FI106566B - Process for improving and controlling the adhesion strength of the fibers in cellulose or cellulose synthetic fiber blends in a process for producing nonwoven fabric products - Google Patents

Abstract

The new method combination is aimed at improving and regulating the adhesion between similar or different fibers in connection with a method for producing hydroentangled and thermobonded fabrics from cellulose and synthetic fiber blends. Improvement of the fiber adhesion aims at providing highstrength and well absorbing, stable, non-linting nonwoven structures containing high cellulose concentrations. In the new method, adhesion strength is improved by increasing kinetically and quantitatively the contact and wetting between molten polyolefin used for cellulose bonding, and the cellulose, and providing in the cooling contact site transcrystallization following heterogenous nucleation of the polyolefin structure. In order to provide for pre-contacts between the cellulose and cellulose-polyolefin fibers, effectivated hydrogen bonding between the cellulose fibers is used, especially when mechanically hydroentangling cellulose using unreacting synthetic fiber (polyamide, ester). In order to improve adhesion strength, the surface structure of the polyolefin and/or cellulose fibers has to be modified. The surface structure of the polyolefins is modified by molecular chain degradation caused by spinning oxidation, in order to decrease the surface energy, viscosity and temperature of the surface melt formed in bonding. The modification of the cellulose surfaces takes place by heat treatment in a polar liquid, whereby in connection with a conversion of the cellulose crystal structure (C-II (C-I) -> C-IV), its surface energy, crystallinity degree and crystal lamellar thickness of its superstructure increase. Hydrogen bond formation is activated with a combined corona and steam wetting-pressure-drying method.

Description

106566

The method is a mixture of cellulose or cellulose synthesis fibers. 5 A novel method combination is directed to improving the adhesion between the fibers of the same and different grades during the production of water-woven and thermosetting fabrics of cellulose or cellulose synthesis fibers.

The process utilizes both natural and regenerated cellulosic fibers and mainly polyolefin and polyester synthesis fibers.

The regenerated cellulose fibers can be blended into the synthetic fibers even before the thermo-bonding or hydroentangling process. The fiber layer of Ly-15 soft wood cellulose fibers, either as such or as a pre-blend with a polyolefin microfiber, is water-spun onto a synthetic fiber substrate by conventional methods, aiming for cellulose to either laminate or as high as possible blending.

The aim of improving the fiber-to-fiber adhesion in a nonwoven product, in addition to its high strength properties, is its high absorptive capacity and the production of a stable and dust-free, high cellulose product structure. Improvement of adhesion is based on a combination of several simultaneous or sequential sub-processes on fibers and / or knitted products in the context of hydroentangling and thermosetting processes.

Textile fabrics for medical applications, comprising fibers, monofilament and multifilament yarn, woven.

and nonwoven products and composites. The main requirements for medical textiles, depending on the intended use, are absorbency, strength, flexibility, softness, intermittent biostability or biodegradability. Cotton, wood and silk fiber are the 35 most common natural materials in medical textiles. These, together with regenerated cellulosic fibers (including rayon viscose), have been extensively used in surgical, non-imaging and health care and hygiene products. The synthetic materials used in medical textiles are mainly polyesters, polyamides and polyolefins.

5 The new adjustment method is mainly related to surgical, health care and hygiene textiles. The previous group includes e.g. wound dressing textiles, gauzes, patches and the latter surgical clothing textiles, duvets, incontinence diapers, protective clothing, clean room towels, etc.

10 As nonwoven products, these medical textiles are mainly manufactured using two sets of processes, namely thermosetting and water needle methods. The use of liquid binding polymers or similar binders in medical textiles is mainly avoided for reasons of hygiene and also product property. Liquid, short-chain binders particularly cover and encapsulate absorbent fibers and also prevent the formation of semipermeable, absorbent textiles (surgical clothing textiles).

Due to the manufacturing technology, the fine-cellulosic dust from the structure of nonwoven textiles 20 is extremely harmful. Dust formation mm. caused by e.g. low cell length, microfibrillation and other factors of natural and synthetic cellulose fibers. The air purity requirements of hospitals and some special wards set 25 quite narrow limits, eg. particle emission of medical textiles. Ic. US Federal Standard 209E, 1992 defines a cleanroom purity class of 100 for air containing particles of d ≤ 0.5 µm up to 100 pcs / Cu * ft or 3531 pcs / m3. This value is, for example, extremely difficult for ve-30 knitted fabrics (50 wt% cellulose, 70 g / m 2) containing wood fibers, as measured by conventional test methods. reach. In addition, regardless of variations in the manufacturing process, the water-woven fabric is very labile due to the short and wide length distribution of the wood cellulosic fibers, and is particularly sensitive to bending and shearing and the corresponding loading methods (and test methods, respectively).

The new control method is a combination of several sub-methods and is based on technical measurements and observations 3 106566. The features of the invention are set forth in the appended claims.

The invention thus relates to a method for improving and adjusting the fiber-to-fiber adhesive strength of cellulose or cellulose synthesis fiber mixtures, in particular polyolefin fiber mixtures, wherein the bonding of webs formed by said fibers and / or fiber mixtures to gauze and / or formats is applied. or a body of mosquito bonding methods which, prior to the binding process, increases the surface energy values of the cellulosic fiber by simultaneously increasing the crystallinity and long identity period of its surface layer and converting its crystalline structure from cellulose II or cellulose I to by pulping the cellulosic fiber in a polar, cellulose-non-soluble liquid at elevated temperature, prior to the binding process, the length of the molecular chains of the synthetic fiber surface layer used for binding the cellulose is reduced, to reduce the surface energy, melt viscosity and melting point of the bonding melt by subjecting the fiber surface in its spinning step, melt state, to adjustable oxidative chain degradation 25, before the bonding process, the synthesized and cellulose fibers involved in the melt bonding and pre-contact with one another, melt-bonded synthetic fiber melt cellulose surface wetting, surface nucleate; and and to verify transcrystallization, by conventionally adjusting the linear pressure between the rolls, and by adjusting the hydroentanglement between the cellulose fibers, as an on-line process by means of the following Korona steam wetting-pressure-drying process which enhances hydrogen bond adhesion.

Characteristic features of the new process include: - Improving adhesion between cellulose and polyolefin fibers is achieved by increasing the wetting between the molten polyolefin and cellulose and providing transcrystallization of the cooling contact site to the polyolefin structure. The wetting between the fiber surfaces is improved by modifying the surface structure of the polyolefin and / or cellulosic fibers. The sub-process is carried out in conjunction with the drying process (flow-through or suction process) of the water needling process or as a separate but on-line process.

15 - The surface modification of a polyolefin (especially polypropylene) fiber is based on large-scale degradation of the molecular surface chains of the fiber surface layer by spinning oxidation (FI application no. 974169 / 07.11.97) and the corresponding melting point and melt phase phase viscosity of the layer. The partial process is carried out in connection with fiber production.

The surface modification of the cellulosic fiber is mainly based on the thermal conversion of the regenerated (if necessary also natural) cellulose crystal structure, C-II (C-I), to C-IV, by treating it in a polar liquid phase. Transformations. As a result, the surface energy of the cellulosic fiber increases.

The modification can be carried out in the manufacture of cellulosic fiber using saturated high pressure steam or, depending on the conditions, as a separate heat treatment process.

30 - As a result of heat treatment of the cellulosic fiber (C-I, C-II) in the liquid phase, e.g. besides increasing the free surface energy, increasing the crystallinity of the structure * ', the cellulose superstructure becoming clearly lamellar, and at the same time increasing the structure over a long period.

The increase in the long period and degree of crystallinity of the surface structure of the cellulose results in an increase in crystalline lamellar thickness, which in turn provides the heterogeneous nucleation required for transcrystallization (e.g.

Improvement of adhesion between cellulosic fibers is based on the surface modification of cellulosic fibers by high-power corona treatment resulting in oxidative degradation of the molecular chains of the cellulose structure. increase in surface area by mechanical processing caused by bombardment of charged ions and electrons. The wetting of the fiber mixture following the corona treatment and the drying under pressure cause a very effective increase in velocity bond adhesion. The corona and other related treatments are carried out on a woven, dry cloth. When used in combination with a wood cellulose-polyolefin microfibre blend, good pre-contact (before melt wetting and transcrystallization) is achieved in a cellulose synthesis fiber system. In particular, the effect of the corona treatment on the fabric surface extends only to the thin surface layer, but the formation of hydrogen bridges adheres the surface fibers so that the cellulose fibers under the surface layers are "encapsulated" and the release of the cellulose dust 20 stops. The absorption capacity and velocity of the corona-treated product fabric are increased by the above mechanism. The corona and related subprocesses (including the wetting and transcrystallization processes) are carried out as an on-line process of the conventional water needling process.

25 - Cellulose-polyolefin fiber blends behave in a ter-. in the same manner as the synthetic polymer fibers, but the involvement of the cellulose in the blends is low (i.e., only a very small part of the cellulose surface is covered by the polymer melt, thus not disturbing the absorption processes). The thermal bonding of the fiber mixtures is controlled as indicated in patent FI 101087/1998.

- ·

In the new adjustment method, not all of the modification processes described are necessarily carried out in every fabric quality manufacturing process, although the partial processes alone are usually not sufficient to produce the desired result. Each subprocess can be adjusted for its effect and thereby control the end result as well as the subprocesses that can be selected to achieve it.

6 106566

Utilizing adhesion and adhesive bonding between synthetic and natural polymeric fibers to clarify the state of the art, the scientific grounds for adhesion binding and the use of cellulosic fibers in nonwoven nonwoven products, in particular from cellulosic fibrous webs, will be briefly reviewed.

10 The scientific basis of adhesion binding is elaborated here based on the critical review of S. Wu / 1 /.

The ideal strength of the two-phase adhesion bond is in terms of adhesion work (Wa) and equilibrium distance (Zo) 15 between the phases oad = K x Wa / Zo where / 1 /

Wa = Y! + γ2 - γ12 and Yj, γ2 and γ12 are the surface energies of each phase and the interface between them.

The characteristic values of the polymers give this ideal strength only about 104 N / mm 2. However, the strengths achieved in practice are of the order of magnitude lower. The perfect molecular contact required for an ideal adhesive bond is practically difficult to achieve.

There are several theories about the formation and influence of practical adhesion strengths, - each of which contributes to the function of this rather complicated group of phenomena. In order to understand the novel adhesion binding process contemplated, three experimentally demonstrated partial theories, which have a significant effect on the adhesion strength of ad-30, are briefly explained below.

• *

According to Fractura theory, the difference between the ideal and practical adhesive strength is due to the fact that the fracture process is not reversible and that there are always defects in the grain boundary and bulk regions. The strength of the adhesive bond is determined by the size of the defect and the energy lost in the irreversible deformation during the fracture process, i.e. f = K [E £ / d] 1/2, where / 2/7 106566 E is the elastic modulus, d is the microfracture length, ζ is the breaking energy: ζ = Wa + ψ, where ψ is the total work of irreversible processes (ψ »Wa, so ζ ~ ψ).

According to the wetting contact theory, van der Waals forces are sufficient to provide strong adhesion, provided that there is a molecular contact between the phases and that the energy of wetting affects the extent of the interface contact and thus the adhesion strength.

The driving force for wetting is assumed to be the spreading factor λ12, i.e. λι2 = γ2 - (Ύι + Yi2) / where 13 / λ12 is the phase 1 spreading factor for phase 2.

If the size d of the non-wetted interface pore with respect to the refractive index of le-15 is given by d = D0 [1- (λ12 / γ2)] n, where d0 and n are constants, we obtain equation f = K [E for the adhesion strength £ / d0] 1/2 [1- (λ12 / γ2)] 'n / 2, / 4 / i.e. the wettability is directly related to the adhesive strength, which has also been experimentally demonstrated.

The interface pore wetting rate can be given as an exponential damping function (dy / d) 1/2 = 1-a exp (-t / x), where / 5 / d and dy are the pore sizes at t and the infinite time, a 25 and τ are constants. Placing the / 2 / adhesion cell · / - hair into the equation / 5 / yields a change in strength over time t. It can be seen that the increase in adhesion strength follows first order kinetics, which can also be experimentally demonstrated.

30 According to diffusion theory, molecular chain or segment diffusion through a phase interface is a prerequisite for strong ad-. »For the formation of a hesian bond, that is to say: the molecular contact at the interface alone is not sufficient.

A prerequisite for interdiffusion to occur is the compatibility of the components hh-35. However, most polymer pairs are incompatible. Statistical thermodynamics requires that diffusion motions in the interface layer minimize the interface energy. The thickness of the polymer-diffusion interface layer is inversely related to the interaction parameter of 106566 tea (Flory-Higgins). As component compatibility increases, the interaction parameter decreases, interpenetration increases, and the interface layer thickness increases. On the other hand, the interaction parameter is proportional to the square of the difference in solubility pa-5 parameters. Decreased adhesion cellularity between polymers has been observed as the difference in phase solubility parameters increases.

Similar dependencies are found in the wetting-contact theory. Obviously, matching the solubility parameters reduces the interface tension and thus increases the wetting driving force and adhesion strength.

The diffusion kinetics of adhesion bond formation are given by 15 f = 5.5 x V x [(2p1 / M1) 2 / 3Dj1 / 2 + (2p2 / M2) 2 / 3D21 / 2] x ft xt (1'p, / 2, / 6 / where f is the adhesion strength at time t = t, V is the frequency domain, p is the density, M is the molecular weight, D is the diffusion constant, ft is the adhesion bond separation rate, β is constant (often β «1/2). increases as contact time 20 increases, molecular weight decreases, and test rate increases Diffusion can occur only in the presence of contacts Adhesive bond formation can occur in two steps, the first step containing wetting to obtain an interface contact, and the second step containing interdiffusion 25 to form a diffusion interface. it can be clearly demonstrated that adhesion strength continues to increase after the formation of a complete interface contact.

30 A further chemical: adhesion may be added to the group of observed partial or rin-coagulation processes that affect adhesion binding. The bond energy of a chemical bond is typically about 80 kcal / mol, while the van der Waals attraction is only 2.5 kcal / mol. It can be experimentally shown that the strength of the adhesive bond can be increased 35-fold by the effect of the chemical bond.

Chemically bonded interfaces include well-known coupling agents based on silanes, titanates, chromium complexes, and functional groups such as amino, carboxyl, hydroxyl, epoxide, isocyanate, and the like. element.

In addition to the polymer / solid contact and wetting step, solidification of the molten polymer in the solid contact and related phenomena are important in the adhesion process of the invention.

Solid surface-induced primary nucleation of spherulites on a well-defined foreign surface is called transcrystallization. The proximity of many nucleation sites on the foreign surface prevents lateral growth of spherulites, whereby crystallization can occur only in the normal direction of the nucleating surface. The formation of such a transcrystalline surface layer naturally promotes foreign surface / poly-15 marine adhesion and, accordingly, the strength of the entire composite. In this context, the factors controlling the transcrystallization process of polypropylene will be considered in more detail, with reference to the results of critical experimental studies (Goldfarb: / 2 /).

20

The nucleation-free energy of the formation of a rectangular heterogeneous embryo is AGn = -ablAgf + 2bly + 2abye + alAo, where / 7 /

a, b and 1 are rectangular dimensions, Agf is the free energy of melting per unit volume, γ and ye are the surface:: free energies per unit surface for b1 and ab levels, AG

is the total free energy of nucleation and Δσ is the energy diffraction function Δσ = γ «+ ycm - yms, where / 8/30 ycs is the free energy per unit area of the crystal / substrate, Ycm is the free energy of the crystal / molten surface per unit area. and Yms is the free energy per unit area of the molten substrate interface.

In the case of primary nucleation, the magnitude of the free energy gap is obtained by differentiating the equation / 7 / for the rectangular dimensions and assigning the critical dimensions (a *, b *, 1 *) from the differentials and placing them in the equation / 7 /, i.e. ÄGn * = 16 x Δσ x oe x σ x Tm2 / (AHf x ΔΤ x pc) where / 9/10 106566 the free energy of melting is replaced by declaring the melting entropy with a temperature independent term for the material, with a density ps, Tm being the melting point of the polymer and ΔΤ being the degree of sub-cooling You).

5 The critical variables for a given polymer are thus the variables ΔΤ and Δσ. The effect of the degree of supercooling is obtained by varying the crystallization temperature and varying the free energy of the substrate surface by varying the nucleating medium.

According to measurements, crystalline and amorphous surfaces produce almost identical nucleation densities, indicating that the energy diffraction is the same on the substrate surfaces used in the study. This is in contrast to early results which show that different substrates have significantly different nucleation activities (e.g. Schonhorn: / 2 /). However, in this study, (unlike others) particular attention has been paid to the equivalence of substrate surface areas and the prevention of substrate poisoning. The nucleation densities of the assay represent the natural nucleation potential of the medium used 20 more than its effective value.

The Fowkes / 2 / model is used in the study to estimate the surface energy values of various substrate components, where only dispersion interactions are assumed to be critical in the hydrocarbon / substrate interaction, i.e.

Yms = Ym + Ys - 2 (Ymd x ysd) 1/2 where / 10 /

• I

Yms is the free energy at the interface of the miscible phases m and s, Ym and ys are the surface tensions of the phases m and s and Ymd and Ysd are the surface stresses due to the dispersive component of the free energy at the interface.

By sliding the component equations / 10 / to / 8 / and: assuming that the components ymd and ycd converge, the energy difference equation Δσ = 2 (yc - Ycd) + 2 (Ysd) 1/2 [(Ymd) ) 1/2 - (Ycd) 1/2] / 11/35 The determinant part of the substrate free energy difference consists of the first, finite, positive constant term, 2 (Yc - Ycd), the second variable term being negligible compared to the first.

n 106566

Since, after repeated thawing and crystallization, certain, identical positions of spherulites are observed, a fixed number of active nucleation sites on the surface of the vessels must be assumed. Since the model corresponding to equation / 7 / assumes a planar nucleation surface of α x 1 units, at least these dimensions are required for nucleation conditions. Any material that prevents contact between the substrate and the polymer melt will prevent spherulitic nucleation. The nucleation site may be destroyed by an impurity component that inhibits the wetting of the interface or changes the critical dimensions of its io level region. On the other hand (in one way or another, "poisoned" medium can produce active nucleation sites by increasing the degree of subcooling, ΔΤ. Equation / 9 / was formed by the critical dimensions of the free energy of the system, Ut:

Ui = Ci x Tm / (AHf x ΔΤ x pc) where / 12 /

The C 1 values were for different dimensions a, 1 and b, respectively: 4γ, 4γβ and 2Δγ.

According to equation / 12 /, magnification of ΔΤ: η reduces the planar dimensions (a, 1) necessary for spherulitic nucleation.

It should also be noted that nucleation densities remained constant over the temperature range of the study, but there were significant differences in nucleation activity at different temperatures. Activity variations were measured as the inverse of the nucleation incubation times, and the results were consistent with the classical rate equation.

30 To summarize the results considered, - transcrystallization is a general phenomenon that occurs on the base. with good contact between tan and polymer melt - the natural activity of the medium is independent of its chemical nature 35 - the Fowkes equation for comparing the activities of the media - the classical rate equation is consistent with the measured nucleation density and incubation time values.

Consider two novel υ 106566 studies of transcrystallization of polypropylenes with different grades of cellulose and graphite fibers related to the new process.

Transcrystallization of polypropylene on various cellulosic fibrous surfaces (cotton, ramie, forisane, rayon, wood 5 fibers) was studied (Gray: / 2 /) by immersing them in thin molten polypropylene film, cooling the film to crystallization temperature (hot table) and observing (photo) transcrystalline crystal growth by polarization microscope. The study showed that preferential nucleation occurs on a natural cellulosic surface, with an unbleached cellulosic surface, apparently due to the presence of hemicellulose and lignin components. The surfaces of regenerated cellulose fibers and mercerized cotton had very poor nucleation surfaces. Various physical and chemical treatments of pin-15 nan did not induce nucleation with regenerated cellulose. There is no evidence for the effect of different crystalline morphologies on the nucleating surfaces, but the large-scale geometric property of the surfaces could control transcrystallization.

20

The study of polypropylene nucleation in two PAN-based graphite fiber grades (Hobbs: / 2 /) is of interest. The poorly nucleating fiber quality consisted of small disoriented graphite cores of about 25 Å and the highly nucleating fiber quality strongly towards the fiber axis. large grained graphite plates over 100 Å in size. The large difference in nucleation capabilities of these graphite grades appears to be due to differences in size and orientation of the graphite levels in their structure. The adsorption of polypropylene directly to the base level of the graphite support can be justified by crystallization of the polypropylene in a monoclinic lattice system, where the molecular chains assume a three-fold helix conformation, as well as molecular orbital calculations showing preferential adsorption of hydrogen on thiothites. The spiral mole chain of polypropylene can be placed on the surface of the graphite lattice so that all hydrogen atoms in contact with the surface are located at the lowest energy points on the surface (i.e., along the c-c bonds).

13 106566

The utilization of different grades of cellulose fibers in nonwoven products made by thermal bonding of gauze webs is reviewed by technical publications.

The process according to U.S. Patent No. 3,507,943 / 1970, / 3 is an early, but very widespread, innovation in the field of thermosetting of production fiber webs. The method involves thermo-bonding with a pair of rolls having one or both rolls engraved and heated to the required temperature. The process comprises, in addition to conventional thermosetting of fibrous webs, impregnation, lamination, opening, folding, etc. in the manufacture of nonwoven products. Thermosetting gauzes usually contain a certain amount of binding thermoplastic fibers 15 (polypropylene) and absorbent fibers (0-75% cotton, wood fiber) for absorbent wiping. Laminates are utilized as substrate materials e.g. nonwoven and woven products, organic film, paper, tape, etc.

The innovation of U.S. Patent No. 3,501,369 / 1970, / 3, includes a nonwoven product and a process for making it. The new nonwoven product with high wet and dry strength values consists of a thermally bonded polypropylene-cellulose fiber web in which the proportion of cellulose fibers is 25-95% by weight. Pulp 25 fibers are either short natural fibers (eg cotton). or synthetic fibers (including rayon). The manufacturing process comprises tearing the fiber mixture, subjecting the gauze to heating (163-204 ° C) and pressure bonding (36-360 kg / m) by hot or cold rolling.

According to the process description, in the product, the polypropylene binder fibers are wrapped around cellulose fibers and, when fused together, give the product a strength, i.e. the bonding of the cellulosic fibers is mainly mechanical. The product has good absorbency for wiping, surgical purposes, etc.

J.P. Moreau / 4 / studied the thermal bonding of polypropylene-cotton blends (20, 30, 50, 75, 100 wt% PP) as a function of temperature on a pair of rolls, one of which was a pattern and the other a smooth roll.

14 106566

The banding speed of the web was 30.5 mm / s and the linear pressure between the roll was 66 kN / m. The weights of the bonded nonwoven fabrics were 40, 60 and 80 g / m2.

Central fiber mixing of cotton and polypropylene 5 proved difficult in the test series. The use of a binder polymer in the form of a film with a cotton gauze resulted in a better polymer-cellulose distribution compared to the fiber blend. The cotton-fiber-polymer film laminate gave better longitudinal and transverse strength values to the corresponding fiber blend product.

The tensile strength, elongation, stiffness and absorbance of the products were measured and the effects of doping level, product surface and temperature on the product properties were determined by statistical analysis. It should be noted that the tensile strength values tabulated in Moreau (/ 4 /, 1990) satisfactorily implement the control equation shown by the thermo-bonding model according to FI patent application No. 961252 / 18.03.96, / 5 /. The gauge thermal bond control equation simulating the results of the publication is obtained with respect to MD tensile strength σ = 5, 476 x 1012 x [PP] 1.131 x exp [1.045 x 10'2 xw] x T2 x exp [-20 36010 / RT], where / 13 / σ, N is the tensile strength of the fabric; [PP], w-% is the polymer content of the fiber mixture; w, g / m2 is the weight of the fabric; T, k is the oil temperature of the roll and E, cal / mol is the dimension of the activation energy.

25 T.F. Gilmore et al., 1992, / 4 / discuss the benefits, use and promotion of cotton in nonwoven products. In this case, thermo-bonding is an economical and important alternative to water-weaving processes which are known to best maintain the favorable textile properties of cotton in 30 products. In this case, in particular, the use of heterophilic bicomponent staple fibers as thermosetting binders provides products with good textile and strength properties. In the experimental part of the publication, a thermal grafting of cotton gauze is carried out using polypropylene-polyester-35 bicomponent fiber (20% by weight) as the bonding fiber. Thermal bonding tests were performed as a function of the linear pressure between the roll and the temperature at a nominal weight of 85 g / m2. Binding fabrics used both duo and trio rolling, with the gauze moving in the outward direction via hot, engraved and hot, is 106566 smooth roll and pre-bonded fabric back through the above hot smooth and unheated elastic roll. As a result of the review, it was found that trio rolling does not offer any significant advantage over dueling. Publication 5 assumes that the binding mechanism is the mechanical attachment or encapsulation of the cotton with polypropylene.

The use of cellulosic fibers in products obtained by hydroentanglement processes is well known. From the very broad state of the art both in these methods and in the products, there are a few examples.

The process and products of U.S. Patent No. 3,485,706 / 1969, / 3 are often regarded as the basic inventor of the production 15 fitting of fluid needling processes. The process utilizes cellulosic fibers either as such or as a blend and laminate with synthetic fibers. The cellulosic fibers used are mainly cotton and rayon fibers as well as short wood pulp fibers in the form of tissue paper. Synthetic fibers are a wide variety of homo and copolymer fibers (mono or bicomponent, continuous filaments or staple fibers) of a wide range (polyester, polyamide, polyacrylic, polyolefin, etc.).

25, U.S. Patent No. 4,442,161 / 1984, / 3. the process produces nonwoven products with improved liquid barrier properties. The method employs more conventionally spaced nozzle sets and a high-low-pressure jet combination. The process utilizes polyester fibers either as continuous filaments or staple fibers, and wood fibers mainly in the form of Harmac paper. Binding between cellulose and synthetic fibers is assumed to be completely mechanical in nature. In the example of the method, the "self-bonding" temperatures of the polyester grades are given, but apparently for the purpose of selecting the drying temperatures of the products.

The process according to U.S. Pat. No. 4,902,564 / 1988, / 3, provides a strong, highly absorbent, finished towel product (100-270 g / m 2) of a fiber blend containing 50-75 wt.% Wood pulp and 25-50 wt.% Synthetic fiber. . In the method, the wet-applied gauze is led to water-nailing. Wood fibers, 3-5 mm in length, are particularly suited for recovery because they are best knit and the products have the best tensile and abrasion resistance and sufficient wet strength. The process utilizes polypropylene, polyamide and polyester fibers as synthetic fibers. The bonding between the fibers is completely mechanical.

The invention according to U.S. Patent No. 5,459,912 / 1993, / 3, includes textured weaving fabric products made from synthetic fibers and wood pulp fibers, as well as a process for making them.

The product fabrics have very low wet and dry particle number counts and good absorption capacity. Minimum particle number values are given as dry, 83 x 10 5 pieces / m3 and wet 6.5 x 10 'pieces / m2, with minimum absorption rates and capacities of 0.1 g / (gs) and 300%, respectively. The amount of wool in the fabric products is 5-50% by weight. Synthetic fibers utilize 20 polyester, polypropylene, polyamide and polyacrylic fibers and combinations thereof.

In the first step of the patented manufacturing process, the gauze web comprising the cellulose and synthetic fiber layers is needled to the fiber side of the fabric (maximum: 75 mesh), at a nozzle pressure range of 6.9-138 bar, with a total jet energy of 50 kJ x N / g. In needling, the fibers of the wood pulp layer are hydraulically entwined with the fibers of the synthetic fiber layer. The pre-blended web obtained in the second step of the process is supported on a wood pulp perforated Ku-30 web having an aperture in the range of 40 to 10 mesh and water-meshed at a total energy of at least 53 kJ * N / g. In needling, the fibers move laterally and vertically from their original positions toward the openings of the pattern member (i.e., wire), whereby the pattern is formed into the product fabric. The web speed in the ve-35 spinning process is at least 18 m / min (range 90-180 m / min). In order to improve the absorption properties of the product fabric, the process is subjected to vacuum dewatering of the fabrics.

The product and methods of U.S. Patent No. 5,459,912 disclose that they do not contain any significant novelty to prior art products or applied hydroentangling technology. The declaration of maximum particle number values for products does not unambiguously indicate the quality of the fabric in terms of cellulosic fiber release, 5 since the fiber emitted by the fabric has both size and weight distribution. Since no correlation is used between the (non-standardized) particle measurement method and other measurement methods (including those based on the weight change of the fabric sample), it is impossible to perform a regulatory comparison of the products of the method with prior art.

In a brief review of the publications related to cellulose-synthetic fiber binding, no comprehensive or comparable method for improving the core adhesion binding of different fibers was found in the novel process. Some of the operating principles of the new control method combination used in the manufacture of nonwoven products are discussed in more detail in the examples below.

Part example 1.

In Example 1, Wide and Low Angle X-ray Scattering (WAXS and SAXS) and heat treatment experiments are considered. structures of the cellulose fibers involved in the control process; and the kinetics of polymorphic changes in cellulose and their effect on fiber structures. The example demonstrates, as a new innovation, an increase in the energy level of the cellulosic fiber surface layer by lattice transformation, raising the degree of crystallinity, and exceeding the critical minimum size of adhesion surfaces, which functions are partially interrelated.

35 The innovation under consideration involves three polymorphic forms of the cellulose crystal structure, i.e., native cellulose, i.e. cellulose I (C-I), which occurs in most natural fibers such as cotton, wood, ramie, flax and various hemp fibers.

is 106566 - hydrate cellulose, i.e. cellulose II (C-II), a form which occurs e.g. in regenerated and mercerized cellulose, high-temperature cellulose, i.e. cellulose IV (C-IV), which can be prepared at elevated temperature, in the presence of polar liquid phase 5 from both native and hydrated cellulose.

Celluloses I and II have a monoclinic crystal lattice shape and differ mainly in lattice constant c and (a / c-) axis angle β. The lattice form of cellulose IV has not been confirmed but has been considered tetragonal or ortho-rhombic. The C-IV and C-I lattice constants of the cellulosic lattices are very close to each other, but the C-IV lattice lacks plane reflection (101). Table 1 shows the lattice constants of said cellulose grades and the relevant plane reflections corresponding to the Mills ler indices calculated from them. In addition to the identification of cellulosic lattice forms based on WAXS scattering, samples were determined at an angle of 2Θ to 10-30 ° based on the sum of scattering intensities, crystallinity degrees. WAXS (and SAXS) measurements were performed on natural cellulosic fibers, crude cellulose fibers, tissue and non-recycled regenerated cellulose fibers and related cellulose membranes to check cellulosic structures. The degree of crystallinity of the cellulose samples was significantly different from that of the regenerated cellulose fiber (C-II lattice: 23 samples), with a significantly lower crystallinity than natural cellulose fibers: cotton: 68-70%, pine, aspen cellulose: 53-65%, xanthate: 35-40%, NMMO-based rayon: 50-55% and carbamate-based rayon: 35-45%.

30

The structural change in the crystal lattice of cellulosic fibers, C-II (C-I) / C-IV, is dependent on a number of factors along with fiber quality. Generally speaking, the lower the crystalline order and the less energy it requires, the more complete the transformation. Thus, regenerated cellulosic fiber (C-II) is easier to restructure than mercerised or untreated natural fibers (C-I).

The ray viscose fiber, when dry up to 300 ° C, is nearly 19,106,666 unchanged in structure, but when treated in liquids at a temperature in the range 140 ° (80 °) to 300 ° C, the degree of C-II / C-IV transformation increases with fluid polarity. In mercerin, cellulose molecules separate from one another by the action of swelling agents, whereby the anhydroglucose molecules are more easily rotated back to the ablate plane during transformation.

The method according to the new innovation has a low degree of C-10 II / C-IV transformation required because the objective is to obtain a thin, high surface energy cellulose IV layer on the fiber surfaces.

For viscose fibers, the CX-IV / C-II concentration ratio of the crystalline phase was measured by WAXS intensity ratios of 15 (including (101) plane reflection intensities) after both glycerine and water autoclave treatment. The equation for simulating intensity ratios with sufficient accuracy (in this context) was given by I (C-IV) / 1 (C-II) = F exp [-E / RT], where / 14/20 of the viscose fibers examined had an activation energy of E = 4676 cal ( mol, the constant F was dependent on the fiber quality. The values of the constant F were obtained for the two xanthate-based fiber grades A-71 and Cs-88, respectively: F = 381.3 and 194.6. F = 213.4.

. The ratio of the scattering intensities of fiber grade A-71 (101) levels to glycerin after heat treatment at 266 ° C was S = 5.05 (equation 14: S = 4.85), which corresponds to a conversion rate of about 90% in the crystalline part of the structure. Thus, the C-IV concentration of the crystalline moiety was 57.6% (the degree of crystallinity before and after heat treatment were 38; and 64%, respectively). Under the same conditions, the fiber grade L-71 has a lower scattering ratio (2.71) but a higher crystallinity (55 and 70%, respectively, before and after treatment), so the C-IV concentrations of the fiber grades do not differ significantly. .

In this context, it should be noted that the effect of heat treatment in a polar fluid is e.g. the crystallinity of cellulose II increases to correspond to the crystallinity of cellulose I 10 106566. When dried dry, the degree of crystallinity of the cellulose structures does not increase. The effect of the heat treatment time on the C-II / C-IV conversion was so low that it did not, e.g. considering the degree of crystallinity error, significantly influence the ratio of intensities. It should be noted that the method used in this context for measuring C-IV / C-II concentrations provides mainly qualitative values because e.g. the degree of crystallinity growth of each crystal system is different as a function of temperature (and time) and the degree of crystallinity, in the rapid measurement method used, is inaccurate.

To examine the C-I / C-IV lattice transformation of the dry natural cotton (C-I) crystal structure, some heat treatment experiments were performed on glycerin (200 ° C / 2h). Heat treatment yielded lower intensity ratios than the C-II transformation discussed above, but a shift of (101) level (CI) scattering density toward higher 20 values and loss of (10) level (CI) scattering density were well apparent from WAXS analysis When the IV lattice was born.

Cellulose lattice C-II is not in the same proportion as the polymorphic form of cellulose as lattice C-I and C-II, but C-IV is less stable and can be considered as a defective and disordered form of cellulose-I. On the other hand, the C-II / C-IV transformation of cellulose undergoes a change in the superficial structure of the cellulose to a more organized lamellar structure, which can be easily detected by low-angle X-ray scattering measurements.

SAXS analysis of both natural (C-I) and regenerated (C-II) cellulosic fibers usually shows monotonically decreasing. intensity (I) / scattering angle (e) function. Thus, in synthetic fiber polymers, the conventional, perpendicular to the fiber direction, periodic lamellar structure is often not detected with cellulosic fibers. The poor formation and visibility of the long identity period on the cellulosic fibers is due to the low density difference between the crystalline regions and, in particular, the arrangement of the channels between the amorphous regions and the microfibrils along the fiber axis (e.g. cotton and the like).

Partially disassembled (e.g., expanded solutions of alkaline solutions) cellulose structures show inflection points and discontinuities, especially when using the Lorenz correction (IeVe function) of the scattering results.

Samples of production fibers were used in the SAXS scattering tests performed. Thus, partly for practical reasons (curling, sample preparation, etc.), the si-10 misalignment result does not represent cases where the radiation level is perpendicular to the direction of the fiber axis, since some of the fibers in the sample are completely misaligned.

The SAXS curves of the native cellulosic fibers exhibited a more or less sharp peak in the IeVe function of both natural and regenerated fibers or plotted at a scattering angle range of e = 17-19 mrad, corresponding to the Bragg period, L (Z) = 45-40 Å. In addition to the above line, the SAXS curve of the regenerated cellulose fiber exhibited a distinct peak, which corresponded to a scattering angle of e = 1.0 ± 0.5 mrad or (L) Z = about 771 Å. For cotton fibers, ha-20 was found to be mild by applying in scattering applications also in the range: e = 9-11 mrad and L (Z) = 86-70 Å.

Cotton and rayon fibers (IS and A-71) were heat treated in a thermostat (200 ° C / 4h) under a nitrogen atmosphere. The heat treatment did not bring the lattice planes to the WAXS scattering angles. significant changes. A slight increase in crystallinity was observed in the samples: IS: 69-71% and A-71: 40-42%. SAXS scattering of dry heat-treated regenerated cellulose fibers showed no significant changes compared to the parent fibers. However, the scattering function of the cotton fiber showed an enhanced intensity, corresponding to a scattering angle, e = 7.5 mrad or L (Z) = 103 Å.

As noted above, at elevated temperatures, the polar liquids cause a significant change in the crystalline structure of the cellulose from C-II and C-I to C-IV and, in particular, a significant increase in the crystallinity of the regenerated fibers. At the same time, there is considerable organization of the cellulose superstructure, as indicated by the sharpening of the intensity peaks of the SAXS scattering curves 22 106566 and the consequent enhancement of the lamellar structure. As the processing temperature increases, the values of the Ie2 / e functions shift towards low scattering angles and the corresponding values of the 'long identity-5 period', L (Z). As the degree of crystallinity of the structure increases at the same time, the increase in lamellar alkalinity means a significant increase in the crystalline lamellar thickness.

The change of the long period as a function of temperature followed the equation-10 in the form L (Z) = - M + Ν / (ύ0-δ) / 15 /

The value of the constant N for rayon fibers was constant within the accuracy of the measurement, i.e. N = 43390 Å / ° C. Similarly, the constant "character" temperature was? 0 or f) 0 = 414.5 ° C. The value of constant M was a function of fiber quality (also with cotton fibers). The xanthate based ribbon fiber A-71 had a constant value, M = 110.2 Å. The exemplary heat conditions had a Lorenz-corrected long period length: L (Z), equation measurement / ° C: 182.0-181.4 / 266, 144.3-140.2 / 244, 94.0-102.0 / 202 and 44.5-42.8 / 134.

As an example, the M values obtained for three other xanthate-based fibers are 120.9 / Lnz, 145.4 / Cs-88 and 110.8 / Cs-75. NMMO solvent-based rayon fiber, L-71 had a constant M value, M = 150.2 Å, i.e., long-term values were significantly lower than fiber A-71.

25th As a general result of SAXS analyzes, in particular by adjusting the annealing temperature (with less importance of annealing time) in the polar fluid, the crystalline lamellar thickness of the cellulose can be adjusted, whereby critical dimensions of the nucleation levels of heterogeneous cellulose surface can be exceeded.

* Part example 2.

35 In Part Example 2, as a new process, the wettability of cellulosic surfaces with molten polypropylene, the spread of contact melt, and the kinetics of spread are considered. A high degree of adhesion between the cellulosic surface and the polypropylene is a prerequisite for the formation of a sufficient contact surface.

23 106566 in a reasonably short period that is technically easy to implement. These requirements, on the other hand, require sufficient wetting between the cellulosic surface and the polymer melt, spreading the melt sufficiently on the contact surface, and correspondingly, upon solidification of the polymer melt, the formation of an epitaxial "grain boundary" (transcrystallization).

In this context, the amount of poorly known surface energies of the various structural forms of solid cellulose surfaces, and the high polarity of the cellulose, play an important role in the quality of the energies, so measurements are mainly focused on finding out.

The driving force for the spontaneous, fluid distribution of a liquid to a solid surface is the unbalanced interface forces, i.e., 15 fd * Ysv - Ysl - Ylv cosO, where / 16 / fd is the driving force affecting the unit length of the liquid front,

Ysv is the solid surface tension with the saturated vapor of the liquid, ysl is the solid-liquid interface tension, YLV is the surface tension of the liquid and Θ is the instantaneous contact velocity.

Applying the equilibrium equation to / 16 / Young gives / 1,12 /: fd = Ylv (cos0e - cos0), where / 17 / 0e is the edge angle corresponding to the equilibrium state.

25 Not composed of polar and polar components. due to the additivity of intermolecular energies, the formation of boundary surface energy (ysl) gives the equation Ysl = Ysv + Ylv ~ 4 (ysd * yLd) / (Ysd + YLd) -4 (YsP + YLp) / (YsP + YlP), / 18 / where applying the Tonng equation gives 30 Ylv (1 + COS0) = 4 (ysd · YLd) / (Ysd + YLd) + 4 (Ysp · Ylp) / (Ysp + YLP), / 19 / where Ysd, YLd and γ3ρ, ylp are the dispersive and polar components of solid and liquid surface tensions.

In this context, the aforementioned harmonic mean-35 power (/ 19 /: partially empirical: S. Wu) is used to combine the dispersion and polar forces of the solid and liquid phases, since the cellulosic surface is highly polar and the conventional geometric mean is thus unsuitable for processing.

Very useful is the empirical dimensionality, i.e., critical surface tension of solid surface wetting, yc, developed by Fox and Zisman / 12/106566. It was observed that the function given by the homologous series of fluids on the solid support: cos0 / yLV is generally straight, which, when extrapolated to cos0 = 1, gives 5 specific yLV surface stresses, i.e. the aforementioned critical stress, yc. Thus, liquids with a lower surface tension than yc are spread on the solid surface.

In the case study, glycerin, formamide, methylene iodide, tetrabromoethane, α-bromo and α-chloronaphthalene, the first two of which are highly polar, were used as organic liquids in the surface energy ratio measurements of the cellulose. The surface tensions of the liquids and their dispersive and polar components corresponded to values of known literature (Wu, Toussaint-Luner: / 12 /).

The regenerated cellulose fibers used in the studies were based on xanthogen and N-methylmorpholine oxide (types A71 and L-71) as well as refined cotton. Some of the fibers studied were heat treated in polar fluids. The pulp-20 loose fibers were conventional, commercial grades from which avivants were extracted. The heat-treated fibers were cleaned from their surfaces by ethanol-ether leaching. Dynamic edge angle measurements of the fibers were performed using the above liquids on a Cahn DCA-322 analyzer.

25th From the angles measured in non-polar fluids, the PV of cellulosic fiber grades A-71 and L-71 and natural cotton fibers were obtained as the critical surface energy, respectively: yc, MJ / m2: 33.5 and 39.5 and 39.8. The dispersion of the measured values was noticeable, but its effect on the critical surface energy values is not significant, however. The measured values correspond to a var; You very well have literary values.

* The measured values for both regenerated cellulose (CI structure) and hemicellulose are numerical and also compatible with cellulose grade A-71 for the cos0-ecst-35 rapolization lines (Luner et al .: woodcast, Avicel: yc = 35.5, cotton-cast) : 41.5, SW-Xylan: yc = 35, etc.). The critical surface energy values for cotton and wood fibers (C-I structure) vary in the literature according to the polarity values of the measuring solutions used. Douglas dust fibers are given a value of (Nguyen et al.), Measured in polar fluids, yc = 52.9 and non-polar fluids, yc = 39.3. For the γ-components of cotton (Westerlind et al.), A value of yc = 38.6 mJ / m2 is obtained for non-polar fluids.

As a result of heat treatment in polar fluids (glycerin, water), the critical surface energy values (not measured in polar fluids) of the test series A-71 and L-71 significantly increased: yc, MJ / m2 / y, ° C: 10 A-71: (CH2 2CH (OH) 3: 33.5 / 21, 37.5 / 200, 37.0 / 202, 39.5 / 222, 44.1 / 244 and H 2 O: 37.8 / 145 L-71: (CH 2 ) 2CH (OH) 3: 39.5 / 21, 43, 1/202, 41, 6/222, 44.2 / 244 and H 2 O: 39, 7/145

While critical surface tension should be considered from the foregoing review, it is apparent from the test series that the surface energy of the cellulosic fibrous surface is increased by heat treatment in polar liquids, with the amount of growth decreasing as the degree of crystallinity of the parent fiber increases. Thus, the critical surface energy of the regenerated cellulosic fiber due to the transformation of the lattice-20 by heat treatment approaches the corresponding values of the natural fibers.

When not performing critical surface energy determinations on polar fluids, it was found that by applying the Wun harmonic method, only a part of the obtained surface energy component values fit the corresponding literature results. For comparison, Table 2 shows some calculated ysd and Ysp values for the cellulosic surface. From the results 30, it is found that the dispersive component of surface energy is approximately equivalent to literature values. The polar surface energy component of • the samples under examination is, except for cotton, • lower than normal. Low values apparently result from the presence (or addition) of polarity-affecting impurity components on the surfaces of the technical cellulosic fibers (also natural cellulosic surfaces often have hemicellulose or lignin residues). Some surface energy values obtained with alkyl ketene dimer coated cellulose films are listed in Table 2 (Toussaint 26 106566 et al ./12/: 1.6-2.1-2.4 µg AKD: surface hydroxyl groups replaced with AKDs up to 36 l) , which show a sharp decrease in the polar energy component as a function of the surface "degree of coverage", with the dispersive component 5 remaining approximately constant.

Mention should also be made in the polypropylene melt / cellulose system, in Table 2, of the values of the driving force (fd) and the adhesion work (Wa) (mJ / m2): fd-Wa / fiber: 6.15-48.9 / PV-1.5, 58-48.3 / A-71-LK-200 ° C, 9, 23-52, 0 / A-71-LKA-10 145C, and 11.7-54.2 / A-71-LK-244 ° C. .

Surface energy measurement results generally indicate that, except for cotton, the surface energy values of cellulose surfaces and polypropylene feathers are so close that the effect of the impurity components needs to be monitored for surface energy measurements. In the technical field, cellulose impurities or additions can be monitored and utilized in process control.

In addition to clarifying surface energy ratios, the exemplary aspect of the present invention is the rate of dispersion of a polyolefin melt on cellulosic surfaces, which is essential for the realization and control of the adhesion process.

Polymer dispersion measurements were made by si-25 milligrams of polyolefin on: various types of cellulosic surfaces (regenerated, inoculated cellulose membranes, and thin cellulose extrudates of natural cellulose), melting the polymer, and transferring it to the desired temperature with thermostatic control. The melt droplet propagation was recorded as a function of time and temperature with a CCD camera, the information was transferred to magnetic tape, and the recordings were measured by image analytical techniques. The edge angle change of the solidifying melt and the final edge angle with the polymer in the solid state were also measured for the 35 controls using an edge angle analyzer.

Kinetic analysis of polymer dispersion was carried out as described in [1,12] below.

By combining the equations of spontaneous spreading of the liquid on the solid surface with the retardation force of 27 106566 due to the viscosity of the liquid, the equation of change in the wetting angle of the system at c-sin can produce: equilibrium edge angle, yL is the surface energy of the liquid, η is the viscosity of the 5 fluids, and L is the scaling length.

In the integrated form, equation / 20 / thus l-cos0 / cos0e = ax exp [-ct] where / 21 / c = Yi / ti * L and a = l-cos0o / cos0e and 0O is the edge angle at the point of departure (t = 0).

According to Equation / 21 /, the rate reaction of the change in the angular cosine is directly proportional to the surface tension of the wetting polymer melt and inversely proportional to its low shear rate viscosity. The temperature dependence of the surface tension of the polymer is low, so that the thermal dependence of the velocity factor under consideration is mainly determined by the Akti butter energy (PP: E ~ 8000 cal / mol) of the viscosity of the polymer melt. The surface tension of the polymer is only slightly dependent on its molecular weight, except for its low values (Mn <5000). The effect of molecular weight on the viscosity of the polymer melt is so-called. above the critical molecular weight (PP: M „, c ~ 5000) is quite remarkable. In the low shear range (D = Is'1), the viscosity of the polypropylene melt can be described by η = Ma3'49 x 4.720 x 10'20 x exp [8000 / RT], Pa-s / 22/25 By adjusting the surface energy of the polymer (additives) -: To a limited extent, affects the rate of its spread on a solid surface. By adjusting the viscosity of the polymer, the rate of solid surface wetting can be significantly reduced by lowering the weight average molecular weight of the wetting polymer, Mole-30, while utilizing a decrease in the melting point of the polymer (14). In practical technology I, the degradation of the molecular chains of the surface layer of polyolefin fibers can be accomplished in conjunction with fiber spinning by melt spinning oxidation / 15 /.

35

The spread of the polymer melt on the surface of the solid may be determined by many solid structural factors or by the presence of natural or added chemical impurities (lignins, hemicellulose, finishing agents, etc.) on the surface as well as mechanical barriers to the solid surface.

The kinetic measurements of this sub-example specifically examined the behavior of conventional, mostly impure, cellulose surfaces in connection with the spreading of molten polypropylene droplets. No primary or secondary edge films that prevent droplet propagation were detected in the measurements. The observations did not look for equilibrium edge angles, mainly due to film impurities and unevenness, but the edge angle (0e) was taken as the angle at which d0 / dt 10 appeared to be constant. For the necessary practical values, the procedure cannot be significantly incorrect.

Some of the results of the spreading experiments are noted in Table 3. The membranes no. 1 and no. 2 in the table are C-II membranes based on cellulose carbamate. Nitrogen concentrations in the membranes are 1.6 and 0.18 l, respectively. The nitrogen is present as an isocyanic acid additive in the 6-carbon of cellulose (CH 2 O-C H 2: 16). Membrane no. 3 is a C-II membrane based on cellulose xanthogenate. Samples no. 14 and 22 in the table are fine and unbleached fine cellulose fiber (C-I structure) as a cellulose sample.

The MWD analyzes of the polypropylene grades treated in the kinetic studies are as shown in the table below. The table also shows the viscosities according to equation / 22 / at 180 ° C. The table shows the relative velocity constant values for the wetting rate constant of the viscous cellulose fiber (no. 14) of Table 3, which is the viscosity value: and the time required to reach the θ value, the rate equation / 21 /.

The sample pairs no. 9 and no. 3 in Table 3 differ primarily in the molecular weight distribution of the polypropylene melt. Their velocity constants, C (3) / C (9) = 3.24, should thus be inversely proportional to the corresponding viscosities. The following table gives a viscosity ratio, η (22) / η (21) = 4.65, so sufficient agreement with respect to velocity constants and viscosities is obtained.

29 106566 Sample MFR MWD "" "η" C t (? 0) g / 10 min M „- D Pa * s min" 1 s PFTI - Ί5ϋ - 1244 5ϋ ~ - 37 S3 - Ζϋ7 ---- 52- PP 211 Μϋ 98410 - 4.44 51 2,269 Π ΤΓΎ2 ---- 193300 - 5.53--9S0--57715 - ΊΜ— 5 Tm-- £ 74--407500 '- 7.00 - Γ757Ί5 --ÖTTTTS - Γ577— Λ ”ΡΡ" '24 --- = - 5ϋϋϋΌ - Μ - 73 - Γ71- MFR: ASTMD 1238 ίο Note that according to Table 3, the wetting angles of sample pairs no. 3 and no. ratios of change velocities (at Θ = 70 °) to the time needed to reach the edge angle are 4.48 and 4.14, respectively.

According to the results of Table 3, the wetting rate of the bleached cellulosic fiber (# 1514) is slightly higher than that of the unbleached (# 12). In the accompanying table, a change in velocity coefficient corresponding to bleached cellulosic fiber (C-I structure) is calculated as the wetting polymer changes in weight average molecular weight and melt viscosity values, respectively, to lower and higher values for the reference 20 polymer. The surface layers of peripherally oxidized polymeric fibers have a molar weight of / 15 / in the range, M „= 500,000 to <10,000. Thus, by adjusting the molecular weights * 25 of conventional technical polymers or spun-oxidised fibers, the rate, amount and wetting times of wetting between the polypropylene melt and cellulose can be adjusted over a very technically feasible range. From the results of Table 3 it can be further stated that the carbamate nitrogen content of the sample membranes (1 and 2) has a lower effect on the wetting rate constants, i.e., xanthogenate-based membrane (3) under nitrogen and air: N2: 0.00 N / no 15/0 (15) - 0.18 N / no 16 / 0.63 x C (15) - 1.60 N / no 3 / 0.41 x C (15) 35 Air: 0.00 N / no 6 / 0 (6) - 0.18 N / no 5 / 0.84 x C (6) - 1.60 N / no 4 / 0.79 x C (6)

In the atmospheric atmosphere, the wetting rate constants are reduced relative to the nitrogen atmosphere in all series of experiments. Another notable effect of the atmospheric air 106566 is the almost complete elimination of the rate-reducing effect of the structural nitrogen of the film (the surface impurity component oxidizes and evaporates, the film surface oxidizes, etc.). Under the influence of oxygen 5, the value of the equilibrium edge angle is also reduced in the test series samples. Effect of both structural nitrogen of the films and atmospheric oxygen on the wetting rate due to changes in surface energy components. Adjustment of the surface energy values can thus influence the kinetic properties of the wetting but apparently to a lesser extent than the viscosity control of the polymer melt.

It should also be noted that after wetting measurements, upon cooling of the contact samples, a solidification temperature of up to 30 ° C above the usual solidification temperature (~ 110-115 ° C) could be observed, and the degree of supercooling of the polymer melt decreased accordingly. This is a consequence of the heterogeneous nucleation of the polymer melt on the cellulosic surface. It is also noteworthy that this nucleating effect of cellulose 20 decreased as the molecular weight of the polymer increased; for example, the polymer PP 23 in the accompanying table had a melt solidification temperature (air atm) of 113 ° C, a polymer PP 22 (N 2) of 133 ° C, and a polymer PP 21 (N 2, no 3) of 142 ° C.

25 Part Example 3.

In Example Example 3, the thermal bonding of fiber mixtures made from different grades of regenerated cellulose fibers, cotton fibers and conventional and skin-core polypropylene fibers is discussed in order to clarify the key inter-fiber bonding effects.

! The devices and their functions used in the fabrication of fabrics and fibers corresponding to Examples 3 and 4, the methods of performing, following and adjusting the thermosetting, hydroentangling and spinning oxidation processes are described in detail in EP 95663 (EP 0 667). 406 A1) and FI 101087 (EP 0 799 922 A1) and in FI patent applications Nos. 953288/030795 (EP 0 753 606 A2) and 974169/071197.

31 106566

For the examination of the binding results of the test fabrics, a binding equation (FI 101087) which simulates the measurement results in the form: Φ = cx T2 x exp [-E / RT], where / 23/5 Φ T is the absolute temperature, c is a function of the speed and weight of the gauze web, the tensile ratio of fiber manufacture, the fiber orientation of the polymer polymer and the molecular weight distribution, the proportion of binding fibers in the fiber mixture, etc.

The binding equation is also well suited for use in the temperature range of fabrics (i.e., bonding maxima, 6m, above the corresponding temperature, TB, where the amount of binder polymer is high melting).

15

The first set of tests (A) corresponding to Example Example 3 was made using a spot patterned and smooth pair of steel rolls. The results of the test series using the binding equations are shown in Table 4 and Figure 1. The properties of the fibers corresponding to the test series are shown in Table 6.

In test series (A), two different grades of rayon viscose grades (R1 and R2), one based on cellulose xanthogenate and one recovered from NMMO solution, and purified cotton fiber (PV, structure C-I) were used to prepare the binding series. Three different types of polypropylene fibers (PP-5, -1 and -8) were used for the binding, of which PP-5 was a conventional, homogeneous polypropylene fiber and the others were skin-core (PP-8 highly peripheral oxidized fiber). In addition to fiber blends, the results also include binding results for the polypropylene fiber components alone. The binder fiber content of the blends was 50% by weight.

When conventional polypropylene fibers are used, the bonding strengths of the fiber blends corresponding to each of the rayon fibers are approximately the same on both sides of the temperatures. The activation energies of the binding-35 processes in the thermal states below Tm are equal to each other and quite close to the activation energy of the binding of the polypropylene fiber component alone. In the high temperature range, the activation energy for bonding rayon fiber alloys drops significantly below the activation energy of polypropylene bonding 32 106566, while indicating the involvement of cellulosic fibers in the binding process. The skin-core polypropylene fiber, PP-1, in the respective fiber blends have the same binding activation energies in the temperature range, T <Tm, with cellulosic fiber blends (R1, R3 and PV) and close to the binding activation energies of the PP-1 component. gia-value. The bonding strengths of the alloys are also close together. The temperature corresponding to the maximum bonding strength of the Raion cellulose blends (TJ rises well above the temperature corresponding to the binding fiber while the cotton blend behaves in the opposite way. In the high temperature range,

The bond strength ratios [(R1 + PP) / PP] were for polypropylene fiber, respectively: PP-5: S = 8.16 x 105 x exp [-12000 / RT] PP-1: S = 4.81 x 102 x exp [- 6060 / RT] PP-8: S = 0.453 At 162 ° C, the ratios from the equations: 0.375 / PP-5, 0.434 / PP-1 and 0.453 / PP-8 indicate the order of the participants involved in cellulose binding (low at temperatures the order is approximately the opposite).

25 Peripheral Oxidized Fiber Quality (PP-8) is very similar to the melt qualities obtained with the other properties of the process according to FI Application No. 974169 (Part Example 1.5, pp. 37-39).

30 It should be noted that, due to the low total surface area of binding, the low contact surface of the individual binding site, and the short delay times of the binding 1, the point bonding method used in the experiments provides low final strength for both rayon and cotton glass blends. : infection). However, spot-binding experiments show the central dependence of the main binding agents, the proprietary bonding system of polypropylene fibers and the cellulosic alloy bonding system, both on the location of maximum bond strength values and on activation energies.

33 106566

The second set of test runs (B) corresponding to part example 3 was performed using a pair of rolls of cotton and steel rolls. The results of the test series are shown in Table 5 and Figure 2. The properties of the fiber qualities corresponding to the test series are given in Table 6.

5 The results of test series (B) lack the results corresponding to the polypropylene components alone, since the cotton-steel-Vals system uses polypropylene film as the binding result for the polypropylene gauze. The temperatures in the test series (A) and (B) do not match. The temperature of the unheated cotton roll during the bonding rises to about 80 ± 5 ° C, so to bring the amount of bonding required to the system, the steel roller temperature is raised to about 25 ° C above the normal steel roller temperatures. The series (A) has a temperature gradient between the rollers of about 5 ° C, but the series (B) has a temperature gradient of about 90 ° C.

In test series B, two grades of ray viscose (R2 and R4), one based on xanthogenate and one based on NMMO solution, and two grades of polypropylene (PP-3 and PP-6), one of which was skin-core, type and another (PP-6) conventional homogeneous fiber.

From both the results in Table 5 and Figure 2, it can be seen that in the low temperature range (T <TJ bond strengths are approximately equal for the three blends, the other for one fiber blend (R2 / PP-3), the bond strengths are significantly higher. 25 types of polypropylene fiber, PP-3, low temperature range (T <TJ and strength increase continues to higher temperatures than conventional homogeneous fiber.

When performing cellulose leaching from product fabrics with phosphoric acid, it can be noted that at low temperatures, leaching does not appreciably affect the strength of R / PP-6 and R4 / PP-3 nonwovens, so that strength is mainly provided by the central bonding of polypropylene fibers.

Leaching of the cellulose component of the nonwoven fabric, R2 / PP-3, significantly reduces the fabric strength at both low and high bonding temperatures, indicating that cellulose is involved in fiber bonding along with polypropylene. At high binding temperatures, the binding result of the fiber mixture R4 / PP-4 also indicates the involvement of cellulose in the binding. In the high temperature range, the activation energy term for the bonding equation 34 106566 of said alloy 34 has a negative sign, i.e., the bonding strength is further increased above the Tm temperature. This effect is removed from the results after the phosphoric acid solution.

One of the reasons for the binding activity of the cellulose component of the R4 / PP-3 mixture is the cellulose IV structure on the surface layer of the cellulose fiber, R4, which is well visible in WAXS analysis. It should also be noted that when bonded with a cotton roll system, the bonding surface is quite large and that, due to the plastic bonding needle, the polypropylene particle melt spreads easily around the fiber, each of which contributes its own to the final product.

Part example 4.

15

In Example Example 4, the improvement and regulation of cellulose fiber adhesion by high-power corona treatment is discussed.

Improvement of adhesion between cellulosic fibers is essential, especially when the higher basis weight water-woven nonwoven non-woven synthetic polymer binding fibers are cellulose-inert polyester, polyamide or the like. Pre-mixing of the polyolefin microfiber with cellulose and after the needling process can then be utilized to prevent cellulose dust from loosening. the cellulose-polyolefin contact melt-wetting transcrystallization process. Thus, the improvement of cellulose-cellulose adhesion also promotes the formation of a pre-contact with the cellulose-polyolefin mixture. Said combined process can advantageously be utilized in the manufacture of absorbent and, at the same time, mechanically strong nonwoven laminate fabrics.

35 pilot-scale corona equipment (Sherman High Frequency cy Generator: 20 + 5 kHz, D-2 kW) was used to study cellulose fiber adhesion. Cellulose dust release studies were performed using a Gelbo Flex Test (5000 ES) (EDANA 220.0-96: Linting tendency).

106566 In this context, consideration is given to cellulose fiber adhesion in a conventional water-woven polyester-wood pulp non-woven fabric (50 wt% PES; 70 g / m 2), wherein the cellulose fiber format was hydroentangled for 5 polyester webs. The product had a high degree of mixing of the components, but the amount of cellulose dust removal varied on different sides of the fabric (A and B sides).

For the basic reference series, the starting fabric was treated exclusively with the SHFG as a function of power. Cellulose dust particle numbers removed from product lane 10 received (N) /

Cu * ft) increased slightly as a function of electrical work on the fabric (W, wh / m2), i.e. N (A) = 1010 + 143W and N (B) = 3635 + 98W.

To demonstrate the effect of corona treatment, the amount of dust discharged from the source fabric was increased by moistening the fabric with saturated water vapor and drying by hot rolling (115 ° C, 0.1-40 kN / m.). Dust values were set to N (A) = 37867- (4183-5748) W and N (B) = 20328- (1857-2713) W, where the 'duty factor' values in parentheses correspond to the maximum and minimum values obtained.

Similarly, the lower dust values of the starting fabrics behaved in the above-mentioned manner when treated.

According to the test results, the corona, wetting and drying treatment can be used to increase the cellulose-cellulose fiber adhesion very efficiently, and even with a low electrical workload on the fabric, the amount of finely divided cellulose dust exiting the fabric can be practically reduced; looking at zero.

The size distribution of the cellulosic dust emitted by the test fabrics appeared to be almost constant and also dust-independent, with a minimum size of d = 0.5 µm for 5 minutes. In contrast, the dust size distributions taken as minute averages of the test series showed quite a significant difference from the sum distribution, with the percentage difference as a function of 36 106566 decreasing as the particle size increased. With a particle size in the range of 0.3-0.5 µm, the aforementioned percentage difference over time turned out to be the opposite of the other particle size classes, indicating the special importance of large dust classes below 0.5 µm in the distribution system. It is particularly noteworthy that the corona-treated fabric dust sizes did not exhibit the aforementioned percentage dispersion in different size classes as a function of the tester (which also contributes to the effect of the treatment on the dust size distributions).

10

When evaluating the adhesion results, it should be noted that the amount of dust is clearly a function of the mechanical bending and cutting work performed on the fabric (further processing, etc.), so that the actual dusting result is not the same as the test result. There is also a notable decrease in the degree of crystallinity of cellulose as well as its surface energy due to electrical work, which may decrease the wettability of the polyolefin-cellulose contact and. transcrystallization using the corresponding sub-method in addition to the corona treatment method.

As a result, the absolute efficiency of the applied wetting-pressure-drying method and its wide range of adjustment and application can be observed from the test series.

The method description has demonstrated the implementation of a new combined control-25 method for both fibers and fabrics.

It should be noted that the method of adjusting the central adhesion of fibers according to the invention can be varied in many ways, while still remaining within the scope indicated by the examples and claims.

30 The phenomena related to the control method have been attempted both in the description of the prior art and in the examples by means of theorizing! da to provide a scientific picture of the method according to the new invention. However, it is self-evident that not all phenomena related to the method have been explained, either because of their unknown nature or due to the lack of sufficient techno-scientific measurements, and the criteria given in the explanation of the new method cannot be relied solely on.

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Makromol. Chem. 181, 1980, 1752-1762; 179, 1978, 2297-2303 H. Schonhorn, F.W. Ryan; J. Polym. Sci., A2, 6, 1968, 231-240; 7, 105-111, 1969

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Claims (10)

A method for improving and adjusting the adhesive strength of cellulose or cellulose synthesis fiber mixtures, in particular polyolefin fiber mixtures, in a method of manufacturing nonwoven fabric products, wherein bonding of webs and / or webs of said fibers and / or characterized in that: a. the cellulose fiber is heat treated in an elevated temperature in a polar, cellulose-insoluble liquid; 15b. the molecular chain surface layer of the synthetic fiber surface layer used for cellulose binding is reduced by adjusting the fiber surface during melt spinning, the web (s) formed from the fibers or alloys of the fibers treated in accordance with (a) and / or (b) above are bonded by a thermo-bonding and / or hydroentangling process; 25 d. the number of cellulose / synthesis fiber contacts is increased and at the same time the separation of short cellulosic fibers from the surfaces of nonwoven laminates and alloy fabrics is prevented by applying a Corona steam wetting pressure drying to the resulting fabric. 30 Process according to Claim 1, characterized in that the polar liquid is an organic liquid containing OH groups, in particular water in equilibrium with its saturated vapor, at a temperature in the range of 100-250 ° C. 35 Method according to Claim 1, characterized in that the cellulosic material is heat-treated in a polar liquid such that at least the surface layer of the cellulosic fibrous material has a crystallinity of 48 106566 corresponding to a degree of crystallinity of natural cellulose, 60-75%. Method according to Claim 1, characterized in that the cellulosic fibrous material is heat-treated in a polar liquid such that at least the value of the long-term iderity period of the surface layer of the cellulosic material material is at least 50 Å. The process according to claim 1, characterized in that the amount of molecular chain degradation in the surface layer of the polyolefin fiber used as the synthetic fiber corresponds to an average degree of polymerization of the product of 1000, i.e. an average molecular weight of polypropylene of about 42,000. The process according to claim 1, characterized in that the weight average molecular weight of the polyolefin used as the synthetic fiber is reduced by melt spinning of the fiber to a value where the viscosity of the polymer at 170 ° C is between 1300-5 Pa * s with a shear rate of less than 1 s. A process according to claim 1, characterized in that the melting point of the surface layer of the polyolefin fiber used as the synthetic fiber corresponds to an average degree of polymerization 1000 resulting from the degradation of the molecular chains produced by spinning oxidation. Process according to Claim 1, characterized in that the surface energy of the surface layer of the polyolefin fiber 30 used as the synthetic fiber corresponds to the number average molecular weight obtained by the degradation of spun oxidation molecular chains with average polymerization degree and dispersion values of 1000 and 3-8, respectively. mJ / m2 at 170 ° C. The method according to claim 1, characterized in that 106566 49 a. In thermosetting fiber blends, besides the binding polyolefin fiber, is rayon viscose as a cellulosic fiber or blend, cotton, long natural cellulosic fiber, wood fiber 5b. , amide and / or polyolefin fiber, short wood pulp fiber alone or in combination with short polyolefin staple or microfibre, rayon fiber alone or in combination with wood pulp fibers and polyolefin fibers. A method according to claim 1, characterized in that, after bonding, an electrical workload of 2 to 12 Wh / m2 is applied to each surface of the nonwoven product at least at a periodic frequency of 20 ± 5 kHz with oxidizing corona equipment. The method of claim 1, characterized in that after bonding, both surfaces of the dry nonwoven product are wetted with corona oxidation and machining with saturated water vapor at a temperature in the range of 100-110 ° C. Method according to Claim 1, characterized in that the nonwoven product is dried after corona working and steam wetting at a temperature of 100-160 ° C at a linear pressure of 0.1-40 kN / m with gentle loading. Patentkrav 106566 50