US3595854A - Acetate filaments of improved resistance to hydrothermal delustering and the process for preparation thereof - Google Patents

Acetate filaments of improved resistance to hydrothermal delustering and the process for preparation thereof Download PDF

Info

Publication number
US3595854A
US3595854A US779271A US3595854DA US3595854A US 3595854 A US3595854 A US 3595854A US 779271 A US779271 A US 779271A US 3595854D A US3595854D A US 3595854DA US 3595854 A US3595854 A US 3595854A
Authority
US
United States
Prior art keywords
delustering
filaments
flakes
hydrothermal
cellulose acetate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US779271A
Other languages
English (en)
Inventor
Masao Matsuzaki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Teijin Ltd
Original Assignee
Teijin Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Teijin Ltd filed Critical Teijin Ltd
Application granted granted Critical
Publication of US3595854A publication Critical patent/US3595854A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/22—Post-esterification treatments, including purification
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
    • D01F2/28—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate
    • D01F2/30—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate by the dry spinning process

Definitions

  • This invention relates to a process for the preparation of acetate filaments having excellent resistance to hydrothermal delustering, with good reproducibility, in which the inherent deficiency of cellulose acetate, filaments, i.e., hydrothermal delustering, is conspicuously eliminated without detrimental effect on the filaments favorable properties such as silk-like hand, luster, clarity of dyed color and practical strength, etc., and also relates to such improved filaments.
  • the filaments of the invention exhibit no appreciable delustering phenomenon, which subjected to, for example, a treatment with hot water of 110 C. under an elevated pressure.
  • the invention relates to a process for the preparation of acetate filaments of which hydrothermal delustering property is improved, comprising dissolving acetone-soluble cellulose diacetate flakes in a solvent system composed chiefly of acetone, and spinning the solution into acetate filaments, the characteristic features residing in that the flakes are subjected to a heating posttreatment in a dilute aqueous acid solution until their refined parameter at the stability of 0.08% is reduced to no higher than 80, and then removed of the treating liquid by washing, followed by the said dissolving and spinning steps, and relates also to thus obtained cellulose acetate filaments.
  • Cellulose acetate filaments possess such favorable properties as silk-like hand, luster, clarity of dyed color, and
  • delustered filaments exhibits inconveniently remarkable abnormalities in their fiber properties, particularly reduction in strength and increase in elongation. Such tendency is more conspicuous at advanced degree of delustering. Thus this drawback incurs indeed heavy limitations on the utility of cellulose acetate filaments.
  • the so treated flakes provide novel type of cellulose acetate filaments having high resistance to hydrothermal delustering as described in the foregoing. It is furthermore discovered that the filaments of the strength quite satisfactory for practical purposes can be obtained by suitably selecting the acetyl value of the flakes before the dilute acid treatment.
  • the cellulose acetate filaments prepared from the flakes which have been so post-treated until the specified parameter is satisfied exhibit always excellent resistance to hydrothermal delustering and fully satisfy 4 the reproducibility of the high quality.
  • the measured values of the said parameter of commercially available cellulose acetate flakes are no less than 150, normally above 200.
  • the object of the invention is to provide novel cellulose acetate filaments having excellent resistance to hydrothermal delustering, good qualitative reproducibilty and practically satisfactory fiber strength, and a process for the preparation of such filaments.
  • cellulose diacetate flakes (which may be hereafter referred to as acetate flakes) include all forms of dry cellulose diacetate used as the spinning material, for example, powder, granule, pellet, foil, short staple, etc.
  • the acetate flakes are subjected to a heating post-treatment in dilute aqueous acid solution, for example, dilute aqueous solution of a mineral acid such as sulfuric, nitric, phosphoric, and hydrochloric acids, or of a lower fatty acid such as acetic acid. It is permissible to perform the post-treatment in the concurrent presence of similarly dilute aqueous solution of bleaching agent, such as of sodium hypochlorite, hydrogen peroxide, potassium permanganate, etc. Or, the flakes may be treated with such bleaching or reduction bleaching agent, after the specified dilute acid post-treatment.
  • dilute aqueous acid solution for example, dilute aqueous solution of a mineral acid such as sulfuric, nitric, phosphoric, and hydrochloric acids, or of a lower fatty acid such as acetic acid.
  • bleaching agent such as of sodium hypochlorite, hydrogen peroxide, potassium permanganate, etc.
  • the flakes may be
  • the concentration of acid in the dilute aqueous solution for the heating post-treatment may range from approximately 0.l% to approximately 0.001%, in case mineral acids are employed.
  • the concentration can be suitably varied, depending on the type of acid, shape of flakes, heating temperature, etc.
  • the preferred concentration is normally around ODS-0.005%, inter alia, approximately 0.040.0l%.
  • it may range approximately 100.5%, preferably 60.8%, inter alia, in the order of 4-l%.
  • the heating temperature ranges about 200 C. Preferred range is about 180 C., inter alia, in the order of 90-160 C.
  • the temperature is suitably selected depending on such factors as heating time, type and concentration of acid, shape of flakes, etc.
  • the treatment can be performed batchwise or continuously.
  • the flakes may be suspended in a tank filled with the aqueous acid solution, to be heattreated.
  • heated aqueous acid solution may be caused to flow down through a column packed with the flakes.
  • the flakes continuously supplied from the top portion of a treating column may be countercurrently contacted with the aqueous acid solution supplied from bottom portion of the column as an upward flow.
  • heated, dilute aqueous acid solution may be sprayed on the acetate flakes which are being transferred on a movable belt. in short any optional method can be employed, so far as the aqueous acid solution and the solid flakes can intimately and uniformly contact with each other.
  • the treatment can be performed under either atmospheric or elevated pressure. Also if desired, it is permissible to employ a slightly reduced pressure condition under which the aforesaid heating temperature can be maintained.
  • Duration of this post-treatment is suitably varied or selected according to such factors as type and concentration of the acid, shape and amount of the flakes, treating system, pressure condition, etc., but in all cases it must be long enough to satisfy the aforesaid parameter.
  • Any treatment not satisfying the parameter is not within the scope of subject process.
  • the products fail to show the resistance to hydrothermal delustering at temperatures exceeding C., and qualitative reproducibility is impaired.
  • the acetate flakes must be post-treated, until their refined parameter at the stability of 0.08% is reduced to no more than 80.
  • the flakes are thoroughly washed to remove the treating liquid remaining thereon.
  • Warm water shows better washing efficiency than cold water.
  • warm water of about 4095 C. can be advantageously used.
  • a dilute alkaline aqueous solution can be used for the same purpose.
  • treated acetate flakes are normally dried, and dissolved in a solvent system composed chiefly of acetone by the means known per se.
  • the cellulose acetate filaments spun therefrom exhibit no appreciable delustering in hot water of above 100 C., for example, 110-150 C. (under elevated pressure). Such cellulose acetate filaments are never before produced, although very much wished for.
  • the filaments can be imparted with strength suflicient for practical purposes.
  • that the refined parameter at the stability of 0.08% is no more than 80 signifies that the numeral value measured and calculated by the following method is no more than 80.
  • the water obtained through the identical procedures as above except the addition of the sample is omitted is similarly quickly neutralization titrated by way of a blank test, and the first titration value is corrected by subtracting the blank titration value therefrom.
  • the percentile acetic acid content (A) per sample weight is calculated.
  • g. of the same sample is precisely weighed and is immersed in 100 cc. of pure water at room temperature for 3 hours and filtered. Then the solid component of the sample is washed with 50 cc. of pure water, and the filtrate and washing are combined. The liquid is also neutralization titrated with 0.01 N aqueous caustic soda solution, using phenolphthalein as the indicator. Separately a blank test is conducted. The percentile acetic acid content (B) per sample weight is then calculated.
  • the hardness of the water for immersing the flakes can be suitably selected to secure the intersection of the said curve with the 0.08% stability level. That is, when the stability of the sample flakes is above the level of 0.0 8%, plural types of water having hardnesses exceeding 2.5 times of the alkalinity corresponding to that stability are selected. And, if the stability of the sample flakes is below the level of 0.08%, the hardnesses of less than 2.5 times the corresponding alkalinity are selected.
  • the curve showing the correlation of stability with alkalinity of the sample obtained as described in the foregoing resembles a hyperbola for which the axis of abscissa and a straight line perpendicularly crossing therewith are the asymptates.
  • the location of the straight line perpendicularly intersecting with the axis of abscissa varies, depending on the composition of acetate flakes employed.
  • the SP value of the acetate flakes in accordance with the present invention provides a highly reliable, excellent parameter for prediction of hydrothermal delustering and qualitative reproducibility of the cellulose acetate filaments prepared from the same flakes.
  • the filaments made from the flakes satisfying this parameter exhibit excellent resistance to hydrothermal delustering and high qualitative reproducibility. More specifically, the filaments show the degree of delustering (Whcih will be defined later) of no more than grade 1.5 in hot water of 110 C., for example, grade 0.3 or 0.2 which means substantially no appreciable delustering.
  • the sample cellulose acetate filaments of 100 deniers/ 25 filaments are mechanically wound onto a frame into six layers, over a width of 3 cm. without gaps.
  • the frame is then immersed in hot water in an autoclave wherein the temperature is controlled to 95 C.
  • the autoclave is immediately closed airtightly, and inside temperature thereof is raised to 110 C. during the following 30 minutes.
  • the frame is withdrawn and air-dried at room temperature for 30 minutes.
  • the filaments are dried in a constant temperature drying oven of C. The degree of delustering of the filaments is then graded in comparison with the standard samples.
  • the result is referred to as the degree of hydrothermal delustering at C.
  • the testing temperature is 100 C.
  • the result is the degree of hydrothermal delustering at 100 C.
  • the standard samples are prepared to have successively increased degree of delustering with rise in the numerical grade, starting from the grade zero denoting the status of filaments before the hydrothermal treatment, to enable 8 Degree of delustering: Factor Per one sample exceeding grade 1.5 to grade functional determination of the grade. .At the delustering 3.0 "a- +0.3 grade 5, the filaments are substantially milky white.
  • the specimens were boiled in 0.02% solvent system composed chiefly of acetone and spinning aqueous sulfuric acid solution, each 2, 4, 10, 20 and th am n accordance w accepted Practice, P088685 30 hours. Then the sulfuric acid was completely washed heretofore unknown high resistance to hydrothermal demi fro th specimens with water. Then SP parameter of lustering, such as the degree of hydrothermal delustering 35 each specimen was measured. They were subsequently at 110 C. of grade 1.5 or less. Also the grade shows exdissolved in acetone and spun in the accepted manner.
  • Control 4I Example 7 Control 5
  • Control 6 Control 7
  • r Control 9 i The before treatment and after treatment respectively mean before and aiter the hot Water treatment of a skein yarn in the same manner as the measurement of hydrothermal delustering degree at 110 C. The strength is a dry strfingth both before and after treatment.
  • a process for the preparation of cellulose diacetate filaments which have a degree of hydrothermal delustcring at 110 C. of not more than grade 1.5 and a qualitative 5 reproducibility of 97-l00% which comprises:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
US779271A 1967-11-28 1968-11-26 Acetate filaments of improved resistance to hydrothermal delustering and the process for preparation thereof Expired - Lifetime US3595854A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP7663267 1967-11-28

Publications (1)

Publication Number Publication Date
US3595854A true US3595854A (en) 1971-07-27

Family

ID=13610731

Family Applications (1)

Application Number Title Priority Date Filing Date
US779271A Expired - Lifetime US3595854A (en) 1967-11-28 1968-11-26 Acetate filaments of improved resistance to hydrothermal delustering and the process for preparation thereof

Country Status (6)

Country Link
US (1) US3595854A (enrdf_load_stackoverflow)
BE (1) BE724592A (enrdf_load_stackoverflow)
BR (1) BR6804410D0 (enrdf_load_stackoverflow)
ES (1) ES360759A1 (enrdf_load_stackoverflow)
FR (1) FR1593742A (enrdf_load_stackoverflow)
GB (1) GB1229634A (enrdf_load_stackoverflow)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4269972A (en) * 1978-06-09 1981-05-26 Daicel Ltd. Process for producing cellulose diacetate having improved resistance to delustering phenomenon in hot water

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4269972A (en) * 1978-06-09 1981-05-26 Daicel Ltd. Process for producing cellulose diacetate having improved resistance to delustering phenomenon in hot water

Also Published As

Publication number Publication date
BR6804410D0 (pt) 1973-01-16
DE1811531A1 (de) 1969-07-24
GB1229634A (enrdf_load_stackoverflow) 1971-04-28
ES360759A1 (es) 1970-07-16
DE1811531B2 (de) 1977-06-02
BE724592A (enrdf_load_stackoverflow) 1969-05-02
FR1593742A (enrdf_load_stackoverflow) 1970-06-01

Similar Documents

Publication Publication Date Title
JPH07506629A (ja) 二酸化ケイ素を含む製品およびその製造方法
US2112116A (en) Production of cellulose fiber of low solution viscosity for conversion into cellulose derivatives
US3595854A (en) Acetate filaments of improved resistance to hydrothermal delustering and the process for preparation thereof
US4269972A (en) Process for producing cellulose diacetate having improved resistance to delustering phenomenon in hot water
US2869318A (en) Voluminous yarn
US2087263A (en) Cellulose pulping system and product thereof
US3720661A (en) Process for producing acetylated regenerated cellulose articles
US3631023A (en) Continuous esterification of cellulose
US3403145A (en) Acetylation of cellulose
US3255158A (en) Preparation of acrylonitrile polymers using a catalytic system containing a high ratio of activator/catalyst
US2198660A (en) Treatment of textile and other materials
US2092749A (en) Process and composition of matter
US2694060A (en) Process of bleaching cellulose esters with chlorites
US3305433A (en) Cold caustic refining of cellulose
US1576529A (en) Manufacture of filaments and films from viscose
GB340324A (en) Improvements in the production of artificial materials by wet spinning processes from solutions of organic derivatives of cellulose
DE1811531C3 (de) Verfahren zur Herstellung von Cellulosediacetatfäden
US2516267A (en) Process of sizing textiles and composition therefor
US2180517A (en) Making cellulose derivatives
US1749003A (en) Mercerized wood-fiber tissue and process of preparing same
US1668945A (en) Process of esterifying hydrated cellulose with lower fatty acids
US2176850A (en) Preparation of cellulose derivatives
KR920010264B1 (ko) 심색성(深色性) 폴리에스터 필라멘트사의 제조방법
US2592305A (en) Method of lowering the viscosity of hydrolyzed cellulose esters and product
US1995732A (en) Process of manufacturing cellulose acetate