CN117758383A - Colored regenerated cellulose fiber filament and colored resin matrix composite material - Google Patents
Colored regenerated cellulose fiber filament and colored resin matrix composite material Download PDFInfo
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- CN117758383A CN117758383A CN202311870033.7A CN202311870033A CN117758383A CN 117758383 A CN117758383 A CN 117758383A CN 202311870033 A CN202311870033 A CN 202311870033A CN 117758383 A CN117758383 A CN 117758383A
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Abstract
The invention provides a colored regenerated cellulose fiber filament suitable for being used as a reinforcing phase of a resin-based composite material and a colored resin-based composite material prepared from the colored regenerated cellulose fiber filament. The regenerated cellulose fiber filaments are dyed by dye, the twist of the regenerated cellulose fiber filaments is 0-100 twists/meter, and the linear density is 550dtex-50000dtex; the colored resin matrix composite comprises a continuous phase and a reinforcing phase, wherein the reinforcing phase is a regenerated cellulose fiber fabric, and the regenerated cellulose fiber fabric contains the colored regenerated cellulose fiber filaments. The colored cellulose fiber filament can enable the composite material to have excellent appearance effect and good mechanical property, the filament itself has color, the filament can be used for producing the colored composite material without additional treatment, and the texture and special gloss of the fabric can be displayed on the composite material while the color of the composite material is enriched.
Description
Technical Field
The invention relates to the field of fiber manufacturing, in particular to a colored regenerated cellulose fiber filament suitable for preparing a colored composite material, a colored resin matrix composite material and a preparation method thereof.
Background
The composite material is a novel material formed by molding two or more different materials through a composite process technology. The preparation method not only can keep the main characteristics of the original material, but also can obtain the properties which the original components do not have through the composite effect. Composite materials are now widely used in many fields of industrial manufacturing, aerospace, automotive, wind power, sports and leisure, construction, etc., and will also continuously serve the production activities of humans.
The resin-based composite material is a composite material which takes resin as a continuous phase and high-strength fibers as a reinforcing phase, is the type of the composite material which is industrialized by human forefront, and the reinforcing fibers mainly comprise glass fibers, carbon fibers, aramid fibers and the like. With the increasingly wide application of resin matrix composite materials, users have put higher demands on appearance conditions such as color or texture of the composite materials. For resin-based composite materials, the material obtained by dyeing the resin has single appearance color, and is difficult to show patterns or textures on the surface of the material, so that in order to make the composite material have good appearance effect, a scheme of dyeing reinforcing fibers is generally adopted in the prior art. For example:
the patent CN114222780a prepreg and the preparation method thereof relate to a preparation method for improving the designability of a molded appearance part formed by fiber reinforced resin and giving a high-grade sense, but the color structure is that the color resin is coated on the surface of a fiber fabric and a transparent surface layer is combined to achieve the effect, but the method does not have a color structure of the fiber itself, and can not give the color of a composite material and simultaneously show the texture effect of the fiber; and a layer of resin is required to be additionally coated on the surface of the fiber fabric, so that the preparation process of the composite material is more complex. The reinforcing fibers are known fibers such as carbon fibers, glass fibers, aramid fibers, boron fibers and polyethylene fibers, and the materials are difficult to degrade and have no tendency to degrade.
The patent CN113234280A cellulose reinforced polypropylene resin matrix composite and a preparation method thereof relate to using colored rayon (regenerated cellulose fiber) staple fibers as a filler, so that the product has uniform matte appearance and bicolor effect. But the addition amount of the regenerated cellulose fibers is smaller and the length is very short, only random color effects can be displayed, the controllability is not strong, and the improvement of the mechanical properties of the short fibers serving as the reinforced relative composite material is limited.
Some natural fibers with higher strength, such as hemp, are reported as reinforcing phases of composite materials, but the color of the hemp is too heavy, so that proper colors are difficult to dye and dye, and many colors are difficult to dye.
Therefore, the fiber used as the reinforcing phase of the color composite material in the prior art has the defects of difficult dyeing, nondegradable property, difficult process increase, poor reinforcing effect and the like. There is a need to develop a colored fiber suitable for preparing composite materials.
Disclosure of Invention
The regenerated cellulose fiber filament is prepared by taking natural cellulose as a raw material and regenerating the natural cellulose after physical or chemical dissolution, has the characteristics of wide raw material sources, regeneration and excellent mechanical properties, and can realize complete degradation under certain conditions. The regenerated cellulose fiber has good combination with dye, is convenient to dye, is used for reinforcing composite materials, and can meet the requirements of light weight and degradability of reinforcing fibers.
In order to solve the technical problems, the invention provides a colored regenerated cellulose fiber filament, a preparation method thereof and a composite material prepared from the colored regenerated cellulose fiber filament. The specific scheme is as follows:
a colored regenerated cellulose fiber filament, characterized in that the regenerated cellulose fiber filament is dyed with a dye, the twist of which is 0-100 twists/meter, and the linear density of which is 550dtex-50000dtex.
For resin matrix composite materials, the presence of twist in the fibers or yarns as reinforcing phase makes it difficult to fully infiltrate the liquid resin, resulting in a decrease in the bonding interface between the reinforcing phase and the continuous phase, and the mechanical properties of the reinforcing phase cannot be fully utilized, thereby adversely affecting the mechanical properties of the prepared composite material. However, during the production of the fiber or yarn, there is always an inevitable twist in the steps of drawing, winding and dyeing, and thus twisting of the reinforcing yarn should be avoided as much as possible during the production. Conventional cotton, hemp and other natural fiber yarns are usually formed by twisting short fibers, high twist is inevitably present in the spinning process, and regenerated cellulose fibers can be spun into bundled filaments, so that the twisting of the filament bundles can be avoided to the greatest extent without additional twisting in the production process. Compared with natural fibers, the regenerated cellulose fibers have smaller linear density deviation and more uniform and stable mechanical properties. Accordingly, regenerated cellulose fiber filaments are selected as the composite reinforcement phase in the present invention.
In order to give full play to the mechanical properties of the filaments as possible, the twist of the filaments should be controlled between 0 and 100 twists/meter, preferably between 0 and 50 twists/meter, more preferably between 0 and 30 twists/meter, most preferably between 1 and 15 twists/meter. If the linear density of the filaments is too small, the subsequent weaving and composite material forming process is more complicated, and the production efficiency is too low; however, too large a fineness means that the number of fibers in the filament bundle is large and dense, which causes difficulty in penetration of the resin when the filament bundle is mixed with the continuous phase resin, and that part of the fibers are still in a dry fiber state, so that the properties of the material are hardly fully exerted, and thus the linear density of the filaments in the invention is 550dtex to 50000dtex, preferably 1000dtex to 30000dtex, and more preferably 1500dtex to 24000dtex.
Alternatively, the regenerated cellulose fiber filaments have a linear density deviation of 15%, preferably 10%, preferably 5%, most preferably 3%
Optionally, the regenerated cellulose fiber has a tensile break strength greater than 6cN/dtex.
In order to ensure the mechanical properties of the prepared composite material, regenerated cellulose fibers with high strength are selected, and preferably the tensile breaking strength of the regenerated cellulose fibers is more than 6cN/dtex.
Optionally, the elongation at break of the regenerated cellulose fiber is 2% -15%.
Optionally, the elongation at break of the regenerated cellulose fiber is 2% -8%.
Optionally, the elongation at break of the regenerated cellulose fiber is 8% -15%.
When the rigidity of the product is required, the elongation at break is selected to be lower, such as 2-8%, and when the impact resistance of the final composite material is required to be improved, the elongation at break is selected to be higher, such as 8-15%.
A process for the preparation of colored regenerated cellulose fiber filaments as described above, comprising the steps of:
1) Dissolving cellulose raw material, spinning and regenerating to obtain regenerated cellulose fiber filaments with the linear density of 550dtex-50000dtex, wherein the filaments are not twisted in the spinning process;
2) Winding the regenerated cellulose fiber yarn spun in the step 1) to obtain a regenerated cellulose fiber yarn package, wherein filaments are not twisted in the winding process;
3) Dyeing the package warp cone yarn in the step 2) to obtain color regenerated cellulose fiber filaments;
the cone yarn dyeing process comprises the steps of fiber cone loosening, cone loading, dyeing, rinsing and drying, and filament twisting is avoided in the dyeing process.
The creel dyeing is adopted because other dyeing methods such as untwisted regenerated cellulose fiber filament, hank dyeing and the like are easy to intertwine filaments in filaments when the untwisted filaments are dyed, so that filament bundles cannot be extracted from hank yarns for weaving, and the problem can be avoided when the creel dyeing is adopted.
Further, the fiber loosening step adopts a fast reciprocating type loosening machine, and the winding speed is 100-1500m/min, preferably 200-800m/min, and most preferably 200-500m/min.
The rapid reciprocating type cone loosening machine does not have a grooved roll, yarn winding is controlled through the cycloid device, and the rapid reciprocating type cone loosening machine is needed to ensure that fibers smoothly pass through at high speed and have smaller abrasion due to higher linear density of the selected yarns. In the process of loosening the drum, the winding speed is lower than 100m/min, the production efficiency is low, the speed exceeds 1500m/min, the yarn stacking density cannot be well ensured, yarn breakage and fuzzing are easily caused, and the yarn performance is affected.
Further, the dyeing can be carried out by using commonly used acid dyes, neutral dyes and reactive dyes, preferably reactive dyes.
The colored resin matrix composite material comprises a continuous phase and a reinforcing phase, and is characterized in that the reinforcing phase is regenerated cellulose fiber fabric, the regenerated cellulose fiber fabric comprises dyed regenerated cellulose fiber filaments, the twist of the regenerated cellulose fiber filaments is 0-100 twists/meter, and the linear density is 550dtex-50000dtex.
Alternatively, the linear density deviation of the dyed regenerated cellulose fiber filaments is ± 15%, preferably ± 10%, preferably ± 5%, most preferably ± 3%.
Optionally, the regenerated cellulose fiber fabric is made from at least two colors of regenerated cellulose fiber filaments, wherein at least one of the regenerated cellulose fiber filaments is spun dyed.
Optionally, the regenerated cellulose fiber fabric is one of plain weave fabric, twill weave fabric or satin weave fabric.
Optionally, the regenerated cellulose fiber fabric has a pattern woven by the regenerated cellulose fiber yarns with the same or different colors.
The preparation method of the color resin matrix composite material is characterized by comprising the following steps:
a) Weaving a colored regenerated cellulose fiber fabric, wherein yarns adopted by the fabric comprise colored regenerated cellulose fiber filaments;
b) Impregnating the fabric produced in step a) with a liquid resin;
c) Curing the resin-impregnated fabric prepared in step b) to obtain a color composite.
Further, in the step a), the fabric is woven by a weaving method, and the weaving method is preferably a rapier loom.
Since the tow of the regenerated cellulose fiber filaments used in the present invention is thick, it is difficult for a conventional loom for weaving directly, so that a rapier loom is preferably used for weaving a fabric.
Further, the weave structure of the colored regenerated cellulose fiber fabric is one or more of plain weave, twill weave and satin weave.
Further, the width of the colored regenerated cellulose fiber fabric is 400mm-2000mm, preferably 400-1500mm.
Further, the colored regenerated cellulose fiber fabric may have a thickness of 0 to 0.6mm, preferably 0.1mm to 0.4mm.
Further, the surface density of the colored regenerated cellulose fiber fabric can be 80-400g/m 2 Preferably, youOptionally 100-300g/m 2 。
The surface density is lower than 80g/m 2 The thickness is convenient to adjust, the places needing corner-bending layering are small in fabric wrinkles, mechanical weakness is not easy to generate, the process design is enhanced, but the number of times needing layering is increased, the workload is increased, the process is complicated, and the thickness is higher than 400g/m 2 The ply can generate folds and the resin is difficult to impregnate, mechanical weakness is generated, process designability is poor, and the use of the final composite material is affected.
Further, the color resin matrix composite material can be compositely molded in a prepreg mode, and can also be directly molded by adopting a fabric and resin direct molding process.
Further, the resin of the colored resin-based composite material can be a thermosetting resin, such as epoxy resin, unsaturated resin, vinyl resin and other conventional resins, and can also be a polymethacrylate, polycarbonate and other thermoplastic resins.
Further, the resin can be transparent resin, so that the texture structure of the fabric can be well presented. The light transmittance is greater than 30%, preferably 50%, more preferably 80%, and in preferred 90%, most preferably greater than 95%.
Further, the resin used may be a bio-based thermosetting or thermoplastic resin to prepare an all bio-based composite.
Further, the molding process of the composite material can be a conventional molding process, a resin transfer molding process and the like.
The beneficial effects are that:
the colored cellulose fiber filament provided by the invention is suitable for preparing colored composite materials, can ensure that the composite materials have excellent appearance effect and better mechanical properties, and has the advantages of biological sources, degradability and the like compared with the traditional reinforcing fibers such as carbon fibers, glass fibers, aramid fibers and the like. And the colored cellulose fiber filaments are colored, so that the filaments can be used for producing the colored composite material without additional treatment.
Compared with the mode of preparing the fabric firstly and printing and dyeing the fabric, the color fabric is prepared by the color fibers, and then the composite material is prepared, so that the texture and special gloss of the fabric can be displayed on the composite material while the color of the composite material is enriched.
Detailed Description
Conventional resin-based composite materials generally adopt carbon fibers, glass fibers, aramid fibers and the like as reinforcing phases, and the fibers have the problem of difficult coloring, so that the fibers are difficult to be used for preparing color composite materials. Conventional cellulose fibers typically have limited reinforcement of the resinous material in the form of staple fibers as the reinforcing phase, or yarns spun from staple fibers as the reinforcing phase. In the present invention, unless otherwise specified, "yarn" means a bundle of fibers which are twisted/untwisted into a staple fiber/filament and which are suitable for knitting.
The invention provides a colored regenerated cellulose fiber filament, wherein the regenerated cellulose fiber filament is dyed by dye, the twist degree is 0-100 twists/m, the linear density is 550dtex-50000dtex, and the linear density deviation rate in the filament is +/-15%, preferably +/-10%, preferably +/-5%, and most preferably +/-3%.
The colored cellulose fiber filament is made into a fabric which is used as a reinforcing phase of a resin material, and because the surface of the regenerated cellulose fiber is more uniform than that of natural fiber, the linear density deviation is small, the strength is higher, the twist of the filament is low, the orientation of the filament along the length direction is good, the liquid resin is easier to infiltrate, the contact interface between the filament and the resin is large, and the mechanical property of the filament can be fully exerted. And the regenerated cellulose fiber is easy to dye, and the color composite material with corresponding colors and textures can be prepared according to the needs.
Specifically, the colored regenerated cellulose fiber filaments and colored resin-based composites may be prepared by the methods described below.
The preparation of colored regenerated cellulose fiber filaments can be roughly divided into two steps of filament preparation and filament dyeing.
Preparation of regenerated cellulose fiber filaments:
the regenerated cellulose fiber is fiber obtained by taking natural cellulose as a raw material, dissolving the natural cellulose to obtain spinning stock solution, and then spinning. Common regenerated cellulose fibers are viscose, lyocell, cuprammonium, etc. Natural fibers such as cotton and hemp are usually carded and twisted into yarns by short fibers, the fibers are tightly cohesive, and resin with high viscosity is difficult to permeate between fiber monofilaments; the regenerated cellulose untwisted filaments have weak cohesion among single fibers and large gaps, resin is easy to soak, a composite material form which takes the resin as a continuous phase and the fiber as a disperse phase is formed, and the mechanical properties of the fiber and the stress transfer function of the resin can be fully exerted.
In addition, compared with natural fibers, the regenerated cellulose fibers are more uniform, the linear density deviation among fiber monofilaments in the formed fiber bundles is small, and the prepared composite material is more stable in performance.
The preparation of regenerated cellulose fibers generally requires the steps of dissolving, spinning, washing with water, drying, winding, and the like.
Dissolution of cellulose is mainly physical dissolution and chemical dissolution. Physical dissolution is to directly dissolve cellulose with solvents, common solvents are aqueous NMMO solutions and ionic liquids. Chemical dissolution is a viscose spinning dope prepared by dissolving cellulose in a specific solvent through a series of chemical reactions to form soluble substances, for example, cellulose becomes cellulose xanthate through a series of reactions. The cellulose used as a raw material may be a dissolving pulp derived from natural cellulose such as wood, or may be a recycled cellulose fabric. The dissolution of cellulose into a spinning dope can be regenerated into regenerated cellulose fibers in a coagulation bath by wet or dry spray wet methods.
The dissolved spinning dope is discharged through a spinneret and regenerated into continuous regenerated cellulose filaments in a coagulation bath. The coagulation bath can be selected adaptively according to the dissolution mode. For example, aqueous NMMO is used as the solvent for the dope, and the coagulation bath is usually water or aqueous NMMO; the coagulation bath of the viscose dope is usually a bath containing H 2 SO 4 、Na 2 SO 4 、ZnSO 4 Three-component coagulation bath.
The stock solution trickle sprayed from the spinneret is regenerated into regenerated cellulose fiber filament in a coagulating bath, then is conveyed to a water washing device through a plurality of conveying rollers or drawing rollers, residual solvent and/or coagulating bath in the fiber are washed out through water washing, and then is dried to a specified water content through a drying device, and is wound into regenerated cellulose fiber filament packages through a winding device.
For the composite material, the higher the strength of the fiber used as the reinforcing phase is, the better the strength is, so that regenerated cellulose fiber with the tensile breaking strength of more than 6cN/dtex is preferable as the reinforcing phase, and the crystallinity and the orientation degree can be improved through the selection of raw materials and the adjustment of spinning process parameters, so that the fiber has higher tensile strength. When the product is required to have rigidity, the pulp with high crystallinity can be selected as a raw material for spinning, so that the fiber with the final elongation of 2-8% is obtained; when it is desired to improve the impact resistance of the final composite, a high elongation fiber should be selected, such as an elongation of 8-15%.
The fibers ejected from the spinneret can typically be hundreds to tens of thousands, with a filament linear density typically ranging from 0.5dtex to 20dtex. When the filament is wound into filament packages, a plurality of monofilament fibers are required to be divided into a group to form fiber bundles, and the fiber bundles are wound. Preferably the fiber bundle has a linear density of 550dtex-50000dtex. The yarns used as the reinforcing phase of the composite material are required to be woven into fabrics, the yarn is lower than 550dtex, and the yarns are too thin, so that the weaving efficiency is too low when the yarns are woven into fabrics with the same size and surface density; when the linear density is too high, the resin is difficult to permeate when being mixed with the continuous phase resin, and the mechanical property of each fiber cannot be fully exerted. Compared with taking filaments, the fiber bundle selected by the invention has larger linear density, namely thicker yarns, so that the weaving efficiency is ensured, and the complex working procedures of processing the composite material are reduced, thereby reducing the production cost on the premise of meeting the mechanical property.
Conventional regenerated cellulose fiber filaments for spinning are usually twisted to a certain degree in the winding process as protective twist to improve cohesion between fibers, so that later weaving is facilitated, and for filament bundles for preparing composite materials, in order to improve the resin infiltration degree, filament bundle twisting should be avoided as much as possible, so that fiber monofilaments are wound in a parallel manner as much as possible. Thus, unlike conventional filament production processes, the regenerated cellulose fiber filaments of the present invention require no twisting step to produce, and do not twist the tows.
The filament bundles used as the reinforcing phase of the composite material are preferably untwisted, the orientation degree of the fibers in the twisted filament bundles in the composite material is reduced, and the mechanical property of each filament is difficult to fully utilize; the twisted fiber monofilaments are tightly cohesive, and the liquid resin serving as a continuous phase is generally high in viscosity, so that the liquid resin is difficult to enter around each monofilament, the resin is not fully soaked, and a regular resin continuous phase cannot be formed, so that the bonding interface of the fiber and the resin is influenced, and the mechanical property of the composite material is adversely affected.
Dyeing of regenerated cellulose fiber filaments:
the regenerated cellulose fiber still has a cellulose molecular structure, is the same as that of cotton fiber, has good dyeing effect by common acid dye, neutral dye and reactive dye, has mature dyeing process, and is convenient to dye and has good color fastness compared with common carbon fiber, glass fiber, aramid fiber and the like in composite materials.
In order to reduce the twist of the filaments as much as possible, the filaments are dyed in the present invention by means of cheese dyeing. By means of process control, the cone yarn dyeing process can change the twist little, other dyeing methods such as hank yarn dyeing and the like are easy to tangle among filaments in the filaments when the untwisted filaments are dyed, so that filament bundles cannot be pulled out of hank yarn for weaving, and the problem does not exist in cone yarn dyeing, so that cone yarn dyeing is needed. Unlike conventional cheese dyeing processes, care should be taken not to twist the filaments in the process of the present invention.
The cheese dyeing process comprises the steps of fiber loosening, barrel loading, dyeing, rinsing, drying and the like.
The fiber loosening step adopts a quick-moving reciprocating type loosening machine, the loosening machine does not have a grooved roll, yarn winding is controlled through a cycloid device, and the loosening machine with the grooved roll is difficult to smoothly pass yarns and can cause larger abrasion to fibers because the selected yarns have higher linear density. Therefore, the invention adopts the rapid reciprocating type barrel loosening machine to ensure that the fiber passes smoothly at high speed and has less abrasion. The rewinding speed of the rewinding machine is 100-1500m/min, preferably 200-800m/min, most preferably 200-500m/min. The speed is lower than 100m/min, the production efficiency is low, the speed exceeds 1500m/min, the yarn stacking density cannot be well ensured, yarn breakage and fuzzing are easily caused, and the yarn performance is affected.
The dyeing step can adopt common acid dye, neutral dye and reactive dye, the molecular structure of the regenerated cellulose fiber is the same as that of cotton, and the regenerated cellulose fiber has abundant hydroxyl groups and can form firm chemical bonds with the reactive dye, so that the reactive dye is preferable.
In the whole production process of the color regenerated cellulose fiber filament, as filament tows are conveyed through a multistage device such as a drawing roller, a washing roller, a drying roller and the like, slight twist is inevitably present among the fibers in the filament tows, and in the winding and loosening processes, certain staggering is also present among the fibers due to the rotation of a winding device and the swinging of a swinging piece, so that the filament obtained by winding inevitably has the slight twist. The twist of the colored regenerated cellulose fiber filaments in the present invention should therefore be in the range of 0 to 100 twists/meter, preferably 0 to 50 twists/meter, more preferably 1 to 20 twists/meter, and most preferably 1 to 15 twists/meter.
Because the reactive dye is adopted to dye the regenerated cellulose fiber, the reactive dye can form a chemical bond with hydroxyl on the surface of the fiber, and compared with other chemical fibers, the performance of the dyed fiber is not reduced.
Preparation of color resin-based composite material
The colored regenerated cellulose fiber filaments are suitable for preparing resin-based composite materials, and the preparation of the resin-based composite materials mainly comprises two steps of colored fabric preparation and fabric and resin composite molding.
The colored regenerated cellulose fiber fabric is prepared by adopting untwisted filaments as yarns and weaving by adopting a weaving method in order to ensure that resin can infiltrate the fabric in the subsequent process. The weave structure of the fabric may be designed as desired, such as plain weave, twill weave, satin weave, and the like. The prepared colored regenerated cellulose fiber fabric can be woven by adopting a single-color fabric or can be woven by adopting yarns with different colors. The single color fabric may be formed into a specific texture by a design weaving process; yarns with different colors are adopted for weaving, and specific pattern can be woven on the surface of the fabric; different colors and patterns can be designed on the fabric in an embroidered mode, so that the diversity of the appearance of the color composite material is enriched. Compared with the method for printing and dyeing the patterns on the surface of the fabric, the method has the advantages that the specific pattern is obtained in a braiding mode by adopting the colored fibers, the texture and the luster of the fabric can be better protruded, and the composite material has better differential visual effect.
The width of the colored regenerated cellulose fiber fabric may be 400mm to 2000mm, preferably 400 to 1500mm. The fabric thickness may be 0-0.6mm, preferably 0.1-0.4 mm, and the fabric areal density may be 80-400g/m 2 Preferably 100-300g/m 2 An areal density of less than 80g/m 2 The process design is enhanced, but the process for preparing the composite material is much more complex and higher than 400g/m 2 The process designability is poor and the resin is relatively difficult to impregnate.
Composite forming of fabric and resin
In the invention, the composite forming of the fabric and the resin refers to that the color regenerated cellulose fiber fabric prepared above is immersed in liquid resin, and then the liquid resin is solidified to obtain the color composite material.
The composite molding process can be performed in a prepreg mode, or by a process of directly molding fabric and resin. The prepreg can be prepared by a solution impregnation method or a hot melting method, wherein the solution impregnation method is to pass a colored fiber fabric through a resin glue groove according to a certain speed, then extrude redundant glue solution through a compression roller, and obtain the colored fiber prepreg through processes such as drying, sticking release paper, rolling and the like. The preparation of the color fiber fabric prepreg by the hot melting method is to heat resin to a molten state by adopting a heating mode, scrape-coat the resin on the isolation paper, adhere the resin on the color fiber fabric by a traction roller, attach a layer of isolation paper on the other surface of the color fiber fabric to form a sandwich structure, squeeze and impregnate the resin uniformly by the hot roller, and compact and roll the resin to obtain the color fiber fabric prepreg.
The direct forming process includes the steps of cutting color fiber fabric of proper size according to the requirement of the product, setting the fiber fabric onto mold, sealing the mold, injecting resin into the mold under certain pressure or vacuum condition to impregnate the color fiber fabric, and curing at certain temperature and pressure for certain time to obtain the color fiber fabric composite material.
The liquid resin may be a thermosetting resin such as an epoxy resin, an unsaturated resin, a vinyl resin, etc., and the thermoplastic resin may be a polymethacrylate, a polycarbonate, etc. The full biobased composite can also be prepared using a biobased source of thermosetting or thermoplastic resin.
After the fabric is impregnated, the forming process can adopt methods such as compression molding, resin transfer molding and the like, and the color composite material is obtained after the forming.
The invention is illustrated in more detail hereinafter by means of examples, in which the test methods for the parameters involved are as follows:
the linear density is measured by the method described in GB/T14343-2008 chemical fiber filament yarn density test method;
the twist is measured by the method described in GB/T14345-2008 chemical fiber filament twist test method;
the measurement and calculation of the linear density deviation ratio are carried out by the method described in GB/T14343-2008 chemical fiber filament yarn density test method.
Example 1
Dissolving pulp in an NMMO aqueous solution with the concentration of 87% at 90 ℃, carrying out dry-jet wet spinning, washing with water, drying, and rolling the spun fibers in a form of 1800dtex per bundle without twisting. And unwinding the wound package obtained by winding onto a dyeing pipe at a speed of 200m/min by adopting a fast-moving reciprocating winder, putting the wound package into a cheese dyeing cylinder, dyeing by using a red reactive dye at 70 ℃ (temperature, ph value and the like) for 20min, soap boiling at 90 ℃ for 10min, taking out, drying and winding to obtain the red regenerated cellulose fiber filament. Through testing, the prepared red regenerated cellulose filament has the linear density of 1810dtex, the twist of 0 twist/m and the linear density deviation rate of 3 percent.
The mechanical properties of the regenerated cellulose fiber filaments before and after dyeing are compared with those shown in the following table:
| project | Virgin cellulose fibers | Colored cellulose fibers |
| Denier/dtex | 1800 | 1810 |
| Twist/(twist/meter) | 0 | 0 |
| Dry break strength/(cN/dtex) | 6.1 | 6.3 |
| Elongation at break/% | 5.25 | 5.23 |
| Initial modulus/GPa | 36 | 37 |
As can be seen from Table 1, the properties of the fibers before and after dyeing were not changed much or even slightly improved, because the dye used was a reactive dye, and it was able to form chemical bonds with hydroxyl groups on the surface of the fibers, so that the properties of the fibers were not reduced.
The red regenerated cellulose fiber filament yarn is woven into a twill fabric with the width of 1000mm, the thickness of 0.3mm and the surface density of 200g/m2 by a rapier loom. And (3) soaking the fabric in epoxy resin in a mould, and carrying out hot press molding at 120 ℃ for 30min to obtain the composite material with red appearance, twill knitting texture and luster.
The mechanical properties of the composite material are shown in the following table after testing:
the red composite material prepared by the embodiment can be used in the fields of automobile decoration, computer housings, household appliance housings, case housings and the like.
Example 2
Dissolving pulp in an NMMO aqueous solution with the concentration of 87% at 90 ℃, carrying out dry-jet wet spinning, washing with water, drying, and rolling up the spun fibers in 2200dtex each bundle in a non-twisting mode. And unwinding the wound package obtained by winding onto a dyeing pipe at a speed of 300m/min by adopting a fast-moving reciprocating winder, putting the wound package into a cheese dyeing cylinder, dyeing by using light blue reactive dye at 65 ℃ (temperature, ph value and the like) for 20min, boiling for 10min at 90 ℃, taking out, drying and winding to obtain light blue regenerated cellulose fiber filaments. The test shows that the light blue regenerated cellulose filament has linear density of 2210dtex, twist of 1 twist/m and linear density deviation of 2%.
The mechanical properties of the regenerated cellulose fiber filaments before and after dyeing are compared with those shown in the following table:
| project | Virgin cellulose fibers | Colored cellulose fibers |
| Denier/dtex | 2200 | 2210 |
| Twist/(twist/meter) | 0 | 1 |
| Dry break strength/(cN/dtex) | 6.2 | 6.3 |
| Elongation at break/% | 5.30 | 5.25 |
| Initial modulus/GPa | 35 | 36 |
As can be seen from Table 1, the properties of the fibers before and after dyeing were not changed much or even slightly improved, because the dye used was a reactive dye, and it was able to form chemical bonds with hydroxyl groups on the surface of the fibers, so that the properties of the fibers were not reduced.
The light blue regenerated cellulose fiber filaments, undyed regenerated cellulose fiber filaments, and red regenerated cellulose fiber filaments of example 1 were woven with a rapier loom to a width of 1000mm, a thickness of 0.3mm, and an areal density of 240g/m 2 Satin weave of (c). Then preparing satin fabric prepreg by adopting a hot melting method, cutting the size into 300mm by 250mm, paving 7 layers, setting the molding temperature of a press to 120 ℃, and hot-pressing for 30min for molding to obtain the composite material which is 2mm thick, has three-color knitting patterns, has satin knitting textures and has luster.
The mechanical properties of the composite material are shown in the following table after testing:
| project | Test standard | Performance index |
| Volume content/% | / | 60 |
| Density/(g/cm 3) | ISO1183-1 | 1.4 |
| Tensile Strength/MPa | ASTM D3039 | 160 |
| Elongation at break/% | ASTM D3039 | 2.0 |
| Tensile modulus/GPa | ASTM D3039 | 17 |
| Flexural modulus/GPa | ASTM 7264 | 18 |
| Flexural Strength/MPa | ASTM 7264 | 210 |
The red composite material prepared by the embodiment can be used in the fields of automobile decoration, computer housings, household appliance housings, case housings and the like.
Example 3
Soaking pulp with 18% alkali liquor to generate alkali cellulose, squeezing to obtain redundant alkali liquor, crushing, standing at 35 ℃ for 18 hours, oxidizing and ageing, introducing carbon disulfide gas at an initial temperature of 20 ℃ for sulfonation, and then curing at a temperature of 15 ℃ to obtain cellulose glue, introducing the glue into a spinning component for spinning through a defoaming pump, and then carrying out procedures of coagulating bath, drafting, washing, oiling, drying and the like to obtain 1840dtex viscose fiber. The same dyeing process, post-weaving and composite molding method as in example 1 was then used, wherein the dye was yellow and the texture design was plain weave during weaving. The final result is a composite material that is yellow in appearance, has a plain weave texture and gloss.
The mechanical properties of the regenerated cellulose fiber filaments before and after dyeing are compared with those shown in the following table:
as can be seen from Table 1, the properties of the fibers before and after dyeing were not changed much or even slightly improved, because the dye used was a reactive dye, and it was able to form chemical bonds with hydroxyl groups on the surface of the fibers, so that the properties of the fibers were not reduced.
The mechanical properties of the composite material are shown in the following table after testing:
| project | Test standard | Performance index |
| Volume content/% | / | 60 |
| Density/(g/cm) 3 ) | ISO1183-1 | 1.4 |
| Tensile Strength/MPa | ASTM D3039 | 150 |
| Elongation at break/% | ASTM D3039 | 5 |
| Tensile modulus/GPa | ASTM D3039 | 10 |
| Flexural modulus/GPa | ASTM 7264 | 9 |
| Flexural Strength/MPa | ASTM 7264 | 160 |
The red composite material prepared by the embodiment can be used in the fields of automobile decoration, computer housings, household appliance housings, case housings and the like.
Comparative example 1
This comparative example is similar to the composite preparation of example 1 except that the regenerated cellulose fiber filaments were twisted at 150 twists/meter prior to winding. The mechanical properties of the composite material are shown in the following table after testing:
| project | Test standard | Performance index |
| Volume content/% | / | 60 |
| Density/(g/cm 3) | ISO1183-1 | 1.4 |
| Tensile Strength/MPa | ASTM D3039 | 140 |
| Elongation at break/% | ASTM D3039 | 1.9 |
| Tensile modulus/GPa | ASTM D3039 | 15 |
| Flexural modulus/GPa | ASTM 7264 | 15 |
| Flexural Strength/MPa | ASTM 7264 | 190 |
As can be seen from the data in the above table, the composite material prepared in example 1 of the present invention has better mechanical properties than twisted yarn.
Comparative example 2
The comparative example was similar to the composite of example 1 except that the regenerated cellulose fiber filaments were dyed with hank yarn in the dyeing step, and after dyeing, the yarn was severely entangled and could not be drawn out for weaving.
Claims (10)
1. A colored regenerated cellulose fiber filament, characterized in that the regenerated cellulose fiber filament is dyed with a dye, the twist of which is 0-100 twists/meter, and the linear density of which is 550dtex-50000dtex.
2. The colored regenerated cellulose fiber filament according to claim 1 having a linear density deviation of ±15%.
3. The colored regenerated cellulose fiber filament according to claim 1 having a tensile break strength of greater than 6cN/dtex.
4. A process for the preparation of colored regenerated cellulose fiber filaments according to any one of claims 1 to 3, comprising the steps of:
1) Dissolving cellulose raw material, spinning and regenerating to obtain regenerated cellulose fiber filaments with the linear density of 550dtex-50000dtex, wherein the filaments are not twisted in the spinning process;
2) Winding the regenerated cellulose fiber filaments spun in the step 1) to obtain regenerated cellulose fiber filament packages, wherein the filaments are not twisted in the winding process;
3) Dyeing the package warp cone yarn in the step 2) to obtain color regenerated cellulose fiber filaments;
the cone yarn dyeing process comprises the steps of fiber cone loosening, cone loading, dyeing, rinsing and drying, and filament twisting is avoided in the dyeing process.
5. The method for producing colored regenerated cellulose fiber filaments according to claim 4, wherein the fiber-loosening step employs a rapid-travel reciprocating type loosening machine, and the winding speed is 100-1500m/min.
6. A colored resin matrix composite comprising a continuous phase and a reinforcing phase, wherein the reinforcing phase is a regenerated cellulose fiber fabric comprising colored regenerated cellulose fiber filaments according to any one of claims 1-3.
7. The colored resin-based composite material of claim 6, wherein the regenerated cellulose fiber fabric is one of a plain weave, a twill weave, or a satin weave.
8. The colored resin-based composite material according to claim 7, wherein the regenerated cellulose fiber fabric has a pattern woven from regenerated cellulose fiber yarns of the same or different colors.
9. The preparation method of the color resin matrix composite material is characterized by comprising the following steps:
a) A woven fabric using yarns comprising the colored regenerated cellulose fiber filaments of any one of claims 1-3;
b) Impregnating the fabric produced in step a) with a liquid resin;
c) Curing the resin-impregnated fabric prepared in the step 2) to obtain the color composite material.
10. The method for preparing a colored resin-based composite material according to claim 9, wherein in the step a), the fabric is woven using a rapier loom.
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