from two different factories (" Brunswick " and Leaf River (" LR ")) disappears The pulp viscosity of the function of the percentage peroxide of consumption.Peroxide consumption amount depends on the amount of the peroxide and iron that apply With concentration, reaction time and reaction temperature.

Embodiment 12

Southern Pine pulp is collected from the D1 sections of OD (EO) D (EP) D processes.Originating 0.5% capillary CED viscosity is 14.8mPa·s(DPw 2020).Addition is by the hydrogen peroxide of paper pulp 1% and as CuSO₄·5H₂The 100ppm of 0 addition, 150ppm or 200ppm Cu⁺².Other treatment conditions are 10% consistency, 80 DEG C and 3.5 small the reaction times.As a result in table 13 Displaying.

Table 13

It replaces iron that reaction is caused to slow down using copper and viscosity is made to be even lower, but compared with control (untreated paper pulp) Still there is significant change in viscosity, carboxyl-content and aldehyde.

Embodiment 13

Change E2 (EP) sections of OD (EOP) D (EP) D processes to manufacture ultra low polymerization degree paper pulp.With 150ppm Fe⁺²Apply Add rate to the paper pulp FeSO in D1 sections of washer repulpers₄·7H₂O solution is sprayed.Not simultaneously to E2 sections of addition caustic soda (NaOH) And peroxide application increases to 0.75%.Retention time is about 1 hour, and temperature is 79 DEG C.PH is 2.9.The paper pulp of processing It is washed in vacuum rotary drum washer and then in final D2 sections 0.7%ClO₂It is handled about 2 hours at 91 DEG C.Final drift 0.5% capillary CED viscosity of blank sheet of paper slurry is 6.5mPas (DPw1084), and ISO whiteness is 87.

Embodiment 14

The paper pulp manufactured in embodiment 13 is made on the Fourdrinier type pulp dryers with standard dryer cans At pulp board.Collect control paper pulp and paper pulp (ULDP) sample of the invention and analytical chemistry ingredient and fibre property.As a result It is shown in table 14.

Table 14

Property		Reference substance	ULDP
				R10	%	85.2	81.5
S10	%	14.8	18.5
				R18	%	86.4	84.4
S18	%	13.6	15.6
				△R		1.2	2.9
Carboxyl	meq/100g	4.06	4.27
				Aldehyde	meq/100g	0.43	1.34
Copper valence		0.32	1.57
				Carbonyl calculated value	mmole/100g	0.42	2.50
0.5% capillary CED viscosity	mPa·s	14.2	7.3
				Inherent viscosity	dl/g	6.76	4.37
DP calculated values	DPW	1969	1206
				Glucan	%	83.6	83.6
Xylan	%	9.2	9.0
				Galactan	%	0.2	0.2
Mannosan	%	6.3	6.4
				Araban	%	0.4	0.4
Cellulose calculated value	%	81.5	81.5
				Hemicellulose calculated value	%	18.2	18.1
Lwl fibre lengths	mm	2.51	2.53
				Lww fibre lengths	mm	3.28	3.26
Roughness	mg/m	0.218	0.213
				Wet zero away from anti-tensile	km	9.86	6.99
Freedom (CSF)	mis	720	742
				Water retention value	g H2Op/g paper pulp	0.96	0.84
DCM extracts		0.008	0.007
				Iron	ppm	3.5	10.7
Ash content	%	0.20	0.22
				Whiteness	%ISO	90.4	86.5

Processed paper pulp (ULDP) has higher caustic fusion degree and higher aldehyde in 10% and 18%NaOH With total carbonyl content.By 0.5% capillary CED viscosity measurements, the DP of ULDP is significantly decreased.The reduction of fibre integrity It is determined by the reduction of wet zero tensile.Although DPw is significantly reduced, fibre length and freedom are substantially without change Change.There is no adverse effect to draining or making sheet on machine.

Embodiment 15

Change E2 (EP) sections of OD (EO) D (EP) D processes to manufacture ultra low polymerization degree paper by the similar approach of embodiment 13 Slurry.In this embodiment, by 75ppm Fe⁺²Add FeSO₄·7H₂O, the hydrogen peroxide applied in E2 sections are 0.6%.Place The pH for managing section is 3.0, and temperature is 82 DEG C, and the retention time is about 80 minutes.Washing pulp and then in D2 sections with 0.2% ClO₂It is handled about 150 minutes at 92 DEG C.0.5% capillary CED viscosity of full bleaching paper pulp is 5.5mPas (DPw 914), ISO whiteness is 88.2.

Embodiment 16

By the paper pulp manufactured in embodiment 15 with air-cushion type Flakt^TMThe Fourdrinier type paper pulp of drying machine part Pulp board is made on drying machine.Collection standard paper pulp and paper pulp (ULDP) sample of the present invention and analytical chemistry ingredient and fiber Property.As a result it is shown in table 15.

Table 15

Property		Reference substance	ULDP
				R10	%	86.8	82.4
S10	%	13.2	17.6
				R18	%	87.0	85.4
S18	%	13.0	14.6
				△R		0.2	3.0
Carboxyl	meq/100g	3.13	3.70
				Aldehyde	meq/100g	0.97	2.15
Copper valence		0.51	1.3
				Carbonyl calculated value	mmole/100g	0.73	2.05
0.5% capillary CED viscosity	mPa·s	15.0	6.5
				Inherent viscosity	dl/g	7.14	4.33
DP calculated values	DPW	2036	1084
				Glucan	%	83.0	84.6
Xylan	%	9.0	9.4
				Galactan	%	0.2	0.2
Mannosan	%	5.9	5.3
				Araban	%	0.4	0.3
Cellulose calculated value	%	81.0	82.8
				Hemicellulose calculated value	%	17.5	17.0
Lwl fibre lengths	mm	2.55	2.53
				Lww fibre lengths	mm	3.29	3.34
Roughness	mg/m	0.218	0.234
				Wet zero away from anti-tensile	km	9.38	6.83
Freedom (CSF)	mis	738	737
				Iron	ppm	1.6	4.4
Whiteness	%ISO	89.6	88.2

Processed paper pulp (ULDP) has higher caustic fusion degree and higher aldehyde in 10% and 18%NaOH With total carbonyl content.By 0.5% capillary CED viscosity measurements, the DP of ULDP is significantly decreased and wet zero span breaking length drops It is low.Whiteness is still acceptable value 88.2.Processing maintains fibre length and freedom, is formed and is not operated when drying plate The problem of.

Embodiment 17

Change E2 (EP) sections of OD (EO) D (EP) D processes to manufacture low polymerization degree paper pulp by the similar approach of embodiment 13. In the case with 25ppm Fe⁺²Add FeSO₄·7H₂O, the hydrogen peroxide applied in E2 sections are 0.2%.The pH of processing section It is 3.0, temperature is 82 DEG C and the retention time is about 80 minutes.Washing pulp and use 0.2%ClO in D2 sections₂92 DEG C processing about 150 minutes.0.5% capillary CED viscosity of full bleaching paper pulp is 8.9mPas (DPw 1423), and ISO is white Degree is 89.

Embodiment 18

By the paper pulp manufactured in embodiment 15 with air-cushion type Flakt^TMThe Fourdrinier type paper pulp of drying machine part Pulp board is made on drying machine.Collection standard paper pulp and the present invention low polymerization degree paper pulp (LDP) sample and analytical chemistry at Point and fibre property.As a result it is shown in table 16.

Table 16

Property		Reference substance	LDP
				R10	%	86.8	85.2
S10	%	13.2	14.8
				R18	%	87.0	87.2
S18	%	13.0	12.8
				△R		0.2	2.0
Carboxyl	meq/100g	3.13	3.53
				Aldehyde	meq/100g	0.97	1.24
Copper valence		0.51	1.2
				Carbonyl calculated value	mmole/100g	0.73	1.88
0.5% capillary CED viscosity	mPa·s	15.0	8.9
				Inherent viscosity	dl/g	7.14	5.44
DP calculated values	DPW	2036	1423
				Glucan	%	83.0	85.9
Xylan	%	9.0	8.8
				Galactan	%	0.2	0.2
Mannosan	%	5.9	5.4
				Araban	%	0.4	0.3
Cellulose calculated value	%	81.0	84.1
				Hemicellulose calculated value	%	17.5	16.5
Lwl fibre lengths	mm	2.55	2.57
				Lww fibre lengths	mm	3.29	3.34
Roughness	mg/m	0.218	0.222
				Iron	ppm	1.6	5.5
Whiteness	%ISO	89.6	89.0

Processed paper pulp (LDP) have in 10% and 18%NaOH higher caustic fusion degree and higher aldehyde and Total carbonyl content.By 0.5% capillary CED viscosity measurements, the DP of LDP is lower.Whiteness has few loss.Processing maintains Fibre length does not have operational problem when being formed with drying plate.

Embodiment 19

By the pulp board fibrosis described in embodiment 14 and use Kamas Laboratory Hammermill (Kamas Industries, Sweden) air shapes 4 " × 7 " liner.Then the liner by air forming uses laboratory pressure Machine is compressed in a variety of gauge pressures.After compacting, surveyed using the 200-A model Emveco precision ultrasonics with 0.089psi plantar pressures Thick instrument calliper (Emveco microgage caliper gage) measures liner thickness.It is padded by cushion weight and THICKNESS CALCULATION Density.As a result described in table 17.

Table 17

Data in table 17 are shown in the modified fibre manufactured within the scope of the disclosure and have more compressibility, and generation is more suitable for The thinner and more high density structures of current disposable absorbent products design.

It is without being bound by theory, it is believed that the crystal structure of the Oxidative demage polymer of cellulose makes it become less hard And it is more comfortable.Then become more compressible by the fiber of modified cellulose structure composition, to allow high density absorbing structure Production.

Embodiment 20

Southern Pine pulp is collected from the D1 sections of OD (EO) D (EP) D processes.Originating 0.5% capillary CED viscosity is 14.9mPa·s(DPw 2028).1.0% or 2% hydrogen peroxide of addition and 100ppm or 200ppm Fe respectively⁺².Other processing Condition is 10% consistency, 80 DEG C and 1 hour retention time.Then these Time of Fluff Slurry are beaten with deionized water, wet method is added to filter Net is dehydrated with forming fibrous layer by means of roller press, and is dried in 250 ℉.Use Kamas Laboratory Dry paper is taken off fiber to Hammermill (Kamas Industries, Sweden) and air forming attaches most importance to 8.5 grams (air is dry It is dry) 4 "^×7 " dustless liner.Non-thermoplastic face layer will individually be completely covered to be applied to the one side of each liner and use Carver liquid Pressure tablet press machine, which applies 145psig load, makes sample increase density.

These liners, which are placed in individual 1.6L, has outfit check valve and 1/4 " IDThe sample tap of slot it is impermeable Gas plastic containers.Before fixed container cover, in room temperature by 60 grams of deionized waters and 0.12 gram of 50%NH₄OH dirts are poured into energy " the ID VERTICAL TUBEs of center 1 in enough conveying devices for applying 0.1psi load to entire sample.When dirt fully absorbs, from sample Product remove conveying device, lid (having sealing sample tap) are installed to container, and start count down timer.Terminated at 45 minutes When, from ammonia selectivity short-term gas detection pipe and(the two can be from Draeger for diaphragm pump Safety Inc., Pittsburgh, PA are obtained) sample tap take headspace sample.Data in table 18 are shown, in this public affairs The ammonia amount in headspace can be reduced by opening the modified fibre manufactured in range, generated offer and inhibited often to be cited as wet The structure of unpleasant volatile malodorous compounds in incontinence product.

Table 18

Embodiment 21

Change E2 (EP) sections of OD (EO) D (EP) D processes of commercialization kraft pulp equipment with by the similar of embodiment 14 Method manufactures low polymerization degree paper pulp.In this embodiment, FeSO₄·7H₂O is with 100ppm Fe⁺²Addition, is answered in E2 sections Hydrogen peroxide is 1.4%.Pulp properties are shown in table 19.

Table 19

Property		ULDP
			R10	%	72.5
S10	%	27.5
			R18	%	78.7
S18	%	21.3
			△R		6.2
Carboxyl	meq/100g	3.94
			Aldehyde	meq/100g	4.21
Copper valence		4.25
			Carbonyl calculated value	mmole/100g	6.97
0.5% capillary CED viscosity	mPa·s	3.50
			Inherent viscosity	dl/g	2.49
DP calculated values	DPW	485
			Lwl fibre lengths	mm	2.31
Roughness	mg/m	0.19
			Whiteness	%ISO	88.5

By the modifying chemical fiber element of manufacture with air-cushion type Flakt^TMThe Fourdrinier type paper pulp of drying machine part Pulp board is made on drying machine.The outturn sample and control brown paper pulpboard are used into the de- fibre of Kamas laboratory hammer mills Dimension.By means of the HiRes Fiber that can be obtained from Optest Equipment, Inc. (Hawkesbury, ON, Canada) Quality Analyzer carry out fibre property optical analysis according to the scheme of manufacturer to former and later two Kamas plant samples. As a result described in following table.

Table 20

Property	Control	ULDP	It is compareed after sledge mill	ULDP after sledge mill
					Kink index	1.79	2.29	1.51	2.32
Kink angle	59.15	79.56	48.52	80.26
					The kink number per mm	0.81	1.07	0.68	1.06
Crimp index (length weight)	0.171	0.211	0.149	0.225

As it can be seen that the ULDP fibers prepared according to the disclosure are more fine than the control without iron and peroxide treatment such as in table 20 Dimension has higher kink and curling.

The fiber air forming of the above de- fiber is weighed to 4 " × 7 " liner of 4.25 grams (air-dried).It will be from the poly- of BASF It is intermediate that sodium acrylate high-hydroscopicity (SAP) particle is evenly applied to two 4.25 grams of liners.Non-thermoplastic face layer will be completely covered Material is applied to the upper surface of fiber/SAP matrixes and the 145psig load applied by means of Carver tablet press machines makes liner increase Density.

It (can be by Hardy by dissolving 2% urea, 0.9% sodium chloride and 0.24% foster battalion's meat soup in deionized water Diagnostics, Santa Maria, the Criterion that CA is obtained^TMBoard), and add 1.4 × 10⁷CFU/ml starting bacterias A proteus vulgaris (Proteus Vulgaris) that concentration generates urinates to prepare synthesis.Then above-mentioned liner is placed at Headspace chamber described in embodiment 20 and apply 80ml synthesis urine solution dirts.By chamber after applying dirt It seals and is placed in the environment of 30 DEG C of temperature.Continuously Drager is carried out with the time interval of four hours and seven hours to take Sample.It will test in triplicate, average result is reported in table 21.

Table 21

From data as it can be seen that merging the composite construction of the modified cellulose fibre manufactured within the scope of the disclosure (in structure The urinary incontinence product of upper similar retail) in air ammonia ratio caused by bacterium hydrolysis by urea there is standard brown kraft paper Southern Pine The composite construction of fiber manufacture is lower.Therefore, including according to the structure of the modified cellulose fibre of the disclosure than standard brown kraft paper Southern Pine fiber has more preferably smell domination property.

Comparison of the 4th section of the embodiment 22 to bleaching post-processing

Southern Pine pulp is collected from the D1 sections of OD (EO) D1 (EP) D2 processes.Originating 0.5% capillary CED viscosity is 14.1mPa·s.1.5% and 150ppm Fe of the hydrogen peroxide based on pulp dry weight⁺²Addition.As used herein, " P* " is used To indicate iron and hydrogen peroxide treatment stage.Described in being carried out 1 hour in the 4th section of the process at 78 DEG C in 10% consistency Processing.This is washed out through handling paper pulp and at 78 DEG C with 0.25%ClO₂It is bleached 2 hours in D2 sections.As a result in table 22 Displaying.

Table 22

The above D2 samples restore (brightness also by 1 hour test whiteness in 105 DEG C of baking oven is placed it in reversion).Before and after restoration disposal, measured in vain according to the scheme of manufacturer by Hunterlab MiniScan Degree and L* (white), a* (red to green) and b* (blue to yellow) value.As a result it is shown in following table 23.The b of corrigendum Value indicates more yellow.Therefore, without hope there is higher b values in most of paper and pulp applications.Reported be-low moves back The difference of k/s ratios before and after color value (post color number) expression aging, wherein k=absorption coefficients, s=scattering coefficients, That is post color number=100 { (k/s)_{After aging}-(k/s)_{Before aging}}.See, e.g. H.W.Giertz, Svensk Papperstid., 48 (13), 317 (1945).

23 whiteness of table is restored

Stage	L*	a*	b*	Whiteness	△ whiteness	Post color number
							D1	96.89	-0.28	5.13	85.8
DP*D is initial	97.89	-0.47	2.96	90.8
							DP*D restores	96.08	-0.55	8.01	80.4	10.4	1.92

From as above have it is identical starting capillary CED viscosity identical bleach plant D2 sections collection Southern Pine pulp and Hydrogen peroxide and Fe are used as described above⁺²Processing.Add 1.5% hydrogen peroxide and 150ppm Fe based on pulp dry weight⁺².At this The property of paper pulp is managed described in table 24.

Table 24

The whiteness of test P* paper pulp as described above.As a result described in following table 25.

25 whiteness of table is restored

Stage	L*	a*	b*	Whiteness	△ whiteness	Post color number
							D2 is initial	98.34	-0.61	2.54	92.54
D2 restores	97.87	-0.57	3.67	89.92	2.62	0.26
							D (EP) DP* is initial	97.39	-0.47	4.49	87.68
D (EP) DP* restores	95.25	-0.34	9.78	76.45	11.2	2.76

From data above as it can be seen that acidic catalyst peroxide treatment in the 4th section of five sections of bleach plants and then five The processing of section bleach plant final stage, which is compared, generates beneficial whiteness property.In being handled at the 4th section, lost from the processing section Any whiteness the compensation of final D2 bleach paragraphs can be used still to obtain high whiteness paper pulp.The case where after bleaching is handled, there is 3.4 The notable loss of whiteness of point cannot be compensated.After accelerating whiteness restoration disposal, the latter still reduces with significantly whiteness.

23 intensity data of embodiment

By by according to the intensity of the Time of Fluff Slurry of modified cellulose manufacture of the disclosure with 5.1mPas viscosity with have Traditional Time of Fluff Slurry of 15.4mPas viscosity compares.As a result described in following table 26.

Table 26

	Compare villus	Modified cellulose
			Base weight, gm/m2 AD	65.12	68.15
Base weight, gm/m2 OD	60.56	63.38
			Freedom CSF, mis	732	717
Thickness, in/1000	4.88	5.09
			Body volume, cm3/gm	1.90	1.90
Apparent density, gm/cm3	0.53	0.53
			Porosity, sec/100 mis air	0.59	0.67
Burst factor, (gm/cm2)/(gm/m2)	16.6	14.0
			Tear factor, gf*m2/gm	242	198
Fracture length, km	2.52	2.49
			Extensibility, %	2.76	2.48
Opacity, %	72.1	73.5
			Dust and fibre bundle, mm2/m2	0.3	1.5
Viscosity, cP	15.4	5.1
			ISO whiteness	88.9	88.9
Frazier porositys, cfm	45.4	55.1
			Fibre length, mm	2.636	2.661
Form factor, %	85.8	85.8

The derivatization of 24 modified cellulose of embodiment

By the ULDP samples from embodiment 21 with 0.05 M HCl in 5% consistency and 122 DEG C of acidic hydrolysis 3 hours.It is logical Cross average molecular weight or the degree of polymerization of the following methods test from D1 sections of initial pulp, ULDP and acidic hydrolysis ULDP.

Three pulp samples are milled with by 20 mesh filter screens.Cellulose sample (15mg) is placed in and is equipped with small stirring rod It is dried overnight in individual test tube and at 40 DEG C under vacuum.Then by rubber septum on test tube cap.By means of syringe according to Secondary addition anhydrous pyridine (4.00mL) and phenyl isocyanate (0.50mL).Test tube is placed in 70 DEG C of oil bath and allows to stir 48h.Any remaining phenyl isocyanate is quenched in addition methanol (1.00mL).Then the content of each test tube is added dropwise to 7: 3 methanol/water mixtures (100mL) are to promote the precipitation of derivative cellulose.Solid is collected by filtration, then uses methanol/water (1 × 50mL) is washed, and is then washed with water (2 × 50mL).Then derivative cellulose is dried whole night at 40 DEG C under vacuum. Derivative cellulose is dissolved in THF (1mg/mL), is filtered by 0.45 μm of filter and is placed in 2mL autosampler bottles In, then carry out gpc analysis.Gained DPw and DPn (number-average degree of polymerization) are reported in following table 27.

27 DPn and DPw test results of table

Sample	Mn(g/mol)	Mw(g/mol)	DPn	DPw
					D1	1.4601e5	2.2702e6	281	4374
ULDP	4.0775e4	7.4566e5	78	1436
					Acidic hydrolysis ULDP	2.52.5e4	1.8966e5	48	365

As it can be seen that it can be with 48 DPn according to the modified cellulose of the acidic hydrolysis of the disclosure such as in upper table.

Embodiment 25

By being beaten to fiber, pH to about 5.5 is adjusted, be then added as interim wet strength agent comes from Kemira Handmade paper is made in Leaf River ULDP fibers and standard softwood fiber by the glyoxalated polyacrylamide of Chemicals.Then Fiber is formed, paper and drying are pressed into.The characteristic of the paper is measured by known method.The result is in following table 28 Middle report.

28 handmade paper property of table

As it can be seen that can be used for the manufacture of wet pressing paper according to the ULDP of the disclosure such as in upper table 28.If shown in fig. 2, Wet/dry ratio of comparison paper of wet/dry ratio of the handmade paper formed by ULDP than only being manufactured by standard southern softwood is high.

Embodiment 26

The top layer and bottom that are handled using surfactant and untreated middle layer, it is fine by standard and modified kraft Dimension produces ultra-thin villus core.Table 29 describes the configuration of the ultra-thin villus core of production.As a result it reports in table 30.By Materials Testing Service of Kalamazoo, MI are tested with the testing equipment of their own and program.Profit It is first with the load-carrying of the gauge length of 5.00cm, the Sample Width of 1.3cm, 2.5cm/ minutes crosshead speed and 30kg, in machine The tensile strength and elongation of each product are measured on device direction.It is fine with TQ-2021 processing standards in mark It ties up and handles modified plate with TQ-2028, two kinds of surface-active agents are all provided by Ashland, Inc..By applying to sample Then 0.9% salting liquid of 5ml makes fluid wick 5 minutes and obtains fluid and obtain object.After five minutes, standard laboratory is used Filter paper obtains 2 minutes and returns moisture.

Table 29

Table 30

It is such as visible in upper table 30, have using product is absorbed made from the processed fiber of the surfactant of the disclosure There are improved elasticity, improved dimensional stability, improved wet strength and dry strength to be returned with elongation and improved blood wet Amount.

Other embodiment

Although desired invention limits applicant in the dependent claims at present, it should be understood that can be according to following reality The mode of applying limits the present invention, these embodiments need not be exhaustive or limit those of claimed：

A. a kind of fiber from bleached softwood or hardwood kraft pulp, wherein the fiber have about 13mPas or Smaller, preferably less than about 10mPas, more preferably less than 8mPas, more preferably less than about 5mPas or further more The 0.5% capillary CED viscosity of preferably less than about 4mPas.

B. a kind of fiber from bleached softwood kraft slurry, wherein the average fiber length of the fiber is at least about 2mm, preferably at least about 2.2mm, for example, at least about 2.3mm, or for example, at least about 2.4mm, or for example, about 2.5mm, more preferably from about 2mm is to about 3.7mm, more preferably about 2.2mm to about 3.7mm.

C. a kind of fiber from bleached hardwood kraft slurry, wherein the average fiber length of the fiber is at least about 0.75mm, preferably at least about 0.85mm, or at least about 0.95mm, or more preferably at least about 1.15mm, or about 0.75mm is to about 1.25mm。

D. a kind of fiber from bleached softwood kraft slurry, wherein the fiber has about 13mPas or smaller The ISO whiteness of 0.5% capillary CED viscosity, at least about average fiber length of 2mm and about 85 to about 95.

E. the fiber as described in any one of embodiment A~D, wherein the viscosity is about 3.0mPas to about 13mPas, for example, about 4.5mPas are to about 13mPas, and preferably from about 7mPas is to about 13mPas, or for example, about 3.0mPas to about 7mPas, preferably from about 3.0mPas are to about 5.5mPas.

F. the fiber as described in embodiment A~D, wherein the viscosity is less than about 7mPas.

G. the fiber as described in embodiment A~D, wherein the viscosity is at least about 3.5mPas.

H. the fiber as described in embodiment A~D, wherein the viscosity is less than about 4.5mPas.

I. the fiber as described in embodiment A~D, wherein the viscosity is at least about 5.5mPas.

J. the fiber as described in embodiment E, wherein the viscosity is not greater than about 6mPas.

K. the fiber as described in one in embodiment of above, wherein the viscosity is less than about 13mPas.

L. the fiber as described in one in embodiment A~B and D~K, wherein the average fiber length is at least about 2.2mm。

M. the fiber as described in one in embodiment A~B and D~L, wherein the average fiber length is not greater than about 3.7mm。

N. the fiber as described in one in embodiment A~M, wherein the S10 caustic fusion degree of the fiber is about 16% to about 30%, preferably from about 16% to about 20%.

O. the fiber as described in one in embodiment A~M, wherein the S10 caustic fusion degree of the fiber is about 14% to about 16%.

P. the fiber as described in one in embodiment A~O, wherein the S18 caustic fusion degree of the fiber is about 14% to about 22%, preferably from about 14% to about 18%, more preferably from about 14% to about 16%.

Q. the fiber as described in one in embodiment A~P, wherein the S18 caustic fusion degree of the fiber is about 14% to about 16%.

R. the fiber as described in one in embodiment A~Q, wherein the fiber has the Δ R of about 2.9 or bigger.

S. the fiber as described in one in embodiment A~Q, wherein the fiber has about 3.0 or bigger, preferably from about 6.0 or bigger Δ R.

T. the fiber as described in one in embodiment A~S, wherein the carboxyl-content of the fiber is about 2meq/100g To about 8meq/100g, preferably from about 2meq/100g to about 6meq/100g, more preferably from about 3meq/100g to about 6meq/100g.

U. the fiber as described in one in embodiment A~S, wherein the fiber has at least about carboxylic of 2meq/100g Base content.

V. the fiber as described in one in embodiment A~S, wherein the fiber has at least about 2.5meq/100g's Carboxyl-content.

W. the fiber as described in one in embodiment A~S, wherein the fiber has at least about carboxylic of 3meq/100g Base content.

X. the fiber as described in one in embodiment A~S, wherein the fiber has at least about 3.5meq/100g's Carboxyl-content.

Y. the fiber as described in one in embodiment A~S, wherein the fiber has at least about carboxylic of 4meq/100g Base content.

Z. the fiber as described in one in embodiment A~S, wherein the fiber has at least about 4.5meq/100g's Carboxyl-content.

AA. the fiber as described in one in embodiment A~S, wherein the fiber has at least about carboxylic of 5meq/100g Base content.

BB. the fiber as described in one in embodiment A~S, wherein carboxyl of the fiber with about 4meq/100g contains Amount.

CC. the fiber as described in one in embodiment A~BB, wherein the aldehyde of the fiber is about 1meq/100g To about 9meq/100g, preferably from about 1meq/100g to about 3meq/100g.

DD. the fiber as described in one in embodiment A~BB, wherein the fiber has at least about 1.5meq/100g Aldehyde.

EE.

FF. the fiber as described in one in embodiment A~BB, wherein the fiber has at least about 2.0meq/100g Aldehyde.

GG. the fiber as described in one in embodiment A~BB, wherein the fiber has at least about 2.5meq/100g Aldehyde.

HH. the fiber as described in one in embodiment A~BB, wherein the fiber has at least about 3.0meq/100g Aldehyde.

II. the fiber as described in one in embodiment A~BB, wherein the fiber has at least about 3.5meq/100g Aldehyde.

JJ. the fiber as described in one in embodiment A~BB, wherein the fiber has at least about 4.0meq/100g Aldehyde.

KK. the fiber as described in one in embodiment A~BB, wherein the fiber has at least about 5.5meq/100g Aldehyde.

LL. the fiber as described in one in embodiment A~BB, wherein the fiber has at least about 5.0meq/100g Aldehyde.

MM. the fiber as described in one in embodiment A~MM, wherein the carbonyl of the fiber determined by copper valence Content is greater than about 2, preferably greater than about 2.5, more preferably greater than about 3 or its by the carbonyl content that copper valence determines be about 2.5 to The carbonyl content of about 5.5, preferably from about 3 to about 5.5, more preferably from about 3 to about 5.5 or described fibers determined by copper valence is About 1 to about 4.

NN. the fiber as described in one in embodiment A~NN, wherein the carbonyl content is about 2 to about 3.

OO. the fiber as described in one in embodiment A~NN, wherein the carbonyl of the fiber determined by copper valence contains Amount is about 3 or bigger.

PP. the fiber as described in one in embodiment A~NN, wherein the fiber have about 0.9 to about 1.6 it is total The ratio of carbonyl and aldehyde.

QQ. the fiber as described in one in embodiment A~NN, wherein the ratio of total carbonyl and aldehyde is about 0.8 to about 1.0.

RR. the fiber as described in one in embodiment of above, wherein the Canadian Standard Freeness (" trip of the fiber From degree ") be at least about 690mls, preferably at least about 700mls, more preferably at least about 710mls, or for example, at least about 720mls or About 730mls.

SS. the fiber as described in one in embodiment of above, wherein the fiber is free at least about 710mls Degree.

TT. the fiber as described in one in embodiment of above, wherein the fiber is free at least about 720mls Degree.

UU. the fiber as described in any one of embodiment of above, wherein the fiber has at least about trip of 730mls From degree.

VV. the fiber as described in one in embodiment of above, wherein the fiber has the trip no more than about 760mls From degree.

WW. the fiber as described in one in embodiment A~WW, wherein the fiber has the fibre of about 4km to about 10km Tie up intensity (being measured by wet zero span breaking length).

XX. the fiber as described in one in embodiment A~WW, wherein the fiber has the fiber of about 5km to about 8km Intensity.

YY. the fiber as described in one in embodiment A~WW, wherein the fiber has at least about fiber of 4km strong It spends (being measured by wet zero span breaking length).

ZZ. the fiber as described in one in embodiment A~WW, wherein the fiber has at least about fiber of 5km strong It spends (being measured by wet zero span breaking length).

AAA. the fiber as described in one in embodiment A~WW, wherein the fiber has at least about fiber of 6km strong It spends (being measured by wet zero span breaking length).

BBB. the fiber as described in one in embodiment A~WW, wherein the fiber has at least about fiber of 7km strong It spends (being measured by wet zero span breaking length).

CCC. the fiber as described in one in embodiment A~WW, wherein the fiber has at least about fiber of 8km strong It spends (being measured by wet zero span breaking length).

DDD. the fiber as described in one in embodiment A~WW, wherein the fiber has the fibre of about 5km to about 7km Tie up intensity (being measured by wet zero span breaking length).

EEE. the fiber as described in one in embodiment A~WW, wherein the fiber has the fibre of about 6km to about 7km Tie up intensity (being measured by wet zero span breaking length).

FFF. the fiber as described in one in embodiment of above, wherein the ISO whiteness is about 85 to about 92, preferably from about 86 to about 90, more preferably from about 87 to about 90 or about 88 to about 90ISO.

GGG. the fiber as described in one in embodiment of above, wherein the ISO whiteness is at least about 85, preferably at least About 86, more preferably at least about 87, particularly at least about 88, more particularly at least about 89 or about 90ISO.

HHH. the fiber as described in one in embodiment A~FFF, wherein the ISO whiteness is at least about 87.

III. the fiber as described in one in embodiment A~FFF, wherein the ISO whiteness is at least about 88.

JJJ. the fiber as described in one in embodiment A~FFF, wherein the ISO whiteness is at least about 89.

KKK. the fiber as described in one in embodiment A~FFF, wherein the ISO whiteness is at least about 90.

LLL. the fiber as described in any one of embodiment of above, wherein the fiber has and standard brown kraft paper fiber Roughly the same length.

MMM. the fiber as described in one in embodiment A~S and SS~MMM has more than standard brown kraft paper fiber High carboxyl-content.

NNN. the fiber as described in one in embodiment A~S and SS~NNN has more than standard brown kraft paper fiber High aldehyde.

OOO. the fiber as described in embodiment A~S and SS~MMM, the ratio of the total aldehyde and carboxyl-content that have are big In about 0.3, preferably greater than about 0.5, more preferably greater than about 1.4, or be, for example, about 0.3 to about 0.5, or about 0.5 to about 1, or about 1 To about 1.5.

PPP. the fiber as described in any one of embodiment of above has higher kink than standard brown kraft paper fiber Index, for example, kink index be about 1.3 to about 2.3, preferably from about 1.7 to about 2.3, more preferably from about 1.8 to about 2.3 or about 2.0 to About 2.3.

QQQ. the fiber as described in any one of embodiment of above, length weight crimp index are about 0.11 to about 0.2, preferably from about 0.15 to about 0.2.

RRR. the fiber as described in any one of embodiment of above has lower crystallization than standard brown kraft paper fiber Index is spent, such as about 5% to about 20% is reduced relative to standard brown kraft paper fiber crystallinity index, preferably from about 10% to about 20%, more preferably 15% to 20% is reduced relative to standard brown kraft paper fiber.

SSS. the fiber as described in any one of embodiment of above, wherein the R10 values are about 65% to about 85%, it is excellent Choosing about 70% to about 85%, more preferably from about 75% to about 85%.

TTT. the fiber as described in any one of embodiment of above, wherein the R18 values are about 75% to about 90%, it is excellent Choosing about 80% to about 90%, more preferably from about 80% to about 87%.

UUU. the fiber as described in any one of embodiment of above, wherein the fiber has smell domination property.

VVV. the fiber as described in any one of embodiment of above, wherein the fiber is reduced than standard brown kraft paper fiber Air ammonia concentration have more at least 40%, preferably have more at least about 50%, more preferably have more at least about 60%, particularly have more At least about 70%, or at least about 75% is had more, more particularly have more at least about 80% or more about 90%.

WWW. the fiber as described in any one of embodiment of above, wherein every gram of fiber of the fiber absorbs about 5ppm To about 10ppm ammonias, preferably from about 7ppm to about 10ppm, more preferably every gram of fiber absorb about 8ppm to about 10ppm ammonias.

XXX. the fiber as described in any one of embodiment of above, wherein the MEM elution cytotoxicity examinations of the fiber It tests value and is less than 2, preferably less than about 1.5, more preferably less than about 1.

YYY. the fiber as described in any one of embodiment of above, wherein the copper valence is less than 2, preferably smaller than 1.9, more Preferably smaller than 1.8, more preferably less than 1.7.

ZZZ. the fiber as described in any one of embodiment A~YYY, Kappa number are about 0.1 to about 1, preferably from about 0.1 It is more excellent to about 0.9, more preferably from about 0.1 to about 0.8, for example, about 0.1 to about 0.7 or about 0.1 to about 0.6 or about 0.1 to about 0.5 Choosing about 0.2 to about 0.5.

AAAA. the fiber as described in any one of embodiment of above, have substantially with standard brown kraft paper fiber phase Same hemicellulose level, for example, the hemicellulose level is about 16% to about 18% when the fiber is cork fibrous, or When the fiber is hardwood fiber, the hemicellulose level is about 18% to about 25%.

BBBB. the fiber as described in any one of embodiment of above, wherein the fiber shows antimicrobial acivity And/or antiviral activity.

CCCC. the fiber as described in any one of embodiment B~C or L~CCCC, wherein the DP is about 350 to about 1860, for example, about 710 to about 1860, preferably from about 350 to about 910, or for example, about 1160 to about 1860.

DDDD. the fiber as described in any one of embodiment B~C or L~CCCC, wherein the DP is less than about 1860, Preferably less than about 1550, more preferably less than about 1300, more preferably less than about 820, or it is less than about 600.

EEEE. the fiber as described in any one of embodiment of above, wherein the fiber is more than standard brown kraft paper fiber Have compressibility and/or embossing property.

FFFF. the fiber as described in embodiment A~OOO, wherein the fiber can be compressed at least about 0.210g/ Cc, preferably at least about 0.220g/cc, more preferably at least about 0.230g/cc, the particularly at least about density of 0.240g/cc.

GGGG. the fiber as described in embodiment A~OOO, wherein the fiber can be compressed to than standard brown kraft paper fibre Tie up density up at least about 8% density, particularly higher than standard brown kraft paper fiber density about 8% to about 16%, preferably from about 8% to About 10% or high about 12% to about 16%, more preferably high about 13% to about 16%, more preferably high about 14% to about 16%, especially Ground is high by about 15% to about 16%.

Several embodiments have been described.It should be understood, however, that can be the spirit and scope for not departing from the disclosure the case where Under carry out various modifications.Therefore, other embodiment is fallen within the scope of following claims.

Claims (23)

1. a kind of method of absorbent cores of the manufacture with improved embossing ability, the method includes：

In the core include kraft fibers, the kraft fibers in bleaching process in acidic environment by copper catalysis Agent or iron catalyst and peroxide oxidation, and it is further processed with surfactant,

The wherein described kraft fibers show the specific absorption rate less than 30% after applying the surfactant and increase.

2. the method as described in claim 1, wherein the surfactant is degumming agent or softening agent.

3. the method as described in claim 1, wherein the surfactant is cationic surface active agent.

4. the method as described in claim 1, wherein the surfactant is selected from ethoxylated nonylphenol ether and plant type fat It is one or more in fat acid quaternary ammonium salt.

5. method as claimed in claim 4 is less than wherein the kraft fibers show after applying the surfactant 25% specific absorption rate increases.

6. method as claimed in claim 4, wherein four section internal oxidition of the fiber in five sectional bleaching sequences.

7. the method as described in claim 1, wherein the fiber has at least average fiber length of 2mm.

8. a kind of absorbent cores comprising：

At least three pars fibrosas, the firstth area, the secondth area and third area, wherein under normal use, firstth area is described Fluid is contacted before 2nd area, and secondth area contacts fluid before the third area,

At least one of described area of the wherein described core includes the kraft fibers of oxidation, and the kraft fibers have used surface Activating agent processing.

9. core as claimed in claim 8, wherein the oxidation kraft fibers of surfactant processing are present in the core Firstth area or third area in.

10. core as claimed in claim 8, wherein the oxidation kraft fibers of surfactant processing are present in the core At least twoth area in.

11. core as claimed in claim 10, wherein the oxidized fibre of surfactant processing is present in the core extremely In few firstth area and the secondth area.

12. core as claimed in claim 8, wherein the oxidation kraft fibers of surfactant processing are present in the core At least threeth area in.

13. core as claimed in claim 8, wherein the surfactant is selected from ethoxylated nonylphenol ether and plant type fat It is one or more in sour quaternary ammonium salt.

14. core as claimed in claim 13 is less than wherein the kraft fibers show after applying the surfactant 30% specific absorption rate increases.

15. a kind of Time of Fluff Slurry comprising：

The cork kraft paper fiber of bleaching, the aldehyde for showing 1meq/100g to 9meq/100g, at least carboxylic of 3meq/100g Base content, the 0.5% capillary CED viscosity less than 10mPas, at least 88 ISO brightness and the length weight of at least 2mm are flat Equal fibre length,

The wherein described fiber is handled with surface-active agents.

16. slurry as claimed in claim 15, wherein the surfactant is degumming agent or softening agent.

17. slurry as claimed in claim 15, wherein the surfactant is cationic surface active agent.

18. slurry as claimed in claim 15, wherein the surfactant is selected from ethoxylated nonylphenol ether and plant type fat It is one or more in fat acid quaternary ammonium salt.

19. slurry as claimed in claim 18, is less than wherein the kraft fibers show after applying the surfactant 30% specific absorption rate increases.

20. a kind of Time of Fluff Slurry comprising：

The kraft fibers produced in the following manner：Cellulose kraft pulp is bleached using multistage bleaching process；And Under acid condition the brown paper is aoxidized with peroxide and catalyst at least one stage of the multistage bleaching process Slurry, wherein the multistage bleaching process is included at least one chlorine dioxide bleaching stage after the oxidation stage,

The wherein described fiber is handled by one or more surfactants, and the kraft fibers are applying the surface Show the specific absorption rate less than 30% after activating agent to increase.

21. slurry as claimed in claim 20, wherein the surfactant is degumming agent or softening agent.

22. slurry as claimed in claim 20, wherein the surfactant is cationic surface active agent.

23. slurry as claimed in claim 20, wherein the surfactant is selected from ethoxylated nonylphenol ether and plant type fat It is one or more in fat acid quaternary ammonium salt.