TW201801B - - Google Patents

Description

A 6 It 6 k.01bGi V. Description of the invention (1)? Yanming background The scope of Niming The present invention relates to hydrophobic aromatic polyamide fibers and one of their manufacturing methods. During the manufacturing of aromatic polyamide fiber, it is often processed. For some applications, for example, in the impregnation of the fiber or knitted fabric, the processed material still present on the fiber must be removed. Thereafter, the fluorine-containing compound serving as a water-repellent agent is applied to the fibers of the knitted fabric. The characteristics of the fiber-to-resin interface in the aromatic polyamide compound are very important. It is also known that when the fiber-to-resin adhesion value is properly controlled, it should be used for filament winding structures such as pressurized containers, or hard impact-resistant armor such as aromatic helmets of steel helmets. The performance of amine yarn will be better. Prior art description British Patent Application No. 2, 221, 928 published on February 21, 1990 shows the treatment of textile fabrics with ketene dimers to make them water-repellent. The textiles in this announcement are mainly wool, cotton, and polyester / cotton blends. The textiles in this bulletin are always dried again and have never been swollen with solvent or water. However, the treatment according to this reference is not suitable for the purpose of the present invention in terms of surface friction characteristics, hydrophobicity, and use of the resulting fiber in resin composites. The references mentioned above cannot produce fibers with the required sustainability and ready-to-use. The size of this paper is based on the Chinese S-standard (CNS) ^ H ^ tf} (210x297 gong) installed--5-line-The standard of the Ministry of Economic Affairs: JTA Gongji Cooperative Printing 5i 81. 2. 20,000 3-0180 Λ fi l \ 6 Printed by the Ministry of Economic Affairs and printed by the Cooperative Societies V. Description of Invention (2) Japanese Patent Application No. Kokai 60 — 258 245 relates to a polymer containing ketene dimer and cationic acrylamide Aqueous dispersion of substances and anionic dispersants, which can be used for the treatment of cellulose fiber fabrics, in order to produce softness and water repellency. Therefore, one of the objectives of the present invention is to provide a ready-to-use surface-treated aromatic polyamidamide for applications requiring reduced or no water dynamic absorption and controllable, low-fiber surface paper. Ready-to-use means that the aromatic polyamide fiber does not need to be further processed, such as removing the processed material, applying water repellent, or adjusting the fiber-to-resin value of the composite. Another object of the present invention is to provide a method for manufacturing the ready-to-use fibers. It also provides continuous Burmese (in-line) and batch-by-batch (non-in-line) methods to manufacture the modified aromatic polyamide fiber material. Another object of the present invention is to provide an aromatic polyamide fiber material for reinforcing rubber and composite objects or other polymer matrices (ring gasifiers, polyesters, phenolic polymers) and including Twisting, knitting, weaving loops or weaving operations. Another object of the present invention is to provide a highly processable aromatic polyamide unit (yarn, thread, cord, regular fiber, pulp, staple fiber) as a reinforcing unit for elastomers and traditional composites. The improved processability of this product will result in higher performance in the final package (for example, higher strength conversion in fabrics). Another object of the present invention is to provide aromatic polyamide fibers that can be used without twisting in production lines (which include knitting or weaving operations with a single yarn). When used in a twisted form (eg in the form of a cable), the toughness and modulus of the aromatic polyamide unit in the final cable structure are better than commercial products. m% The size of the paper used is based on China ’s national standard rate (CNS> T4 specification (210x297 male dragon) 81. 2. 20,000 1 4-Λ fi Π 6 丄 _ 5. Description of the invention (3) is fully utilized. Order Surprisingly, it was found that the treatment of undried aromatic polyamide fibers with surface reactants can improve the processability, hydrophobicity, and fiber-resin adhesion value. At the same time, through the use of fluorine-containing repulsion The dangers of poisons produced by water agents, as well as the control of the fiber through the silicone oils used previously-the potential bond decline caused by a resin value can be eliminated. According to the present invention, certain aromatic The coating of the surface reactant reacted on the surface of the polyamide fiber will provide a novel surface-increasing fiber, which not only exhibits excellent processability related to friction, but also has a completely hydrophobic surface. Show low core to And it can improve the glycol resistance, which is very important in the composite materials of automobile radiators. The fiber also shows less discoloration dynamics if exposed to sunlight. At the same time, the fiber tube according to the present invention The hardness (pad density) has also been significantly improved. The use of surface reactants can further eliminate the additional processing steps (thereby processing the fiber-resin adhesion value can be controlled to be used as a reinforcement unit of the composite ), Or eliminate the extra washing and fluorine-treatment of the fabric weaving structure. The fabric made from the renovated surface energy fiber of the present invention shows the comfort of wearing due to the increased air permeability and vapor transport Therefore, the end-use performance of the last system will also be significantly improved. G Yanming Dishu The present invention is about having a high modulus, improved surface friction resistance, improved washability, low abrasion deposition, and low fibrillation High processability and hydrophobicity of the effect (please read ^ Backward Note ^^^^ write ^ Binding · Order_Line-This paper is used in the national standard (CNS) ΤΊ 訊 怙 （210x297 Gonglong) 81. 2. 20,000 -5-LOibOi Λ ίί It 6 Standard of the Ministry of Economic Affairs and only printed by the Cooperative Society 31 V. Description of the invention (4) Aromatic polyamide fiber, which is still pending After the surface of the aromatic polyamide fiber is reacted with a surface reactant to produce a coated fiber, the surface reactant includes the enone dimer CR ^^^ O] of the following general formula ♦ CR ^ R 2i C2〇] (I) wherein each Ri and group may be the same or different, expressed as alkyl, cycloalkyl, aryl, alkenyl, aralkyl, arene with 4 to 32 sulfonic atoms Radical or alkaryl; and each R 2 and R 〃 group may be the same or different, expressed as a hydrogen atom or an alkyl or alkenyl group having 1 to 6 main atoms, (1) is a pure liquid, or ( 2) is a solution of 1 to 60% by weight of an inert organic solvent, or (3) is an aqueous emulsion, the aqueous emulsion can be added by 1 to 60% by weight of the ketene dimer at a pH of 2.5 to 5 of the mixed liquid, this mixed liquid includes (i) 0.25 to 10% by weight of a cationic water-soluble polymer, and (ii) ◦. 0 5 to 5% by weight of alkali metal lignin sulfonate or phosphonium Formaldehyde sulfonate Sodium concentrate was stirred and homogenized and subsequently the particles size of less than 0.5 microns. The description of the invention found that it was prepared from a solution or spun and condensed in an aqueous bath (please read the precautions first and then write the clothing, thread, and paper 5 good scales, and use a S home sample ( CNS) TM specifications (210x297 g) 81. 2. 20,000 Λ 6 Π 6

OlBGi 5. Description of the invention (5) The aromatic polyamide fiber can quickly react with the base of the aromatic polyamide molecule (the fiber of which is in the undried state) deal with. If the reaction between the ketene dimer and the aromatic polyamide on the surface of the dried fiber proves to be less successful, it is obvious that the effective reaction position of the aromatic polyamide on the surface is reduced. In the present invention, the surface aromatic polyamide molecule is reacted with the ketene dimer and the fiber is subsequently dried before providing a layer of coating on the aromatic polyamide fiber. The coating produced by the reaction between the surface of the undried aromatic polyamide fiber and the ketene dimer provides several advantages; first, the coating makes it workable during the manufacture of the fiber; Second, make the resulting fiber hydrophobic; and third, supply the fiber-controlled fiber to one-to-one resin adhesion. Regarding the compound of formula (I) as defined above, the preferred alkyl or alkenyl group R; and RP contain 8 to 24 atoms, and more preferably contain 14 to 24 atoms. Preferably, each R \ RP group may individually represent an alkenyl group or an alkyl group. The alkyl or alkenyl group representing R \ RP is selected from octyl, decyl, dodecyl, tetradecyl, Tetradecenyl, hexadecyl, hexadecenyl, octadecyl, octadecenyl, eicosyl, eicosyl, behenyl, behenyl, twenty-four Alkyl, and tetradecenyl. The preferred alkyl and alkenyl groups R2 and R2 'may be the same or different and contain 1 to 6 atoms; preferably the alkyl group is selected from the group consisting of alkyl C / _C3 and alkenyl one (: 4. However, more preferred R2 and R2 'are hydrogen. The paper standard uses the Chinese national standard iMCNS) T4 specification (210x297 g: ¢) ΒιΤτΤίΟ, ΟΟΟ (please read the notes to be followed first, please fill in the sun also set _ line-Ministry of Economics 屮 央 楳Accurate and ts: industrial treatment cooperation Du Yin 3i II Λ 6 _____ 1 \ 6_ V. Description of the invention (6) In the preferred method according to the present invention, the enone dimer cited is tetradecyl, tetradecyl The ketene dimers of alkenyl, hexadecyl, hexadecenyl, eicosyl, and eicosyl. The surface reactants based on the ene-dimer according to the invention can be coated in different ways Onto the fiber. The ketene dimer can be coated in pure, liquid form. The coating is performed at a temperature below 1 ο ου, and preferably between 40 and 80Ό, if necessary, before coating Melt it first. The ketene dimer is also soluble in a suitable inert organic solvent. Suitable organic solvents are alcohols, Such as isopropanol; 'alkanes, such as n-hexane, heptane, octane, nonane, decane; and aromatic solvents, such as toluene, o-, m-, or p-xylene, 1,3, 5- Trimethylbenzene; and dichloroethane. Usually the concentration of the ketene dimer in the solvent is 1 to 6 ◦% by weight. The ketene dimer can also be adjusted in a pH and contains 0.25 It is emulsified in an amount of 1 to 60% by weight of the ketene dimer in an aqueous mixed solution of 1% by weight of cationic water-soluble polymer and 5% by weight of alkali metal lignin sulfonate. Water-soluble polymers include: starch modified by cationic amines, cationic one-charge ethylene addition polymers, and the like. Cationic-charged ethylene addition polymers include polyacrylamide, polymethylmethacrylate The quaternary salt of acrylamide and the substance modified by Mannich reaction and further quaternized. In the practice of the present invention, the cationic water-soluble polymerization used as the stabilizer and emulsifier of the ene dimer The material can be homopolymer, copolymer, or the standard S 掳 楳 准 (CNS) TM specification (21 0x297mm > ~ 81, 2. 20,000 (31 Read this first and pay attention to this item. Sun ^^ Order_ line, the Ministry of Economic Affairs standard and the β industrial consumption cooperation Du Yin 5Ϊ -8-

Oj-ilQuL Λ β η 6 V. Description of the invention (7) Blends; non-ionic and anionic water-soluble polymers can also be printed with the Yangli Ministry of Economics + Central Standard Engineering Co., Ltd. to print sub-polymerization The combination of substances is used together as long as the total charge of the combination is cationic. The starch modified by the cationic amine is represented by the following formula R s- (0-R3-NR4R3) „where η is within the substitution range of the starch and is 0.005 to 3, R s represents starch , R 3 represents alkylene, hydroxyalkylene, phenylalkylene or alkylalkylene, R4 and R5 represent alkyl, alkenyl, alkaryl, aralkenyl, aryl, aralkyl, Cycloalkyl or hydrogen atom. The starch modified by the cationic amine used as stabilizer and emulsifier in this system will be described in more detail in US Patent No. 3,130,118. Other patents describe cationizers There are No. 3, 821, 〇69; No. 3, 854, 970; No. 4, 〇29, 885. Usually the p Η value of the emulsifier solution is adjusted to 2.5 to 5 with an appropriate acid such as acetic acid or hydrochloric acid 5 Then, the ketene dimer is added in a liquid state. When the addition of the dimer is completed, the mixed liquid is further homogenized to produce an emulsion having a particle size of less than 0.5 microns. Within the scope of the present invention Within, the term fiber is expressed as a continuous filament yarn as well as a single yarn or cord, often-produced fibers, fiber debris (eg It is used to extend the non-continuum method), fine yarn or flat yarn strands, often produced by crimped fiber, pulp, industrial shuttle, twisting, braiding, looping or aromatic polyamide with fiber structure. Paper-scale Happy Use Chinese a Jiayubi (CNS) ΤΊ specification (210x297 gong) 81. 2. 20,000 (please read the precautions first. Sun Kai writes volume -9-/ Λ P ,, A 6 Q jbt ^ _Π6_ V. Description of the invention (8) The finished packaged fabric. The undried aromatic polyamide fiber is in a swollen, non-shrinkable state and contains 15-20% by weight, preferably At least 20, and most preferably 30 to 70 weight percent water relative to the weight of the dry fiber. Aromatic polyamide fibers are polymer fibers that are partially, mostly, or entirely composed of aromatic compounds , The aromatic ring is connected via a carboxamide bridge, or, if necessary, can also be connected via other bridge structures. This aromatic polyamide structure can be illustrated by the general formula of the following repeating unit: (― NH — Αι — NH — C 〇 — Az — CO-) n where Ai and Ba 2 can be the same or different, Represents aromatic and / or polyaromatic and / or heteroaromatic rings, and can be substituted. Typically A: and A2 can be independently selected from 1, 4-phenylene, 1, 3-phenylene, 1, 2-phenylene, 4, biphenylene, 2, 6-pyridene, 1, 5-pyridyl, 1,4-monophenylene, phenoxyphenyl-4,4-diphenylene, phenoxybenzene Group —3, 4 ^ —dipentenyl, 2,5-pyridinium and 2,6-quinolinylidene, which may or may not be substituted by more than one substituent, and the substituents include halogen, Ci—C4 alkyl, Phenyl, carbonyl alkyl, Ci_C4 alkyl, acetyl, nitro, dialkylamino, sulfanyl, carboxy, and sulfonyl. The CONH- group can also be replaced by a carbonyl-hydrazide (CONHNH-) group, azo or azo. More available polyamides are shown in the U.S. Patent No. 1 on the paper side of the standard Chinese Η home brown bi (CNS) f 4 specifications (210x297 g *) (please read the notes on the back #Item 窎 表 定 _ 线. CX Workers' Counseling Cooperative Duo Printing Co., Ltd. of the Central Bureau of Economic Development of the Ministry of Economic Affairs 81. 2. 20,000 10-Standards of the Ministry of Economics and Examination ^ βIndications of the Cooperative Society of the Ministry of Economic Development 3i 丄 一 Λ 6 ______ Π_6_ V. Description of Invention (9) 4 , No. 670 · 343, wherein the aromatic polyaldehyde amine is a copolymer, which is preferably at least 80 mole% in the total amount of A: and 6: 2,4-phenylene and phenylaminobenzene The base 3, 4 · * -diphenylene (which may be substituted or unsubstituted), and the content of phenylaminophenyl-3, 4--diphenylene is 10 to 40 mole%. It is completely aromatic. Fibers derived from amides are preferred. Examples of aromatic polyamides are poly-m-phenylene-isophthalamide and polyone-to-one phenylene pairs of phthalamide. Additional suitable aromatic polyamides are Such as the following structure (-NH-Ari-X-Ar2-NH-C〇-Ar ^ -X-Ar2-C〇-), where X represents 〇, S, S〇2, NR, Ν2, CR2, C〇R Represents H, C2 alkyl and Ar: and Ar2 may be the same or different and selected from 1, 2_ phenylene 1, 3-phenylene and 1,4-phenylene, at least one hydrogen atom of which is replaced by halogen and / or Ci_C4 alkyl. The additive will be used together with the aromatic polyamide. In fact, it has been found that Up to 10% by weight of other polymer materials may be blended with the aromatic polyamide, or a copolymer of diamine having 10% of other diamines in place of the aromatic polyamide or 10% of other Diaromatic gas is used to replace the copolymer of diacyl chloride of the aromatic polyamide. Furthermore, the present invention relates to a method for manufacturing a highly processable water-repellent aromatic polyacetal fiber as defined above, which Including steps

(Please read the back and pay attention to the matter # 記 写 I 装 · 线 线-This paper has 5 good scales and is easy to use in the country. The Chinese National Completion (CNS) 1M regulations (210X297 male dragon) 81. 2. 20,000 11-

Printed by the OibG Ministry of Economics Standards 揓 A 工 消 t \ ·· Cooperatives V. Description of the invention (10)-Coat the ketene dimer surface reactant as defined above on the aromatic polyamide fiber for one order The fiber is heated to between 30 and 400¾, and at the same time-the surface reactant can be re-coated at least once if necessary, and-the fiber can be re-heated repeatedly after each coating if necessary. The aromatic polyamide fiber Coating with the ketene dimer surface reactant of the present invention can be done in various ways, but more preferably according to the following method. The ketene dimer surface reactant can be a "in the pipeline" or a non-line " to coat; --- in-line tube-one means that the fiber is coated during the spinning process, the non-line means that the fiber is removed from the spinning process, and then by the spool or bobbin Coated in medium or similar. In the process of the present invention, the ketene dimer surface reactant is applied to the undried fiber, and then the fiber is dried; if necessary for some special reasons, it can be extended and / or heat-treated. Aromatic polyamido cellulose is usually spun into an aqueous coagulation bath, as shown in U.S. Patent No. 3,767,756, and then the water-swelled fiber is washed and neutralized before the enone treatment of the present invention Of it. Are found. When the water-swelled fiber is neutralized with sodium monate, the fiber product produced by the method of the present invention exhibits a better overall quality than the product neutralized with sodium hydroxide. Although the reason for the difference in product quality is not fully known, it is believed that there is a modified reaction with the surface of the ketene dimer and the master salt-neutralized aromatic polyamide fiber (please read first) On the other hand, please note that the size of the paper is 4. Pack. The size of this paper is based on the Chinese national «JMCNS) T4 specification (210X29 / male ¢) 81. 2. 20,000 -12-Attachment 2: First-1_ ^ Patent Application Dish Chinese manual correction page

L01BGI 民 园 81. Amendment V. November, November 5. Description of the invention (11) *, (Please read the precautions on the back before filling in this one)> As required, the coating of the surface reactant can be repeated after the drying step cover. According to the method of the present invention, the coating of the surface reactant is carried out by using a surface coating apparatus, or a roller coating apparatus under the condition of a dryer layer, a snake tube system, or any other known device or method in this field. Use or do not need to set the scraper) on the cleaned fiber substrate. Ultrasonic strips and devices known in this art can also be used to improve the uniformity or penetration of the reagent. 5 重量 ％。 The value of the surface reactant on the fiber should be in the range of .05 to 8% by weight, preferably 0.25 to 2.5% by weight. Drying can be accomplished by convection, heat conduction, ultraviolet radiation, and the like. Usually the heating operation of the coated fiber can be from a few seconds to a few minutes, depending on the degree of dryness required and the additional treatment required. Du Yin, Ministry of Economic Affairs, Central Bureau of Standards, Industrial and Consumer Cooperation * In a preferred embodiment of the off-pipeline method, 1 670 dt ex (1500 denier) of un-dried aromatic polyamide yarn is passed through the containing ene_ The dimer surface reactant impregnated material is Zell-impregnated for coating, and then dried and cooked in an air-heated chamber at 160 ° C with a tension of 3 gpd. Depending on the immersion concentration, it can be between 1 and 30% by weight in water, and the speed can be adjusted between 15 and 50 m / min. The fibers according to the present invention can be used as water pipes, belts, ropes and cables (including optical reels), rubber articles, composite structures (such as lotus equipment, medical supplies, construction and audio materials, civil engineering and military) Application of lotus and defense equipment) and reinforcement of protective clothing. This paper scale is applicable to the Chinese National Standard (CNS) A 4 specifications (210 X 297 male) 81.9.25,000 a 13-

01BC Λ 6 Η 6 The Ministry of Economic Affairs, the central government, and the employees' cooperation and cooperation. Du Yinnu. 5. Description of the invention (12-year-old residence: > Xi Fen Fen Pian example illustrates the preparation of ene dimer at room temperature, 177 Grams of triethylamine or 250 grams of tripropylamine are added to 1 100 grams of freshly distilled toluene. Then, 400 grams of brownish brown gas is slowly added to this toluene-tertiary amine mixture with stirring. Maintain the temperature at about 5〇υ for 2.5 hours and gently stir it. Under 5◦—6 ΟΊΟ, add 290 g of acid solution prepared from 260 g of distilled water and 30 g of concentrated hydrochloric acid, and Stir another 45 minutes. Decant the organic layer and vacuum distill while keeping the temperature as low as possible (4 0-6 0 C). Order toluene and other components of this mixture from the enone Separated from the dimer. The reaction weight is approximately 90% compared with the theoretical calculated value. The thus obtained ketene dimer based on palmitic acid (tetradecyl ketene dimer) has a melting point of about 4 310. This method can also be used to make other ketene dimers such as tetradecenyl, hexadecyl, hexadecenyl, eicosyl, icosyl Alkenyl, and the like. Preparation of an enone dimer emulsion At 901, in 2250 grams of distilled water, 150 grams of cationic tapioca starch (such as the product labeled STAL0K 400 sold by AE Staley corporation) or Cook the same quality cationic maize starch or any commercial cationic etherified starch (such as / 5 -diethylamine ethyl chloride hydrochloride ether maize starch) for about 1 hour. Then cool this solution to 6 ° C, Or it is higher than the melting point of ketene dimer by about 5 to 10C, and it is kept at this temperature during the entire emulsification process. This paper is used in the SHSH standard (CNS) TM specification (210X297 male dragon) 81. 2. 20,000 (please read the precautions Λ-pot to write 4 packs first. Thread--14-01BC ju V. Invention description (13) Ρ Η value by adding acetic acid (sufficient amount to get 3-5 p Η) to adjust. Add 29 grams of sodium phosphonium formaldehyde sulfonate concentrate or 24 grams of sodium lignosulfonate to the starch mixture. Additionally, 360 grams of cetyl ketene dimer or fourteen Alkyl ketene dimer or other ketene dimer as prepared above or Any commercially available ketene dimer is heated to melt and maintain approximately 65 °. The molten ketene dimer is slowly and continuously poured into the starch solution (maintained at 60 ° C) under vigorous stirring. By substantially increasing the shear rate of the mixture, it is further homogenized for 1.5 to 2 minutes. The preparation is quickly cooled to room temperature and is preferably kept below 301C, and optimally below 151C This process will provide a dispersion containing particles smaller than ◦. 5 microns and can be used directly to treat fibers that have never been dried by the method of the present invention. In the following examples, the enone dimer surface reactant formulation described below will be used to coat the surface of aromatic polyamide fibers according to the present invention. (a) 6% by weight cetyl ketene dimer (b) 1. 5% by weight cationic modified starch (commercial cationic potato starch) (c) 0.33% by weight lignosulfonate The rest of sodium (d) is water. In the following examples, the test results obtained on the fibers of the present invention will be the same as those obtained on commercial fibers (which were produced under the same conditions and the same time, but without the use of the surface reactant) (to, , The comparison group 〃 means) to compare. The size of this paper is based on China's "CNS" T4 specification (2 丨 0x297cm *) (please read 15 notes beforehand. Sun Dang writes -1. The Ministry of Economic Affairs is approved by the central government and A Gong Xiao ϊν · Cooperative Du Yin ¾ 81. 2. 20,000 -15-b ο ^ IU, -V-, Li i ^ JJJ 一 偒 特特 A6

B. The Central Standards Bureau of the Ministry of Economic Affairs and Industry and Consumer Cooperation * V. Description of the Invention (14) Example 1 In order to prove that the surface reaction performed in the method of the present invention does not have a negative effect on strangulation, let 100. Denier's undried aromatic polyamide yarn was coated in the pipeline at about 650 m / min, and then dried at 175 t :. The toughness of the coated yarn of the present invention is 24.9 grams / denier, while the toughness of the comparative group is 25.2 grams / denier. These results show that the method of the present invention does not cause a decrease in toughness. In the second test, 1140 denier dried aromatic polyamide yarn was coated under the non-pipeline and dried at 200 ¾. The coated yarn of the present invention exhibited a toughness and modulus of 24.7 and 913 g / denier, while those of the comparative group were 25.5 and 885 g / denier. Once again, these results show that the method of the present invention does not cause the degradation of fibrin. The following Examples 2 to 8 show that the fiber manufactured according to Example 1 has improved processability, surface finishing function, and end-use performance. The tests of Examples 2-8 were carried out on the aromatic polyamide produced according to the in-line method of Example 1. Cellar Example 2 In this example, 1 500 Daniel's uncured aromatic polyamide yarn is coated with cetyl ketene dimer to an amount of 0.8% by the method of the present invention, And measure the friction coefficient, and then compare with the yarn of the comparison group. And the other (please read the precautions on the back side first and then fill out the private set · order · < paper size is applicable to the Chinese National Standard (Ci% TS) A " 4 specifications (2U) X:? 97mm) _ _ 81.9.25,000

A6 B6 V. Description of the invention (15) An additional comparison is that a dried 1500 denier aromatic polyaldehyde amine is also coated with cetyl ketene dimer to an amount of 0.8%, and then tested This fiber.

Rot hschi id friction meter R — 1 1 8 2 is used to measure the friction pseudo-number. These yarns are drawn from the friction meter at a rate of 100 meters / minute; and the friction coefficient values are as follows: (Please read the notes on the back first Please fill in our factory for details.) The dried and unsalted aromatic polyimide m mmm of the present invention is one-to-one fiber 0.09 0.18 0.15 fiber pair-gold fiber 0.20 0.40 0.30 sediment (mg / kg) ) 10 55 0.40. Packed. Ordered--Niang. «Printed by the Jibu Central Chuanju 8 Workers’ Consumer Cooperative «of the table> Sediment 〃 is the substance collected on the tribometer at the time of testing. The number of milligrams of material in kilograms of fiber passing through the friction meter. The increased deposits represent a reduction in fiber braid. Fenshi Example 3 In this example, a fabric woven from an aromatic polyamide yarn with 100 denier and 8X8 tails per centimeter will be tested for hydrophobicity. One of these fabrics is woven from an undried state and treated with hexadecyl ketone dimer according to the present invention to an amount of ◦ · 8%, and one is suitable for the size of the original paper China National Standards (CNS) A 4 specifications (210 II vt I, bite) -17 0160 Λ 6 Π 6 V. Description of the invention (16) In dry state and treated with cetyl ketene dimer to ◦. 8 % Of the yarn is woven, and Yi is woven with the yarn of the comparative group. Another additional test is that some of the dried aromatic polyamide yarns are treated to contain 2.5% hexadecenone dimer, but the yarn cannot be woven into fabric. Hydrophobicity is measured according to AATCC ("American Association of Textile Colorists and Chemists") test method 2 2-1 9 8 5. On a grade cut, where 0 indicates complete wetness and 100 indicates no wetness, this invention Yarn and fabric are regarded as 1 0 ◦ and the comparison group is regarded as 0. The overall results of this test are shown in the table below. C Please read the notes before you write 4 sets-Ministry of Economics + Central Government and work only Consumption cooperation Du Yinyu's wet vortex hh of the present invention is 0.8% higher than the dried aromatic polyamide grade 2.5¾ fabric 100 0 40-80 * ** yarn 100 0 variable 100 average 50 Fibre filaments 100 0 Variable 100 average 50 ”Can only be woven at low speed ** Cannot be woven into paper size for ease of use a Η 家 楳 Bi (CNS) T4 regulation (2 丨 0x297cm ¢) 81 . 2. 20,000 —18-LOlbCi

HI A6 B6 V. Description of the invention (17) It is possible to obtain 100% hydrophobic yarn and to maintain this characteristic without any additional treatment at this level of lux is an important advantage of the present invention. Example 4 In this example, the core of the yarn of the present invention (which is in an undried state and treated with hexadecenone dimer to an amount of 1%) will be used in combination with the dried state. The hexaalkyl ketene dimer was treated to 1% and 3% of the yarn, and the yarn of the comparison group was compared. These yarns are all 1 0 ◦ 0 denier aromatic polyamides, which are held at one end and suspended in a 50 gram weight aqueous ◦. 0 5% methylene art solution. Core feedability is the height of the methylene art solution with time as a culprit. Low core feedability is a desired yarn characteristic. This example shows that the fiber of the present invention is superior to other tested yarns. The capillary process is almost completely broken. K to 袢 (height (mm)) (Please read the precautions on the back before writing this. '&Quot; > Printed by the Ministry of Economic Affairs, Central Standards Bureau, 8th Industrial and Consumer Cooperatives * Time of the invention The dry and dried fiber minutes) Vortex Fiber comparison group 1% 3% 0.5 0 10 3-5 0 1 1 16 6-8 2 2 3 18 10-12 4 5 4 34 13-14 5 10 6 52 19-28 8 15 8 6 7 28-36 10 The paper standard is in accordance with the Chinese National Standard (CNS) Flat 4 specifications (both 210 X 297 fathers) ^ 81.9.25,000 ~ 19-Λ 6 Π 6 Printed by the Central Ministry of Economic Affairs, but only by the Consumer Cooperatives. Description of the invention (18) 啻Example 5 In this example, the fabric made from the un-dried aromatic polyacetal yarn of the present invention will be more impact resistant than the fabric made from the yarn of the comparative group. The impact test (V5. Test) for the armor of the valor was conducted in accordance with the NATO standardization agreement STANAG 2920. V5 of the substance or armor. The impact limit speed is defined by the Up and Down firing method (Up and Down firing method) as the penetration probability of the selected projectile is indeed the speed at 0.5, and the calculation method is as follows. Up and down firing method: The first round should include a good amount of fired gunpowder (this amount has been calculated to make the projectile speed equal to the estimated armor V5. Impact limit). If the first round of shooting is a full penetration, then the second round should be loaded with the calculated gunpowder that produces a fixed reduction rate of about 30 meters / second lower than the first round. If the first answer only partially penetrates the shot, the second answer should be loaded with a calculated gunpowder that produces a fixed rate of increase of about 30 meters / second higher than the first turn. When the penetration back set in the first round is reached, the propellant charge should be adjusted to a fixed amount to produce an increase or decrease of approximately 15 meters per second. Then the shooting will be continued according to a given procedure in order to obtain the estimated value of the V〃 (BLP) [protection of impact limit]. V 5. Calculation method: (Please read the back-up notes first and then fill in the .t pack · This paper is used in the standard S Η family standard (CNS) ΤΊ regulations 怙 (2) 0x297 male dragon) 81. 2. 20,000 U 1 -20-^ .Oib〇

A6 B6 Five 'Invention Description (19) After several projectiles have been fired, v5. It is calculated as the average rate of the maximum velocity of 3 ° for partial penetration and the minimum velocity of 3 ° for full penetration, but the prerequisite is that all 6 values must be within 40 meters / second. The following table shows that, in terms of chip resistance, the fabric made of the gauze of the present invention provides the same impact resistance as the fabric made of the yarn of the comparative group; at the same time, it provides a significant increase in terms of bullets Resistance. This impact (bullet) performance (V3 .: refer to the test process) can be improved in the drying stage. 8 Please read the notes on the back before filling in this booklet. Central Standard Operator of the Ministry of Economic Affairs X Consumer Cooperation Du-Shirt «% while wet The stage can be improved by 10%. Broken Η V 0 V 3〇V 5 0 (meters / second) (meters / second) Tak blanket of the present invention comparison group 1 447 451 2 451 450 3 453 451 4 457 458 average 452 452 Each padding is made of 12 layers of fabric (1000 denier aromatic polyamide yarn woven at a density of 8.3 × 8.3 tails per cm). The impact resistance of the fabric is measured according to NIJ (', National Institute of Justice') standard 0 1 〇 1 · ◦ 3. This paper scale is applicable to China National Standards (CNS) Grade 4 (2I0X 297). 21-81.9.25,000

01BC A6 B6

V. Description of the invention (20) Flat and wet VV 5 〇V 5 0 (meters / second> (meters / second> drying / wetting buhling station _ Tai invention drying 457 496 wet 447 4 93 (please read the back Matters needing attention and refill this page) The Ministry of Economic Affairs, Central Bureau of Samples and Crafts, 8 industrial and consumer cooperatives * p * Each pad is made of 22 layers of fabric (from 150 ◦ Daniel aromatic polyamide yarn in fabric style 7 2 8 — 2 2 0 g / m² woven). This example shows that the fabric woven from the aromatic polyamide of the present invention should be the same as the aromatic polyamide fiber (but not affected by ketene Polymer treatment) The woven fabrics show improved impact performance when compared. The strong holding objects are: 9 mm FMJ 124 grains. Example 6 In this example, the fabric woven with the yarn of the present invention and The test panel made will be more impact-resistant than the test panel made of fabric made of comparative yarn. The panel made of 24 layers of fabric (1 500 denier, 22 ◦ g / m²) is dipped in 18 % Phenol resin. These plates were molded at 1601C and 20 bar for 30 minutes. The fabric made by using the yarn of the present invention and the comparative group .. Made of a fabric made in accordance with the previous stapling - Yi Shi Chang countries like China scale applicable registration (CN'S) A 4 size (2U) χ 297 through well) _ 22 - 81.9.25,000 01b〇

¾ U A6 B6 Printed by the 8th Industrial Consumption Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs * 5. The invention description (21) The STANAG 2920 method described in this article projectively shoots 17 fragments on these boards. The ply made with the fabric of the present invention exhibited a 20% higher impact resistance than the ply made with the yarn of the comparative group. Examination Example 7 In this example, a sample of 1500 aromatic aramid fibers of Daniel was immersed in an ethylene glycol solution (50% water to 50% commercial ethylene glycol) maintained at 1201C 3 ◦ days. After immersion for 30 days, the fibers were drained, washed with distilled water, and then dried. Then, the toughness of these fibrous samples was tested. The initial percentage of toughness can determine the anti-glycol exposure of the fiber. By the method of the present invention, the hexadecenone dimer is treated in an undried state to an amount of 1.5 aromatic polyamide fibers exhibiting a 30% higher resistance to ethylene than the comparative group under the conditions defined above. Glycolic. However, the aromatic polyamide fiber treated with cetyl ketene dimer to an amount of 1.5% in the dried state showed only a 5% higher glycol resistance than the comparative group. Evening Example 8 In this example, 1420 Daniel's undried aromatic polyamide fiber yarn was coated in a non-pipeline at a rate of about 3◦0 m / min and at 200 ° C Under dry. These yarns were made into unidirectional strips with 60% by weight of fiber lozenge and 40% by weight of cured epoxy matrix. Use these strips to measure the shear strength of the narrow beam (Sh〇- (please read the precautions on the back before filling in, κ)-丨 install · order. 14. This paper size is applicable to China National Standard (CNS) A4 Specifications (210 X 297 public loan) -23-81.9.25,000; 0ib0 ^ Λ 6 Π 6 Printed by EX Gongxiao & Co., Ltd. of the Central Bureau of Economics and Trade of the Ministry of Economic Affairs. 5. Cooperatives ’description of the invention (22) rt Beam Shear Strength (SBSS) ) And compare with the strips made by the yarn of the comparison group. The characteristics of the fiber-resin interface in the aromatic polyamide compound are very important. In the aromatic polyamide compound, the most appropriate adhesion value depends on the function of the specific compound. Tensile strength and modulus in the composite are the main design criteria, and moderate adhesion values will lead to improved properties. This is particularly important for the composite structure of filament winding, for example, high-performance pressurized containers. In this case, in order to improve the strength displacement, one of the developments is to use low adhesion '' release 〃releused 〃) fibers. The fibers of the present invention exhibit low adhesion to matrix resins and provide significant benefits in these morphological applications. The method commonly used to detect fiber behavior in such applications is to measure the SBSS of composite strips containing these fibers. It can be seen that reducing SBSS by 30 to 50% in the case of pressurized vessels can lead to a final performance improvement of up to 50%. The SBSS of this example was measured according to ASTM D 2344—e Materials Association ") recommended method S MR 8-8 8. It was found that the SBSS of the aromatic polyamide treated with the hexadecenone dimer of the method of the present invention in an undried state to an amount of 1.2% is 33 MPa, while the SBSS of the yarn of the comparative group is 54 MPa . 6%。 The fiber of the present invention can lead to a reduction of 39.6% SBSS. Treated with cetyl ketene dimer in the dry state to the amount of 1.2% and 4%, at about C, please read the notes beforehand. Sun Huang wrote, too " China Η Standard (CNS) A 4 gauge (210x297 g; ":) 81. 2. 20,000 -24 _Π6_ V. Description of the invention (23) 3 0 0 m / min, then dry at 200 C The aromatic polyamide fiber was subjected to the same test, and the SBSS value was 52 MP a and 34 MP a〇C. Please read the precautions before you fill in. This order _ Ministry of Economic Affairs Printed line of β Gongxiaopu Cooperative · 81. 2. 20,000 The standard size of the paper is used for the Zhongming S Jiayubi (CHS) TM (2) 0x297 public release -25-

Claims (1)

6. Attachment 1U of the patent application park): Patent Application No. 811025 No. 10, Amendment of the scope of patent application in Chinese. Amendment in January 1982 1. A surface was coated with the reaction product generated by aromatic polyamide and surface reactant Coated aromatic polyamide fiber, wherein the amount of the surface reactant on the fiber is ◦. 05 to 8.0% by weight and contains the following formula of ketene dimer CR 2 R 2 C 2 Ο] ♦ i R 1 r R ”C 2 Ο] (I) where one or the same group may be the same or different, expressed as an alkyl group, cycloalkyl group, aryl group, alkenyl group, aralkyl group having 8 to 24 atoms Radical, aralkenyl or alkaryl; and each R 2 and radical may be the same or different, and expressed as a hydrogen atom or an alkyl or alkenyl group with 1 to 6 sulfonic atoms. Printed by the consumer cooperative 2. For the fiber of item 1 of the patent application scope, the R1 and RP groups in the general formula (I) are expressed as octyl, decyl, dodecyl, tetradecyl, hexadecyl , Octadecyl, eicosyl, behenyl, tetracosyl, tetradecenyl, hexadecenyl, octadecenyl, eicosyl Docosenyl and tetracosenyl. 3. Fibers according to item 1 of the patent application, wherein the R2 and R2 'groups in the general formula (I) represent Ci-C3 alkyl and Ci-C4 alkenyl , Or hydrogen. 4. For the fiber of item 1 of the patent application scope, the paper size of the ketene dimer is applicable to the Chinese National Standard (CNS) A 4 specifications (210 X 297 mol)-1-81.9.10,000 A7 A7 B7 C7 LOibG D7 VI. The patent application is a tetramer, tetradecenyl, hexadecyl, hexadecenyl, eicosyl or eicosyl diketene dimer. 5 .The fiber as claimed in item 1 of the patent scope, characterized in that the aromatic polyamide is made of repeating units of the following general formula (―NH — Ai — NH — CO — Aa — CO —) η where Αι It can be the same as or different from 八 2, and is expressed as a substituted or unsubstituted aromatic and / or polyaromatic and / or heteroaromatic ring. 6. For the fiber of item 5 of the patent application, it is subject to A / and A2 can be selected from 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 4,4 / biphenylene, 2,6-phenylene, 1 , 5— Support, 1,4-a support, phenoxyphenyl- 4,4 / -bi-support, benzyl-phenyl 3, 4 di-support, 2,5-pyridinium and 2,6-dimorpholine, At the same time, they may or may not be substituted by more than one substituent, these substituents include halogen, C, —C4 alkyl, phenyl, carbonyl group, C / -C4 alkyl group, oxy, nitro, Dialkylamine group, sulfanyl group, carboxyl group and sulfonamide group; meanwhile, the amide group can also be replaced by carbonylamide, azo or azooxy group. 7. If the fiber of item 5 of the patent application, the symptom is that the aromatic polyamide is poly-p-phenylene-isophthalamide. 8. The fiber according to item 5 of the patent application, characterized in that the aromatic polyamide is a poly-one-to-phenylene pair of phthalamide. 9. A fabric woven from the fibers of the first item of the patent application scope (first read the precautions on the back and then fill in this tile, --- installation-line, the Central Standards Bureau of the Ministry of Economic Affairs, the 8th consumer cooperation, and the printed paper size Applicable to China National Standards (CNS) A 4 regulations (210 X 297 fathers) a 2 — 81.9.10,000 Α7 Β7 C7 D7 0X80 Six, apply for a patent Fan Garden 〇10. If the application of the patent scope of the 9th fabric, when Compared with the same aromatic polyamide fiber but not woven with ketene dimer, it exhibits improved impact properties. 1 1. A surface for the manufacture of aromatic polyamide and surface A method of coating aromatic polyamide fiber coated with the reaction product generated by the reactant, this method includes the steps of: (a) coating the surface reactant ketene dimer of the following formula to a weight of 1 5-2 0 0 % Of water (calculated as dry fiber) of the un-dried aromatic polyamidoamine CR 7 R 2C 2〇] ♦ [R ”R2, C 2〇] where each R7 and R / 'groups may be the same Or different, and expressed as an alkyl group having 8 to 2 4 atoms, alkane group, aryl group , Alkenyl, aralkenyl, or alkaryl, aralkyl; and each of the R2 and R2 'groups may be the same or different, and is expressed as a hydrogen atom or an alkyl or alkene having 1 to 6 primary atoms (B) After the coating, the fiber is dried at a temperature of 30 to 4 ° C; and (c) if necessary, recoat the surface reactant at the same or different concentrations at least once, and then at each Dry the treated fiber after secondary coating. 1 2. If the method of item 11 of the patent application is applied, the paper size is applicable to the Chinese National Standard (CNS) A 4 specification (2 丨 0 X 297 Mm) -3-(Jing first read the precautions on the back and then fill out this page. 丨 Installed. Order _ Printed by the Central Standards Bureau of the Ministry of Economic Affairs R and Consumer Cooperative Co., Ltd. 81.9.10,000 A7 B7 C7 D7; 01bo: 6. Apply for a patent model The surface reactant is applied to the undried fiber in pure form. (Please read the precautions on the back before writing this tile, 1 3. If the method of item ii of the patent application is applied, the special feature is the surface reaction The agent is applied as an organic solvent solution with a concentration of 1 to 60% by weight. 1 4 . For the method of claim 11 of the patent application scope, the special emblem is that the surface reactant is applied in an aqueous emulsion of 1 to 60% by weight. The aqueous emulsion contains the ketene dimer dissolved in a p Η 2. 5 to 5 of the aqueous mixed liquid, this mixed liquid includes (a) ◦. 25 to 10% by weight of water-soluble, cation-modified starch R s-(Ο-R 1-NR 'R 5) „.1 · where η is 0.005 to 3, R s represents starch, R R and Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs R3 represents alkylene, hydroxyalkylene, phenylalkylene Or alkyl extension, R4, R5 may represent the same or different hydrogen, alkyl, alkenyl, alkaryl, aralkenyl, aryl, aralkyl or cycloalkyl, and (b) 0.05 Up to 5% by weight of basic lignin sulfonate or certain sodium formaldehyde sulfonate concentrate. 1 5. If the method of claim 14 is applied for, the sign is that the cationic water-soluble polymer is selected from cationic-charged ethylene plus paper. Chimao is suitable for China National Standard (CNS) A4 Specifications (210 X 297 K%) ~ 4-81.9.10,000 OlbO A7 B7 C7 D7 VI. Patent application Fanyuan Chengcheng polymers include polypropylene amide, polymethacryl amide and quaternized salted polypropylene amide and Mannich reaction product of polymethacrylamide. 16. If the method of claim 11 is applied for, the special emblem is that the undried aromatic polyamide fiber is neutralized with sodium masterbatch. (Jing first read the precautions on the back and then write this page. 丨 Installation · Ordering · The Ministry of Economic Affairs, Central Standards Bureau, R, Industry and Consumer Cooperation, Du Printing, and the paper size is applicable to China National Standards (CNS) A 4 specifications (210 X 297 male sewing ) -5-81.9.10,000