• 专利附录
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    • 专利摘要:
    A method of manufacturing a moisture-curing reactive hot-melt polyurethane adhesive for textile lamination, which comprises the steps of: (1) mixing and stirring the polyether polyol 4000E, polyester polyol 3000H, polyester polyol 2000N and an antioxidant, heating the mixture to about 120 ° C and dehydrating for 0.5 hours under a vacuum of less than 100 Pa; (2) adding a tackifying resin, heating the mixture to 135-140 ° C and dehydrating for 1.5 hours under a vacuum of less than 100 Pa; (3) lowering the temperature to 87 ° C, adding 4,4'-diphenylmethane diisocyanate and a catalyst, stirring the mixture, and reacting for 2 hours under a vacuum of less than 100 Pa; (4) reducing the vacuum, adding white carbon black, stirring the mixture rapidly until homogeneity is achieved, and stirring further for 10 minutes under a vacuum of less than 100 Pa; and (5) rapid unloading at a temperature of 85-100 ° C, packaging and then curing for 4 hours at 80-85 ° C to obtain the target product. When used in textile lamination, the product has excellent peel strength, a relatively short open time, good hydrolysis resistance, and desirable storage stability.
    公开号:CH710287B1
    申请号:CH00396/16
    申请日:2014-08-28
    公开日:2017-01-31
    发明作者:Li Zehlong；Zhu Wanyu；Xiao Hupeng；Ma Hongwei；Zeng Zuoxiang；Shen Yan
    申请人:Kunshan tianyang hot melt adhesive co ltd；Shanghai tianyang hot melt adhesive co ltd；Univ East China Science & Tech；
    IPC主号:
    专利说明:

    Technical area
    The present invention relates to a method for producing a moisture-curing, reactive hot-melt polyurethane adhesive for use in textile lamination.
    background
    [0002] Thanks to their properties, such as fast binding, non-polluting, non-toxic and less volatile organic compounds (VOC's), hot-melt adhesives have become increasingly important. Conventional hot melt adhesives are typically based primarily on thermoplastic resins that allow them to cure and bond in a short time. However, hardened layers of such adhesives are sensitive to high temperatures, soluble in organic solvents and have poor adhesive power, which limits the use of such thermoplastic hot-melt adhesives. To overcome these deficits, new moisture-curing hot-melt polyurethane adhesives have been developed which, on the one hand, have advantages comparable to conventional hot-melt adhesives, including a strong initial tack and the ability to cure quickly and be fixed in a specific location, and on the other hand allow chemical crosslinking to occur within the array of physically cured layers, which gives the adhesive layers considerably improved adhesiveness as well as resistance to water and solvents, etc. Therefore, these new hot melt adhesives have the advantages of both conventional, solvent-based adhesives and thermoplastic hot melt adhesives.
    A moisture-curing, reactive hot-melt polyurethane adhesive is a polyurethane adhesive which contains terminal NCO groups. During application, heat is used to melt the adhesive, and in the adhesive layer, which receives the initial tack after it has been cooled and physically cured, the terminal NCO groups within the adhesive layer react with moisture in the air or with active hydrogen compounds on the Surface of the bound object (s), which enables further hardening due to chemical cross-linking. In addition to the advantages of conventional thermoplastic hot-melt adhesives, such as fast bonding and fixing at a certain point and relatively high initial adhesive strength, moisture-curing, reactive hot-melt polyurethane adhesives are also able to harden further through crosslinking, which leads to an extraordinary improvement in adhesion and cohesion strength etc. . of the adhesive layers. Therefore, moisture-curing, reactive hot-melt polyurethane adhesives are used extensively for textile lamination, as well as for gluing in the areas of rubber, plastic, metal, automobile production, textiles, shoes, bookbinding, wood and furniture, electronics, etc. Moisture-curing, reactive hot-melt polyurethane adhesives, which are produced according to the present invention, are essentially used for the lamination of textiles.
    There are two types of moisture-curing, reactive hot-melt polyurethane adhesives that are based on corresponding prepolymers, which are fully polymerized ethers and fully polymerized esters. Hot-melt polyurethane adhesives based on thoroughly polymerized ethers provide advantages such as low and overall stable melt viscosities, high water resistance, low costs, etc., but their initial and final adhesive strength are both inadequate. On the other hand, while hot-melt polyurethane adhesives based on fully polymerized esters have excellent initial and final adhesive strength, their resistance to hydrolysis and flexibility are less desirable. Moisture-curing, reactive hot-melt polyurethane adhesives, which are produced according to the present invention, are in principle advantageous in that they are produced from polyether polyol (s) mixed with polyester polyol (s) and therefore have the advantages of both the polyether-based and polyester-based moisture-curing, reactive hot-melt polyurethane adhesive.
    Summary of the invention
    It is therefore one of the objects of the present invention to address the above problems of conventional adhesives by proposing a moisture-curing, reactive, hot-melt polyurethane adhesive for use in textile lamination.
    It is a second object of the present invention to provide a method for producing such a moisture-curing, reactive, hot-melt polyurethane adhesive for use in textile lamination.
    In order to solve these problems, a method for the production of a moisture-curing, reactive hot-melt polyurethane adhesive for use in textile lamination comprises the following steps: 1) Mixing together of polyether polyol 4000E, polyester polyol 3000H, polyester polyol 2000N and an antioxidant with stirring, Heating to a temperature of about 120 ° C and dehydrating for 0.5 hours under a vacuum of less than 100 Pa; 2) adding a tackifying resin, increasing the temperature to 135-140 ° C and dehydrating for 1.5 hours under a vacuum of less than 100 Pa; 3) lowering the temperature to 87 ° C, adding MDI and a catalyst, stirring the mixture and maintaining the reaction for 2 hours at a temperature of 85-95 ° C under a vacuum of less than 100 Pa; 4) Release the vacuum, add white carbon, stir rapidly until homogeneity is achieved and continue stirring for 10 minutes under a vacuum of less than 100 Pa; and 5) maintaining the temperature at 85-100 ° C, rapid unloading and packaging, and aging for 4 hours in an oven at a temperature of 80-85 ° C, resulting in the target product wherein the polyester Polyol 3000H is a poly (1st grade) , 6-hexane glycol adipate) diol with a molecular weight of 3000, the polyester polyol 2000N a poly (neopentyl glycol adipate) diol with a molecular weight of 2000, the tackifying resin an acrylic resin, the polyether polyol 4000E a polyoxypropylene diol with a molecular weight of 4000, the antioxidant a Mixture of the antioxidant 1010 and the antioxidant 1076 and the MDI 4,4'-diphenylmethane diisocyanate; and wherein the number of parts by weight of the substances based on 100 parts by weight of the target product are respectively: 11-13 parts for the MDI, 37-51 parts for the polyether polyol 4000E, 8-13 parts for the polyester polyol 3000H, 8-13 parts for the polyester Polyol 2000N, 0.22 part for the antioxidant 1010, 0.22 part for the antioxidant 1076, 19-20 parts for the tackifying resin, 0.14 part for the catalyst and 0.5 part for the white carbon.
    According to a preferred embodiment, the catalyst is tin (II) octoate, which is mixed with bis (2,2-morpholinoethyl) ether in a weight ratio of 1: 1.
    The moisture-curing, reactive hot-melt polyurethane adhesives, produced according to the present invention, are in principle advantageous over conventional adhesives in that, due to their moisture-curing, reactive nature, they not only have the advantages of conventional thermoplastic hot-melt adhesives, such as rapid bonding and fixing to a certain point and relatively high initial adhesive strength, but also allow further hardening due to crosslinking, which leads to an astonishing improvement in the adhesion of the adhesive layer, cohesive strength, etc. and because they are made from polyether polyol (s) mixed with polyester polyol (s) that they have the benefits of both the polyether-based and polyester-based moisture-curing, reactive hot-melt polyurethane adhesives, ie stable melt viscosity (ies), high water resistance, low costs, high initial and final adhesive strength and high flexibility. When used in textile lamination, as shown in Table 1, moisture-curing, reactive hot-melt polyurethane adhesives produced according to the present invention have an average peel strength of about 20 N / 2.5 cm (a basis weight of 15 g / cm <2>) and high hydrolysis resistance, as a result of which they meet the requirements of the textile lamination industry for moisture-curing, reactive hot-melt polyurethane adhesives.
    Detailed description
    The present invention is described in more detail below with reference to the following examples, which, however, do not restrict the invention in any respect.
    example 1
    1) In a three-necked flask, 51 g of polyether polyol 4000E, 8 g of polyester polyol 3000H, 8 g of polyester polyol 2000N, 0.22 g of antioxidant 1010 and 0.22 g of antioxidant 1076 were added, homogenized by stirring and heated to a temperature of heated about 120 ° C followed by dehydration for 0.5 hours under a vacuum of less than 100 Pa. 2) 20 g of the tackifying resin was added to the flask and the temperature was raised to 135-140 ° C, followed by dehydration for 1.5 hours under a vacuum of less than 100 Pa. 3) After the temperature had been reduced to 87 ° C, 12 g of 4,4'-diphenylmethane diisocyanate (MDI), 0.07 g of tin (II) octoate and 0.07 g of bis (2,2-morpholinoethyl) ether were added (DMDEE) added and stirred. The reaction was then maintained for 2 hours at a temperature of 85-95 ° C under a vacuum of less than 100 Pa. 4) The vacuum was released and 0.5 g of white carbon added, followed by rapid stirring until homogeneity was achieved and further stirring for 10 minutes under a vacuum of less than 100 Pa. 5) With the temperature kept at 85-100 ° C, the reaction mixture was rapidly discharged and packed in an aluminum foil bag under a nitrogen atmosphere. The bag was then aged in an oven at a temperature of 80-85 ° C for 4 hours to give Product A.
    Example 2
    1) In a three-necked flask, 46 g of polyether polyol 4000E, 10 g of polyester polyol 3000H, 10 g of polyester polyol 2000N, 0.22 g of antioxidant 1010 and 0.22 g of antioxidant 1076 were added, homogenized by stirring and heated to a temperature of heated about 120 ° C followed by dehydration for 0.5 hour under a vacuum of less than 100 Pa. 2) 19 g of the tackifying resin was added to the flask and the temperature was raised to 135-140 ° C, followed by dehydration for 1.5 hours under a vacuum of less than 100 Pa. 3) After the temperature had been reduced to 87 ° C., 12 g of MDI, 0.07 g of tin (II) octoate and 0.07 g of DMDEE were added and stirred. The reaction was then maintained for 2 hours at a temperature of 85-95 ° C under a vacuum of less than 100 Pa. 4) The vacuum was released and 0.5 g of white carbon added, followed by rapid stirring until homogeneity was achieved and further stirring for 10 minutes under a vacuum of less than 100 Pa. 5) With the temperature kept at 85-100 ° C, the reaction mixture was rapidly discharged and packed in an aluminum foil bag under a nitrogen atmosphere. The bag was then aged in an oven at a temperature of 80-85 ° C for 4 hours to give a product B.
    Example 3
    1) In a three-necked flask 44 g of polyether polyol 4000E, 11 g of polyester polyol 3000H, 11 g of polyester polyol 2000N, 0.22 g of antioxidant 1010 and 0.22 g of antioxidant 1076 were added, homogenized by stirring and heated to a temperature of heated about 120 ° C followed by dehydration for 0.5 hour under a vacuum of less than 100 Pa. 2) 19 g of the tackifying resin was added to the flask and the temperature was raised to 135-140 ° C, followed by dehydration for 1.5 hours under a vacuum of less than 100 Pa. 3) After the temperature had been reduced to 87 ° C., 11 g of MDI, 0.07 g of tin (II) octoate and 0.07 g of DMDEE were added and stirred. The reaction was then maintained for 2 hours at a temperature of 85-95 ° C under a vacuum of less than 100 Pa. 4) The vacuum was released and 0.5 g of white carbon added, followed by rapid stirring until homogeneity was achieved and further stirring for 10 minutes under a vacuum of less than 100 Pa. 5) With the temperature kept at 85-100 ° C, the reaction mixture was rapidly discharged and packed in an aluminum foil bag under a nitrogen atmosphere. The bag was then aged in an oven at a temperature of 80-85 ° C for 4 hours to give Product C.
    Example 4
    1) In a three-necked flask 37 g of polyether polyol 4000E, 13 g of polyester polyol 3000H, 13 g of polyester polyol 2000N, 0.22 g of antioxidant 1010 and 0.22 g of antioxidant 1076 were added, homogenized by stirring and heated to a temperature of heated about 120 ° C followed by dehydration for 0.5 hour under a vacuum of less than 100 Pa. 2) 19 g of the tackifying resin was added to the flask and the temperature was raised to 135-140 ° C, followed by dehydration for 1.5 hours under a vacuum of less than 100 Pa. 3) After the temperature had been reduced to 87 ° C., 13 g of MDI, 0.07 g of tin (II) octoate and 0.07 g of DMDEE were added and the mixture was stirred. The reaction was then maintained for 2 hours at a temperature of 85-95 ° C under a vacuum of less than 100 Pa. 4) The vacuum was released and 0.5 g of white carbon added, followed by rapid stirring until homogeneity was achieved and further stirring for 10 minutes under a vacuum of less than 100 Pa. 5) With the temperature maintained at 85-100 ° C, the reaction mixture was rapidly discharged and packed in a bag made of aluminum foil under a nitrogen atmosphere. The bag was then aged in an oven at a temperature of 80-85 ° C for 4 hours to give a product D.
    Application examples
    The technical data for the moisture-curing, reactive hot-melt polyurethane adhesive A for use in textile lamination, for the moisture-curing, reactive hot-melt polyurethane adhesive B for use in textile lamination, for the moisture-curing, reactive hot-melt polyurethane adhesive C for use in textile lamination and for the moisture-curing, reactive hot-melt polyurethane adhesive D for use in textile lamination, which were obtained in Examples 1-4 described above, are shown in Table 1. The moisture-curing, reactive hot-melt polyurethane adhesives A, B, C and D were used for textile lamination through the following steps described below.
    The moisture-curing, reactive hot-melt polyurethane adhesive products A, B, C and D for use in textile lamination, which were produced in Examples 1-4 described above, were heated to a temperature of 120 ° C and then on appropriate polyester cotton cloths Rotary sieve with a mesh size of 0.45 µm applied. The coated polyester cotton cloths were pressed at a temperature of 80 ° C. with a pressure of 3 kgf / cm 2 and placed in an environment of constant temperature of 20 ° C. and constant humidity of 70% for 24 hours. The tissues were then cut into 2.5 cm wide and 20 cm long strips, which were then tested for the basis weight (weight of the adhesives applied to a unit area of the fabric) and the peel strength of the adhesives. The strips were then immersed in water and then tested for the peel strength of the adhesives after immersion. The results of these tests are summarized in Table 1.
    Table 1: Technical data of the moisture-curing, reactive hot-melt polyurethane adhesive and results of the tests of their peel strength after application.
    As indicated by the data shown in Table 1, show the moisture-curing, reactive hot-melt polyurethane adhesive according to the present invention at 120 ° C viscosities of about 5000 mPa · s and allow easy application with minimal penetration when this in the textile lamination be applied. The product with a basis weight of 15 g / m 2 had a peel strength of 19.92 N / 2.5 cm, which did not experience any significant reduction after washing with water, which shows that it had both a high peel strength and had good resistance to hydrolysis. In addition, although the resistance to hydrolysis within the moisture-curing, reactive hot-melt polyurethane adhesives A, B, C and D according to the invention was reduced, these were in any case still relatively desirable. Since Product B had the highest peel strength (ie, the highest peel strength per unit basis weight) and moderate viscosity, Example 2, which resulted in Product B, is considered the most preferred embodiment so that the formulation of Product B is optimal .
    The foregoing description is merely a basic illustration based on the concept of the present invention, and it is believed that any equivalent variant made according to the subject matter of the invention falls within the scope thereof.
    权利要求:
    Claims (2)
    [1]
    A process for the preparation of a moisture-curing, reactive hot-melt polyurethane adhesive, for textiles, comprising the following steps:A) Mixing 4000 molecular weight polyoxypropylene diol, 3000 molecular weight poly (1,6-hexane-glycoladipate) diol, 2000 molecular weight poly (neopentyl glycol adipate) diol and an antioxidant with stirring, heating to a temperature of about 120 ° C and dehydration for 0.5 hours under a vacuum of less than 100 Pa;B) adding an acrylic resin, raising the temperature to 135-140 ° C and dehydrating for 1.5 hours under a vacuum of less than 100 Pa;C) lowering the temperature to 87 ° C, adding MDI and a catalyst, stirring and reacting for 2 hours at a temperature of 85-95 ° C under a vacuum of less than 100 Pa;D) Degradation of the vacuum, addition of white carbon black, rapid stirring such that homogeneity is achieved, and further stirring for 10 minutes under a vacuum of less than 100 Pa; andE) Maintaining the temperature at 85-100 ° C, rapid unloading and packaging and aging for 4 hours in an oven at a temperature of 80-85 ° C to obtain the target product,wherein the antioxidant is a mixture of pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) and octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and the MDI is a 4,4-diphenylmethane diisocyanate; andwherein the number of parts by weight of the substances relative to 100 parts by weight of the target product are respectively: 11-13 parts for the MDI, 37-51 parts for the 4000 molecular weight polyoxypropylene diol, 8-13 parts for the poly (1,6-hexanglylene) -coladipate) diol having a molecular weight of 3000, 8-13 parts for the poly (neopentyl glycol adipate) diol having a molecular weight of 2000, 0.22 parts for the pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4 -hydroxyphenyl) propionate), 0.22 parts for the octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 19-20 parts for the acrylic resin, 0.14 part for the catalyst and 0, 5 parts for the Belarusian.
    [2]
    2. A process according to claim 1, wherein the catalyst tin (II) octoate is mixed with bis (2,2-morpholinoethyl) ether in a weight ratio of 1: 1.
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    同族专利:
    公开号 | 公开日
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2017-09-29| PCAR| Change of the address of the representative|Free format text: NEW ADDRESS: BELLERIVESTRASSE 203 POSTFACH, 8034 ZUERICH (CH) |
    2019-03-29| PL| Patent ceased|
    优先权:
    申请号 | 申请日 | 专利标题
    CN201304690478|2013-09-26|
    PCT/CN2014/085368|WO2015043353A1|2013-09-26|2014-08-28|Preparation method for moisture-curing polyurethane reactive hot melt adhesive for textile composition|
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