Background technology
The protein content of silkworm chrysalis is more than 50%, be higher than normal food far away, and the essential amino acid A wide selection of colours and designs in the protein, silkworm chrysalis protein is comprised of 18 seed amino acids, and wherein 8 seed amino acid content of needed by human are very high, 2 times of pork, 4 times of egg, 10 times of milk, the amino acid nutrient of 8 kinds of needed by human is balanced, ratio is suitable, meets FAO/WHO(FAO (Food and Agriculture Organization of the United Nation) and the World Health Organization) requirement; Silkworm chrysalis also contains potassium, receives, calcium, magnesium, iron, copper, manganese, zinc, phosphorus, selenium and other trace elements, vitamin A, E, B1, B2, carrotene etc.; The content of the unrighted acid in the silkworm chrysalis is very abundant, accounts for 72.5% of total fat.Pupa albumen present stage is mainly used in food additives, cosmetic additive agent and carries out copolyreaction with regenerated celulose fibre, synthetic fiber then obtaining a kind of new weaving new material through spinning.
At present published patent application about " pupa albumen and regenerated celulose fibre blend spinning " mainly contains 201010533320.5,200610021534.8,95111328.3,97107800.9 and 03135631.1.Find according to actual tests, more or less all there is certain problem in these products, such as protein set problem, environmental issue etc.Application number provides a kind of manufacture method of wooden pupa protein viscose staple fibers for 201010533320.5 patent application, this process has only solved the spinning problem of xylon and pupa albumen, and the loss late of protein is still higher in the production process; Application number provides a kind of bamboo pupa protein fiber long, short silk for 200610021534.8 patent application, and it is to contain silkworm chrysalis albumen spinning solution and the bamboo cellulose viscose glue is that raw material is prepared from by following percentage by weight: silkworm chrysalis albumen spinning solution 10-40%, bamboo cellulose viscose glue 60%-90%; Application number a kind of silkworm chrysalis albumen composite long fibre that has been 95111328.3 Patent Application Publication, its component comprises pupa albumen, viscose glue and acrylamide; Application number a kind of method for manufacturing pupa protein viscose filament rayon that has been 97107800.9 Patent Application Publication, it is to utilize silkworm chrysalis albumen spinning solution and cellulose xanthate solution static mixing and spin front injection to carry out spinning, the pupa albumen viscose filament yarn with Real silk properties of making; 03135631.1 Patent Application Publication a kind of manufacture method of protein short staples, it is to utilize silkworm chrysalis albumen spinning solution and cellulose yellow acid vinegar, solution carries out spinning with injection system before imitative and static mixing principle, make the manufacture method of the protein short staples of function admirable, its main raw material is pulp, pupa albumen, sulfuric acid, caustic soda, carbon disulfide, formaldehyde, glutaraldehyde, acrylamide.From above-mentioned patent application, all relate in the processing step and adopt formaldehyde to carry out hydroformylation, and formaldehyde itself is a kind of colourless, the gas that the intense stimulus smell is arranged, belong to the magma poisonous substance, energy and protein bound are behind the suction high-concentration formaldehyde, the serious stimulation of respiratory tract and oedema, eye shouting pain, headache can occur, also bronchial astehma can occur.The direct Formaldehyde Exposed of skin can cause dermatitis, color spot, necrosis.Often suck a small amount of formaldehyde, can cause slow poisoning, the series of problems such as mucous hyperemia, skin irritatin disease, allergic dermatitis, nail angling and fragility, nail matrix finger tip pain occur.Simultaneously, now external from View of International Market, particularly European and American developed countries are to containing or production process adopts the product of formaldehyde clearly not enter.
Summary of the invention
The present invention is intended to overcome the defective of prior art, provides a kind of and utilizes pupa protein liquid and cellulose xanthate solution through static mixing and spin front injection and carry out pupa albumen viscose staple fibre and the manufacture method thereof with Real silk properties that spinning is made.This pupa protein viscose staple fibers, strand is soft, and it is golden yellow that color and luster is.
For achieving the above object, the present invention adopts following technical scheme:
A kind of pupa protein viscose staple fibers, it is characterized in that: by pupa protein liquid and cellulose sulfonate solution by the weight ratio of 1%-60%: 40%-99% through static blend, spinning, solidify, curing and post processing obtain, this pupa protein viscose staple fibers is the loss late of protein<30% in process of production, finished product is after 50 washings, and its celloglobulin expulsion rate is no more than 5%.
The manufacture method of described pupa protein viscose staple fibers is undertaken by following processing step:
The preparation of A, pupa albumen liquid
By 1-10: 1 solid weight ratio takes by weighing pupa albumen and NaOH, first pupa albumen being dissolved in temperature and being 20-80 ℃, concentration is 0.1-20%(w/w) sodium hydrate aqueous solution in, after 30min-6hr obtains pupa albumen solution, again in pupa albumen solution by weight 1: 0.0001-0.5 adds auxiliary agent, stir, filtration obtains the pupa albumen liquid after the uniform modification;
Described auxiliary agent is silane coupler.
B, pupa albumen liquid and cellulose sulfonate solution blending
With pupa albumen liquid and cellulose sulfonate solution respectively after the deaeration, be that the weight ratio of 1%-60%: 40%-99% is carried out static mixing and carried out making viscose glue after the deaeration by pupa albumen liquid and cellulose sulfonate solution again;
C, spinning
Viscose glue adopts the two-bath process wet method to carry out spinning, and namely viscose glue is quantitatively sent into for the sebific duct road by measuring pump and entered spinning machine, by candle filter elimination particle impurities again, and sends into spinneret assembly by curved tube, and viscose glue by spinneret orifice, forms the viscose glue thread under pressure;
D, solidify and curing
The viscose glue thread out after, enter coagulating bath, behind coagulation forming, become nascent strand; Nascent strand is sent to boundling stretching in the fixation bath by draw-off godet, when nascent strand stands to stretch, finally finishes the disintegrating and regeneration process, and namely pupa albumen anchors at cellulose surface, forms the fibre bundle with stable skin-core structure;
Consisting of of described coagulating bath: sodium sulphate 100-500g/L, sulfuric acid 30-250g/L, zinc sulfate 5-100g/L; Temperature 20-80 ℃.
Consisting of of described fixation bath: sulfuric acid 10-200g/L, sodium sulphate 10-300g/L, temperature 30-100 ℃.
E, post processing
Fibre bundle is obtained the pupa protein viscose staple fibers through cut-out, pickling, desulfurization, washing, pickling, after washing, oil, dewater, drying.
Useful technique effect of the present invention shows:
1, the present invention does not all use formaldehyde in whole technical process, thereby has eliminated the ambient influnence that formaldehyde brings.
2, in the preparation process of the relevant pupa protein viscose staple fibers of prior art, the loss late of its protein>40%, even up to 60%, the expulsion rate of celloglobulin then surpasses 10%; The loss late of protein then is lower than 30% in the whole technical process of the present invention, and the final finished fiber is after 50 washings, protein comes off and is no more than the ratio of protein in the relative fiber of 5%(), thereby Effective Raise the anchor effect of pupa albumen at cellulose surface, solved the problem that comes off of protein.
3, because common rayon spinning viscosity is (falling ball method mensuration) about 35S, this viscosity is conducive to spinning moulding, and the viscosity of pupa albumen liquid is generally 18 to 25S, if directly pupa albumen liquid is added in the viscose, then mixed viscose viscosity can drop sharply to 24 ~ 28S, is unfavorable for spinning.The present invention is by after adding auxiliary agent in pupa albumen liquid, the modification pupa albumen fluid viscosity that obtains can reach 30 ~ 38S, and can not cause that viscosity changes after adding viscose glue, thereby has effectively guaranteed spinning moulding.
4, the pupa protein viscose staple fibers that is made by the present invention, strand is soft, and it is golden yellow that color and luster is, quality better.
The specific embodiment
Embodiment 1
A kind of pupa protein viscose staple fibers, by pupa protein liquid and cellulose sulfonate solution by 1%: 99% weight ratio through static blend, spinning, solidify, curing and post processing obtain, this pupa protein viscose staple fibers in process of production loss late of protein is 5%, finished product is after 50 washings, and its celloglobulin expulsion rate is 0.5%.
Embodiment 2
A kind of pupa protein viscose staple fibers, by pupa protein liquid and cellulose sulfonate solution by 60%: 40% weight ratio through static blend, spinning, solidify, curing and post processing obtain, this pupa protein viscose staple fibers in process of production loss late of protein is 25%, finished product is after 50 washings, and its celloglobulin expulsion rate is 4%.
Embodiment 3
A kind of pupa protein viscose staple fibers, by pupa protein liquid and cellulose sulfonate solution by 15%: 85% weight ratio through static blend, spinning, solidify, curing and post processing obtain, this pupa protein viscose staple fibers in process of production loss late of protein is 10%, finished product is after 50 washings, and its celloglobulin expulsion rate is 1%.
Embodiment 4
A kind of pupa protein viscose staple fibers, by pupa protein liquid and cellulose sulfonate solution by 30%: 70% weight ratio through static blend, spinning, solidify, curing and post processing obtain, this pupa protein viscose staple fibers in process of production loss late of protein is 15%, finished product is after 50 washings, and its celloglobulin expulsion rate is 2.5%.
Embodiment 5
A kind of pupa protein viscose staple fibers, by pupa protein liquid and cellulose sulfonate solution by 50%: 50% weight ratio through static blend, spinning, solidify, curing and post processing obtain, this pupa protein viscose staple fibers in process of production loss late of protein is 20%, finished product is after 50 washings, and its celloglobulin expulsion rate is 3%.
Embodiment 6
A kind of manufacture method of pupa protein viscose staple fibers is undertaken by following processing step:
The preparation of A, pupa albumen liquid
Solid weight ratio by 1: 1 takes by weighing pupa albumen and NaOH, first pupa albumen being dissolved in temperature and being 20 ℃, concentration is 10%(w/w) sodium hydrate aqueous solution in, after 1hr obtains pupa albumen solution, in pupa albumen solution, add by weight again silane coupler at 1: 0.1, stir, filtration obtains the pupa albumen liquid after the uniform modification;
B, pupa albumen liquid and cellulose sulfonate solution blending
With pupa albumen liquid and cellulose sulfonate solution respectively after the deaeration, be that 1%: 99% weight ratio is carried out static mixing and carried out making viscose glue after the deaeration by pupa albumen liquid and cellulose sulfonate solution again;
C, spinning
Viscose glue adopts the two-bath process wet method to carry out spinning, and namely viscose glue is quantitatively sent into for the sebific duct road by measuring pump and entered spinning machine, by candle filter elimination particle impurities again, and sends into spinneret assembly by curved tube, and viscose glue by spinneret orifice, forms the viscose glue thread under pressure;
D, solidify and curing
The viscose glue thread out after, enter coagulating bath, behind coagulation forming, become nascent strand; Nascent strand is sent to boundling stretching in the fixation bath by draw-off godet, when nascent strand stands to stretch, finally finishes the disintegrating and regeneration process, and namely pupa albumen anchors at cellulose surface, forms the fibre bundle with stable skin-core structure;
Consisting of of described coagulating bath: sodium sulphate 250g/L, sulfuric acid 100g/L, zinc sulfate 100/L, temperature 20-40 ℃.
Consisting of of described fixation bath: sulfuric acid 200g/L, sodium sulphate 300g/L, temperature 30-50 ℃.
E, post processing
Fibre bundle is obtained the pupa protein viscose staple fibers through cut-out, pickling, desulfurization, washing, pickling, after washing, oil, dewater, drying.
Embodiment 7
A kind of manufacture method of pupa protein viscose staple fibers is undertaken by following processing step:
The preparation of A, pupa albumen liquid
Solid weight ratio by 5: 1 takes by weighing pupa albumen and NaOH, first pupa albumen being dissolved in temperature and being 80 ℃, concentration is 0.1%(w/w) sodium hydrate aqueous solution in, after 30min obtains pupa albumen solution, in pupa albumen solution, add by weight again silane coupler at 1: 0.5, stir, filtration obtains the pupa albumen liquid after the uniform modification;
B, pupa albumen liquid and cellulose sulfonate solution blending
With pupa albumen liquid and cellulose sulfonate solution respectively after the deaeration, be that 60%: 40% weight ratio is carried out static mixing and carried out making viscose glue after the deaeration by pupa albumen liquid and cellulose sulfonate solution again;
C, spinning
Viscose glue adopts the two-bath process wet method to carry out spinning, and namely viscose glue is quantitatively sent into for the sebific duct road by measuring pump and entered spinning machine, by candle filter elimination particle impurities again, and sends into spinneret assembly by curved tube, and viscose glue by spinneret orifice, forms the viscose glue thread under pressure;
D, solidify and curing
The viscose glue thread out after, enter coagulating bath, behind coagulation forming, become nascent strand; Nascent strand is sent to boundling stretching in the fixation bath by draw-off godet, when nascent strand stands to stretch, finally finishes the disintegrating and regeneration process, and namely pupa albumen anchors at cellulose surface, forms the fibre bundle with stable skin-core structure;
Consisting of of E, the described coagulating bath of post processing: sodium sulphate 500g/L, sulfuric acid 250g/L, zinc sulfate 50g/L, temperature 50-80 ℃.
Consisting of of described fixation bath: sulfuric acid 10g/L, sodium sulphate 50g/L, temperature 80-100 ℃.
Fibre bundle is obtained the pupa protein viscose staple fibers through cut-out, pickling, desulfurization, washing, pickling, after washing, oil, dewater, drying.
Embodiment 8
A kind of manufacture method of pupa protein viscose staple fibers is undertaken by following processing step:
The preparation of A, pupa albumen liquid
Solid weight ratio by 10: 1 takes by weighing pupa albumen and NaOH, first pupa albumen being dissolved in temperature and being 50 ℃, concentration is 20%(w/w) sodium hydrate aqueous solution in, after 6hr obtains pupa albumen solution, in pupa albumen solution, add by weight again silane coupler at 1: 0.0001, stir, filtration obtains the pupa albumen liquid after the uniform modification;
B, pupa albumen liquid and cellulose sulfonate solution blending
With pupa albumen liquid and cellulose sulfonate solution respectively after the deaeration, be that 40%: 60% weight ratio is carried out static mixing and carried out making viscose glue after the deaeration by pupa albumen liquid and cellulose sulfonate solution again;
C, spinning
Viscose glue adopts the two-bath process wet method to carry out spinning, and namely viscose glue is quantitatively sent into for the sebific duct road by measuring pump and entered spinning machine, by candle filter elimination particle impurities again, and sends into spinneret assembly by curved tube, and viscose glue by spinneret orifice, forms the viscose glue thread under pressure;
D, solidify and curing
The viscose glue thread out after, enter coagulating bath, behind coagulation forming, become nascent strand; Nascent strand is sent to boundling stretching in the fixation bath by draw-off godet, when nascent strand stands to stretch, finally finishes the disintegrating and regeneration process, and namely pupa albumen anchors at cellulose surface, forms the fibre bundle with stable skin-core structure;
Consisting of of described coagulating bath: sodium sulphate 100g/L, sulfuric acid 30g/L, zinc sulfate 5g/L, temperature 30-50 ℃.
Consisting of of described fixation bath: sulfuric acid 100g/L, sodium sulphate 10g/L, temperature 50-70 ℃.
E, post processing
Fibre bundle is obtained the pupa protein viscose staple fibers through cut-out, pickling, desulfurization, washing, pickling, after washing, oil, dewater, drying.