TW527377B - Manufacturing method for blocked aqueous dispersion of polyurethanes - Google Patents

Abstract

A blocked hydrophillic polyurethane with molecular weight of 500-40,000, 5-70% solid content and 5-200 milliequivalent per l00g polymer of sulfonic acid salt, can be prepared from following reactants: (a) organic isocyanates; (b) polyols, including polyether polyol, polyester polyol, polycarbonate, and polycaprolactone, that can participate in the polyaddition reactions with isocyanates; (c) polyols containing sulfonate group; (d) organic blocking agents capable of reacting with isocyanates. The blocked hydrophillic PU resins formed from above reactants can be applied for the anti-wrinkle treatment of cellulosic textiles with excellent performance.

Description

527377 A7 _B7__ V. Description of the invention () The present invention is that when synthesizing waterborne PU resin prepolymer, a polyhydric alcohol containing diacetate is introduced, and then the blocking reaction and water dispersion are performed. This series of waterborne PU dispersion can be applied to Cellulite-resistant fabrics * can improve the strength retention of fabrics * anti-sag angle and DP (Durable Press) rating. High-f inishing of cellulose-containing fabrics, such as beryllium-proof treatment, is designed to give the fabric the ability to maintain the stability of size and shape under normal use, and to give a smooth feel. Finishing and processing agents must be in the state of aqueous solution for fabric treatment. Therefore, only products that are aqueous-soluble or water-dispersible can be used for anti-crease processing. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). Until now, the substances used for anti-break processing have been Methylol compounds, such as: dimethylol ethylene urea), dimethylol ethylene dicyclohexyl hydrazone (€ 111 ^ 1: 11: / 1〇1 € 11117ca-oxyethylene urea) (DMDHEU), urea-forma lde-hyde ), Melamine-formaldehyde condensates, but after this kind of resin is processed to prevent moth, it will release nail base and endanger human health; In addition, in the presence of catalysts *, polyacids can also be used (Polycarboxylie acid) is used as an anti-brewing agent, as described in US Patent Nos. 49752 09, 4820307, and 5221285, but the use of polyacid as a cross-linking agent will cause the fabric tear strength to decrease. The use of blocked poly isocyanate as a defense agent has been reported in the following literatures:

Textilveredelung, 2 (7), 441 (1976);

Textilveredelung, 13 (11), 454 (1978); 1 2-This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 527377 Printed by A7 B7, Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs )

Ind. Ens. Chem. Prod. Res. Dec., 21 (1), 4-11 (1982) US Patent No. 5508370. Generally, when manufacturing water-based PU resin, an ionic group and / or ethylene oxide can be introduced into the polymer main chain as a hydrophilic group, so that polyurethane can be dispersed in water. Blocking type water-based PU resin is a kind of thermosetting resin, because when the dissociation temperature is reached, isocyanate will be generated, and isocyanate will react with the argonoxy group (0H group) -containing substance. This type of water-dispersible water-blocking PU resin can be used as a textile treatment agent and a surface treatment agent for wood, paper and plastic products. Blocking water-based PU resin used in anti-wrinkle processing of cellulose fibers must cooperate with other processing aids such as smoothing agents, softeners, cross-linking agents and catalysts, so the compatibility of water-based PU resins needs to be considered Therefore, the hydrophilic group of the water-based PU resin is preferably: (1) a compound containing a mineral salt, and / or (2) a structure containing an ethylene oxide. Therefore, the compatibility between the water-based PU resin with a molecular structure and the processing aid is relatively low. Well, when anti-brew processing, the amount of water-blocking water-based PU is about 3 ~ 25% (weight ratio), preferably 5 ~ 17%. Literatures on the use of sulfonate as a hydrophilic group in water-based PU resins include: German Patent 2,446,440, which uses mineral-containing diols as shown below

HfO-CH ~ CH2 ^ OfAVCHfB) 5〇-fCH2--CH--〇 ^ H R1 (CH2) q R2 so3-x + One of them 3 — This paper wave standard is applicable to China National Standard (CNS) Α4 specification (210 × 297 mm) Li) (Please read the notes on the back before filling in this page)

1T 527377 A7 _ _ _ B7_ V. Description of the invention () A and B: aliphatic hydrocarbons of carbon number 1 to 6 R1 and R2: hydrogen or aliphatic hydrocarbons of carbon number 1 to 4 or benzene ring X +: metal cations or money salts n, m: 0 or 1 ~ ^ 30 ο, p: 0 or 1 q: 0, 1, or 2 Japanese Patent Laid-Open No. 5-132537 uses mineral salts with the following structure (M〇3S) a-R- [X- (CH2) b-0H] 2 (M03S) aR- [X- (CH2CH20) m ~ H] 2 CH3 (M〇3S) aR- [X- (CH20iO) nH] 2 where a = 1 or 2 b: 1 to 5 m, n: an integer from 1 to 3 ^

^ a II X * — 0 one, one c — 0 — M: Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs of Lithium or Sodium or Potassium (Please read the precautions on the back before filling out this page) US Patent 5508370 Use 2 -Butyrate-1,4-butanediol (2-butene-1,4-diol) as a raw material mineral derivative. ^^ UPCT / US95 / 00030 5-sulfoisophthal ic acid monos〇dium salt is used as a mineral acid salt to make an aqueous PU resin adhesive. The Zhang scale is applicable _ Jiaxian (cns) 8 4 gauge 2 reads like 297) 527377 A7 B7 V. Description of the invention () US patent 4870129 uses h (-(2-ami noethyl) -2-ami noeth—ane mine Sodium acid salt is used to make water-based PU resins. The water-based PU resins have good spike characterization * and high strength physical properties at low pH (5 ~ 7). U.S. Patent 4,663,377 uses mineral water-containing PU dispersions and Mixing of isocyanate cross-linking agent can improve the heat resistance of water-based PU resin. Because the hydrophilic group of the block-type water-based PU resin has a salt structure, it has good compatibility with processing aids during beryllium finishing treatment. Therefore, the present invention selects diols containing acid salts in the molecule as the basic raw materials for the production of water-blocking water-based PU resins. The structure is as follows: (Please read the precautions on the back before filling this page) ο ο

Hf0CH2CH2 ^ 0C ^ C0f CH2CH20 ^ H S03Na 1 • (I) CH,

CEL | 0 0 _ Hf0-CH-CH2 ^ 0CH ^ C0f CH2 ~ CH ~ 0 ^ 2H S03Na 2 • (H) Printed by the Staff Consumer Cooperative of the Central Bureau of Standardization of the Ministry of Economic Affairs 0 0 HH) ~ CH2CH2CH2CH2 ^ 0 C- (〇 hC Of ch2ch2ch2ch2-o ^ 3h S03Na 呷 1 2? i? ^ f1 hoch2- c ~ ch2-0 c-(oh CO-ch2-c-ch2oh ••…

Ri S03Na CH20 (CH2CH0 ^ R2 where n · ^ 1 ^ —60 * (I) • αν) 1 2 The size of this paper is applicable to China National Standard (CNS) A4 (2 丨 0X297 mm) 527377 Central Ministry of Economic Affairs Standard Bureau employee consumer cooperatives printed A7 B7 V. Description of invention () nx = 1 ~ 100 n3 = 1 ~ 30 = 1 ~ 40 R, = Η or CH3 R2 = CHj 1¾ CH ^ CH2CHaS03Ha The above binary containing stearates Alcohol • It is 5 ~ 200 Meq / 100g in water-based PU resin. Its manufacturing method is 5-sulfoisophthalic acid monosodium salt or 5-sulfoisophthalic acid di-methyl ester sa 11, and diol is esterified (ester ifi cat i on) or vinegar exchange (transester if icat ion) method to form a multi-functional enjoyment containing a dish salt. The diisocyanates used in the present invention include aliphatic diisocyanates, or aromatic diisocyanates, or mixtures thereof: 1. Aliphatic diisocyanates, such as: Isophorone di isocyanate,

Dicyclohexylmethane-1,4'-diisoazepine salt (4,4'-dicyclohexylm-ethane di isocyanate; H / 2 MDI) N hexamethy lene di isocyanate; HDI),

Tetrainethy 1 xy 1 y 1 ene di isocyanate (TMXD I); 2. Aromatic diisocyanates, including: di pheny 1 me thane-4,4 '-dii so -cyanate) (MDI), Toluylene di isocyanate (TDI), 1 6 1 paper size applicable to Chinese National Standard (CNS) M specifications (2 丨 ox297 mm) (Please read the back first (Notes to fill out this page), τ

It printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 527377 A7 B7_. V. Description of the invention () xylylene diisocyanate (XDI) ° Molar ratio of diisocyanate and polyol used in the present invention ^ 〇3 / 01 ^ Is 1.1 ~ 2.5 * where the polyol part includes: 1. ester polyols: polyethylene adipate (PEA) polybutylene adipate (PBA) Polyhexylene adipate (PHA) Copolytr imethylolpropylene d iethylene adipate Copolytr imethylolpropylene d iethylene adipate Copolytrimethylene adipate Copolytrimethylolpropylene ethylene butylene a-dipate Copolytrimethylolpropylene ethylene butylene a-dipate Copolytrimethylolpropylene ethylene butylene a-dipate Copolytrimethylolpropylene ethylene butylene a-dipate Copolybutylene hexylene adipate Copolybutylene hexylene adipate Copolyhexylene neopentyl adipate Copolyhexylene neopentyl adipate Copolyhexylene neopentyl adipate 2 Ether polyol: Polytetramethylglycol ether (po lytetramethylene slycol; PTMG) Polypropylene glycol (PPPG) — 7 — The paper scale is applicable to China National Standard (CNS) A4 specification (210X297 mm) Ir ------ I — (Please read the first Please fill in this page for the matters needing attention) 呑 527377 A7 ^ _B7 _ V. Description of the invention (polyethylene glycol; PEG) 3. Polycarbonate polyol (Please read the notes on the back before (Fill in this page) 4. Polycaprolactone 5. The reaction temperature of the polyhydric alcohol blocking agent and isocyanate mixed on the M is 40 ° CM. Suitable blocking agents include: Religious purpose: female D diethyl malonate 2. Ethyl acetate cool category: such as acetoacet ic acid e-thy1 ester 3. Acetylacetone 4 Oximes: such as acetox i me, methyl ethyl ketone oxime, cyclohexanone oxime, acetophenone ox ime, g Same month issue (benzophenone ox i me) 5 · 内Lactams: such as €: -caprolactam treated cotton fabric, the physical properties of which are tested by standard methods: printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs a. The tear strength is ASTM D 5035-90 method. b. For DP rating (Durable Press) MTCC 124-1992 (l) IVA (2) 4 lb load 5 cycle ° c. Formazan content: Method 34 of the Ministry of Health, Welfare and Health of Japan. cL anti-beryllium angle: the method of ASTMD-1295-67. The water-blocking water-based PU of the present invention is suitable for various kinds of cotton-containing objects. ~ 8 — The paper scale is applicable to the Chinese National Standard (CNS) A4 specification (21Ό × 297 mm) 527377 A7 B7 _ 5. Description of the invention () Water-blocking water-based PU The synthesis of PU and its specific application examples for cotton fabric processing will be illustrated by the following examples and tables: Example 1: In a 1L separation reactor, weigh 20 grams of copolymerized butylene adipate Diol vinegar (copolybutylene hexylene adipate; PBHA, average molecular weight 2000), 80 grams of polydioxin (PPG, average molecular weight 4800), and 30 grams of the aforementioned formula (I), (n / = 25, molecular weight 2232) And pass in nitrogen, search and stir at 80 ° C for 10 minutes, and then add 21 grams of dicyclohexylmethane-4,4'-diisocyanate (H ^ MDI), and react at this temperature for five hours, Then add 9.37 grams of diethyl acetic acid for blocking reaction for two hours. At this time, it can be seen from the infrared spectrum that the absorption of N = C = 0 at 2270 × 11 ^ has completely disappeared, and it is determined that the blocking reaction has been completed. Finally, 480 grams of distilled water was added for water dispersion, and the UPU obtained an aqueous PU resin dispersion with a particle size of 75 nm, a solid content of 255¾, and a Brookfield viscosity (25 ° C) of llcps. Example 2: Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) In a 1L separation reactor, weigh 30 grams of copolybutylene adipate dimethyl Propylene glycol (copo 1 yhexy 1 ene neopenty 1 adipate; PGMA, average molecular weight 2000) * 70 grams of polypropylene glycol (PPG, average molecular weight 6000), and 50 grams of the aforementioned chemical formula (I), (n2 = 85, molecular weight 9832 ) * And 30 grams of polyethylene glycol (molecular weight 1000), and nitrogen gas * search and stir at 80 ° C for 10 minutes, and then add 28.3 grams of dicyclohexyl-4,4'-diisocyanate Salt (HiiMDI), reacted at this temperature for five hours, then added 9.2 g of e-caprolactam, and blocked the reaction for two hours. At this time, it can be seen from the infrared spectrum that the absorption of N = C = 0 at 2260 cm ^ has completely disappeared It is determined that the blockade response has been completed. -9 A paper size is applicable to Chinese National Standards (CNS) A4 specifications (210X297 public envy i 527377 A7 B7. V. Description of the invention) After completion, 650 grams of distilled water is added for water dispersion to obtain 65nm particle size, 25% solid content, Brookfiel viscosity (250CP for 15CP) Aqueous PU resin dispersion of S. Example 3: In a 1 L split-type reactor, 40 grams of polyhexylene adipate (PHA, average molecular weight 2000), 60 grams of Polyglycol (PPG, average molecular weight 3000) »and 30 g of the aforementioned chemical formula (IV), (r ^ = 24, R 丨 = H, R2 = CH), and pass in nitrogen, and mix at 80 ° C For 10 minutes, add 25.8 g of dicyclohexylformamidine-4,4'-diisocyanate (H | ZMDI), and react at this temperature for five hours, and then add 8.3 g of cyclohexanone to block it. The reaction took one hour. At this time, the infrared absorption of N = C = 0 at 2265cm ^ completely disappeared, and the blocking reaction was completed. Finally, 489 g of distilled water was added for water dispersion to obtain a particle size of 80 nm, Aqueous PU resin dispersion with a solid content of 25% and a Brookfield viscosity (25 ° C) of 14 cps. The typical anti-brew processing treatment formula is shown in the attached Table 1. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read first Note on the back then fill out this page) Cut the cotton fabric (130 X 70/40 X 40) into 40cm X 40cm Product, according to the formula shown in Table 1, formulated into a processing solution, immerse the cotton fabric in the processing liquid, first undergo pressure absorption (Padding), then dry at 120 ° C for two minutes, and then perform at 160 ° C. The cross-linking reaction, its add-on, anti-corner angle, tear strength retention rate, formaldehyde content, and DP rating are shown in Table 2 below. According to the data shown in the table, the molecular structure of the water-blocking water-based PII resin of the present invention contains mineral salt groups *, which not only increases the hydrophilic effect of water-based PU resin. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 527377 A7 B7 5. Description of the invention (), and good compatibility with processing aids, applied to the moth-proofing technology of cotton and related concomitant materials, can indeed improve the beryllium-proof effect of fabrics, and improve the industrial applicability of cellulose-containing fabrics. Achieve the intended purpose. To this end, Jiyi has filed a patent application in accordance with the law. Please review it and pray for the early approval of the patent in this case. (Please read the notes on the back before filling out this page) The paper printed by the Central Consumers' Bureau of the Ministry of Economic Affairs's Consumer Cooperatives applies the Chinese national standard (CNS) A4 specification (210X297 mm) 527377 A7 B7 V. Description of invention () Form —: Distilled horizontal slip agent, soft car, underdose magnesium chloride, weight% 79 · 6 1 3 1.8 modified DMDHEU (Note) water-based PU cat · 32 (Note) weight% 6 8 0.6 ::: DMDHEU zdimethy lol dihydroxyethy 1 ene urea cat · 32: Sn-type catalysts Table 2: (Please read the notes on the back before filling out this page) Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Example 1 'Example 2 Example 3 Weight increase rate (96) 1 · 96 2.08 2.10 Dry beryllium angle (Note) Warp beam + Weft beam (degree) 295 288 290 Tear strength retention rate (%) 81 88 85 Formaldehyde content (ppm) 45 30 40 DP rating (grade) 3.9 3.8 3.8 Note Blank cotton cloth dry anti-trafficking angle 210 degrees This paper size is applicable to China National Standard (CNS) A4 specification (2 丨 0X297 mm)

Claims (1)

527377 A8 B8 C8 D8 VI. Patent application scope 3 = 1 ~ 30 114 = 1 ~ 40 Rl = Η or CH3 R2 = CH3 or CH2 CH2 CH2 SO3 Na d · Organic blocking agent; including malonates and acetamidine Acetates, acetone, acetone, and ε-caprolactam; the above-mentioned reactant abc is firstly subjected to a prepolymerization reaction under normal pressure at 70 ~ pieces, and then the reactant is added. Obtain a water-blocking aqueous PU dispersion with a number average molecular weight of 5,000-40, 000. It can be used in cellulose-containing anti-wrinkle processing with good anti-wrinkle effect. 2. The method according to item 1 of the scope of the patent application, wherein the molar ratio of the reactant a · bcd is (11 ~ 2 5) ·!: (〇 "~! 3): (〇 巧, the reaction procedure In order to put the polyol, isocyanate and benzene ring sulfonate-containing polyol in the reaction bottle, react for 2-5 hours between 70 ~ 10 (rc, then add blocking agent for 1-2 hours, and finally disperse in water A blocked aqueous dispersion can be obtained. 3. According to the method described in the scope of the patent application, the content of benzene sulfonate is 5 to 200 milliequivalents per 100 grams of polymer, and the solid content of the aqueous resin is 5% ~ 70%. 4. According to the method described in the scope of patent application, item No. 3, where the blockage-type water-based PU uses a molar ratio of NC0 and 0H in the range of [] ~ ~ ^. 5. According to the patent application The method described in the first item of the scope, wherein the blockade] Water-based PU 'when applied to anti-wrinkle processing composition formula, the added amount is%; preferably 3 to 20%.' (Please read the precautions on the back before filling (This page), 1T 4 Printed by the Consumer Consumption Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -14-