Washable reactive polyurethane hot melt adhesive for fabric as well as preparation method and application of washable reactive polyurethane hot melt adhesive

Abstract

The invention discloses a washable reactive polyurethane hot melt adhesive for fabrics as well as a preparation method and application of the washable reactive polyurethane hot melt adhesive. The polyurethane hot melt adhesive is prepared from the following raw materials in parts by weight: 15-25 parts of isocyanate, 15-25 parts of polyether polyol, 15-35 parts of polyester polyol, 1-10 parts of epoxy resin, 1-10 parts of thermoplastic acrylic resin, 10-20 parts of tackifying resin, 0.01-0.1 part of a stabilizer and 0.05-0.5 part of a catalyst. The content of NCO in the washable reactive polyurethane hot melt adhesive for the fabric is 2.8%-3.5%. The textile fabric adhesive has the characteristics of washing resistance, high initial adhesion and strong adhesive strength, is good in softness and tolerance, can meet the use requirements of textile fabric adhesion, is simple in preparation method, and is easy to realize industrial production.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of polyurethane hot melt adhesive, in particular to a water-washing resistant reactive polyurethane hot melt adhesive for fabric, a preparation method and application thereof, which can be used for bonding of textile fabrics and substrates with water washing requirements. BACKGROUND

[0002] The textile industry, as one of the early application fields of PUR, has widely used PUR for fabric bonding since the late 20th century. This technology is not only applied to the bonding of water-repellent fabrics and breathable membranes of outdoor jackets, but also expanded to the bonding of different fabrics, the bonding of wetsuit fabrics, the bonding of water-washing clothing fabrics, and other aspects. PUR provides strong support for the quality and performance improvement of textiles with its unique bonding performance and stability. The water-washing resistant reactive polyurethane adhesive for fabric can be used for bonding of various textile fabrics and substrates with water washing requirements, and does not produce harmful gas volatilization during the compounding process, which is friendly to the human body and the environment. Traditional hot melt adhesives rely on moisture in the air for crosslinking and curing to form bonding, and the initial adhesion is largely dependent on the selection of polyester. However, the selection of high crystallinity polyester will weaken the final strength and even cause the phenomenon of adhesive failure.

[0003] Therefore, the present application is proposed. SUMMARY

[0004] In view of the shortcomings and deficiencies of the prior art, the present application aims to provide a water-washing resistant reactive polyurethane hot melt adhesive for fabric, a preparation method and application thereof, to solve the technical problems of poor bonding strength and low water washing level in the prior art, and to realize mass production. The present application also has the characteristics of better water washing resistance and strong bonding force.

[0005] To achieve the above-mentioned purpose, the present application adopts the following technical solutions:

[0006] A water-washing resistant reactive polyurethane hot melt adhesive for fabric is prepared from the following raw materials by weight: isocyanate 15-25 parts, polyether polyol 15-25 parts, high molecular weight polyester polyol 15-35 parts, epoxy resin 1-10 parts, thermoplastic acrylic resin 1-10 parts, tackifying resin 10-20 parts, stabilizer 0.01-0.1 parts, and catalyst 0.05-0.5 parts.

[0007] Optionally, the high molecular weight polyester polyol is an alkyd polyester polyol prepared by polycondensation of diols and diacids and derivatives thereof, the alkyd polyester polyol has an acid value less than 1.2 mgKOH / g, a hydroxyl value of 20-100 mgKOH / g, a number average molecular weight in the range of 1000-5000, and a functionality of 2; preferably, the diols are one or more of ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, and hexanediol; preferably, the diacids are polybasic carbon chain diacids or aromatic acids; more preferably, the diacids and derivatives thereof are one or more of terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, adipic acid, and succinic acid.

[0008] Optionally, the polyether polyol is one or more of ethylene oxide, propylene oxide, and butylene oxide obtained by polymerization.

[0009] Optionally, the polyether polyol has a polymer molecular weight in the range of 400-3000 and a functionality of 2; preferably, the polyether diol is an EO / PO copolymer diol with a number average molecular weight of 1000-4000.

[0010] Optionally, the isocyanate is at least one of 4,4'-diphenylmethane diisocyanate, diphenylmethane-2,4-diisocyanate, 1,5-naphthalene diisocyanate, p-toluenesulfonyl isocyanate, and 4,4'-dicyclohexylmethane diisocyanate; preferably, the isocyanate is 4,4'-diphenylmethane diisocyanate.

[0011] Optionally, the thermoplastic acrylic resin is at least one of an amino acrylic resin and a hydroxyl acrylic resin, preferably the hydroxyl acrylic resin.

[0012] Optionally, the epoxy resin is prepared by polycondensation of one of a polyamine, a polyphenol, a polyacid, or a polyol with epichlorohydrin, preferably the epoxy resin is a phenolic epoxy resin.

[0013] Optionally, the tackifying resin is one or both of a phenolic resin, a terpene resin, and a pure monomer petroleum resin, preferably the petroleum resin.

[0014] Optionally, the stabilizer is one or both of phosphoric acid and erucic acid, preferably the stabilizer is phosphoric acid.

[0015] Optionally, the catalyst is 2,2-dimorpholinyl diethyl ether (DMDEE).

[0016] The present application also provides a method for preparing a wash-resistant reactive polyurethane hot melt adhesive for fabrics, comprising the following steps:

[0017] Step 1, respectively, take polyether polyol, high molecular weight polyester polyol, epoxy resin, thermoplastic acrylic resin and tackifying resin by weight parts into the reaction kettle;

[0018] Step 2, control the temperature of the reaction kettle at 100-150 DEG C, the pressure is kept between-0.06-0.095 MPa, melt and dehydrate 1-2h under stirring;

[0019] Step 3, after dehydration, cool to 60-85 DEG C, add catalyst, stabilizer and isocyanate into the reaction kettle, keep the temperature of the reaction kettle at 80-100 DEG C, the vacuum degree is kept between-0.06-0.095 MPa, stirring reaction 1-3h;

[0020] Step 4, stop stirring, defoaming 10-20 min, filter, discharge, get the fabric washable reactive polyurethane hot melt adhesive;

[0021] Step 5, the fabric washable reactive polyurethane hot melt adhesive is placed in a sealed package, filled with inert gas protection.

[0022] The application also provides a device using the fabric washable reactive polyurethane hot melt adhesive, including automatic equipment continuous production line or manual production line suitable for roll coating, spraying, point coating, blade coating.

[0023] The application also provides an application of the fabric washable reactive polyurethane hot melt adhesive, which can be used for bonding of various textile fabrics with washing requirements.

[0024] The beneficial effects of the application are as follows:

[0025] Compared with the prior art, the fabric washable one-component moisture curing reactive polyurethane hot melt adhesive provided by the application has low viscosity, good flowability, and is suitable for spraying, rolling, scraping, point coating and other processes. The adhesive prepared by the application has very high initial adhesion, can provide strong peeling force in the initial stage of bonding and has good bonding stability, high final strength and excellent wash resistance, and can satisfy the non-damage of the substrate after more than 100 times of washing. DETAILED DESCRIPTION

[0026] The technical solutions in the application will be described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the application, not all. Based on the embodiments of the application, all other embodiments obtained by those skilled in the art without creative labor are within the protection scope of the application.

[0027] The washable reactive polyurethane hot melt adhesive for fabric, the preparation method and the application thereof are described in detail below. The contents not described in detail in the embodiments of the present application belong to the prior art known to those skilled in the art. The specific conditions not indicated in the embodiments of the present application are carried out according to the conventional conditions in the art or the conditions suggested by the manufacturers. The reagents or instruments used in the present application are not indicated by the manufacturers, and are all conventional products that can be purchased on the market.

[0028] The washable reactive polyurethane hot melt adhesive for fabric according to the present application is mainly made of the following raw materials by weight: isocyanate 15-25 parts, polyether polyol 15-25 parts, high molecular weight polyester polyol 15-35 parts, epoxy resin 1-10 parts, thermoplastic acrylic resin 1-10 parts, tackifying resin 10-20 parts, stabilizer 0.01-0.1 parts, catalyst 0.05-0.5 parts. The high molecular weight polyester polyol is alcohol acid polyester polyol made by condensation reaction of dihydric alcohol and diacid and its derivatives, the acid value of the alcohol acid polyester polyol is less than 1.2 mgKOH / g, the hydroxyl value is 20-100 mgKOH / g, the number average molecular weight is in the range of 1000-5000, and the functionality is 2; preferably, the dihydric alcohol is one or more of ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, and hexanediol; preferably, the diacid is polybasic carbon chain diacid or aromatic acid; more preferably, the diacid and its derivatives are one or more of terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, adipic acid, and succinic acid; the high crystallinity polyester diol can improve the initial adhesion of the polyurethane hot melt adhesive. The polyether polyol is obtained by polymerization of one or more of ethylene oxide, propylene oxide, and butylene oxide; the polymer molecular weight of the polyether polyol is in the range of 400-3000, and the functionality is 2; preferably, the polyether diol is an EO / PO copolymer diol with a number average molecular weight of 1000-4000. The isocyanate can be at least one of 4,4'-diphenylmethane diisocyanate, diphenylmethane-2,4-diisocyanate, 1,5-naphthalene diisocyanate, p-toluenesulfonyl isocyanate, and 4,4'-dicyclohexylmethane diisocyanate; preferably, 4,4'-diphenylmethane diisocyanate; the isocyanate has high reactivity, and the polyurethane material synthesized from aliphatic isocyanate and aromatic isocyanate has higher strength, wear resistance, and heat resistance. The thermoplastic acrylic resin can be at least one of amino acrylic resin and hydroxyl acrylic resin, preferably hydroxyl acrylic resin. The epoxy resin can be obtained by condensation reaction of one of polyamine, polyphenol, polyacid, or polyol with epichlorohydrin, preferably phenolic epoxy resin. The tackifying resin can be one or two of phenolic resin, terpene resin, and pure monomer petroleum resin, preferably petroleum resin. The stabilizer can be one or two of phosphoric acid, erucic acid, and oxalic acid, preferably phosphoric acid. The catalyst can be 2,2-dimorpholinyl diethyl ether (DMDEE).

[0029] The preparation method of the wash-resistant reactive polyurethane hot melt adhesive for fabrics according to the present application comprises the following steps: Step 1, respectively weighing, in parts by weight, polyether polyol, high-molecular-weight polyester polyol, epoxy resin, thermoplastic acrylic resin and tackifying resin into a reaction kettle; Step 2, controlling the temperature of the reaction kettle at 100-150 DEG C, keeping the pressure at-0.06 to-0.095 MPa, melting and dehydrating for 1-2 hours under stirring; Step 3, after dehydration, cooling to 60-85 DEG C, adding catalyst, stabilizer and isocyanate into the reaction kettle, keeping the temperature of the reaction kettle at 80-100 DEG C, keeping the vacuum degree at-0.06 to-0.095 MPa, stirring for 1-3 hours; Step 4, stopping stirring, defoaming for 10-20 minutes, filtering, discharging, obtaining the wash-resistant reactive polyurethane hot melt adhesive for fabrics; Step 5, placing the wash-resistant reactive polyurethane hot melt adhesive for fabrics into a sealed package, filling with inert gas for protection.

[0030] The equipment using the wash-resistant reactive polyurethane hot melt adhesive for fabrics according to the present application can comprise an automatic equipment continuous production line or a manual production line suitable for roll coating, spray coating, point coating and blade coating.

[0031] The wash-resistant reactive polyurethane hot melt adhesive for fabrics according to the present application can be used for bonding various types of textile fabrics requiring washing.

[0032] Compared with the prior art, the wash-resistant reactive polyurethane hot melt adhesive for fabrics and the preparation method thereof provided by the present application have at least the following advantages:

[0033] (1) The wash-resistant reactive polyurethane hot melt adhesive for fabrics provided by the present application is polymerized by using the prepolymer method and adjusting the molecular weight distribution of the synthesized polyurethane resin, which can greatly improve the initial adhesion and wettability of the polyurethane hot melt adhesive to the bonding surface.

[0034] (2) The wash-resistant reactive polyurethane hot melt adhesive for fabrics provided by the present application uses a specific thermoplastic acrylic resin as a tackifying resin, which can increase the viscosity of the adhesive and the initial adhesion of the adhesive; in order to further increase the initial adhesion of the hot melt adhesive polymer, the tackifying resin is used to improve the adhesion; the bonding strength of the hot melt adhesive is high, which can improve the overall durability and wash resistance after bonding, and can be applied to the bonding of various wash-resistant fabric substrates.

[0035] (3) The present application uses high-molecular-weight polyester polyol, which is synthesized from dihydric alcohol and diacid, wherein the diacid contains polybasic carbon chain diacid or aromatic acid and its derivatives; due to the regular structure of the carbon chain with six or more carbon atoms or the aromatic ring, the prepared polyurethane hot melt adhesive has fast crystallization speed and good hydrolysis resistance, which can meet the requirements of fast polyurethane bonding speed and wash resistance.

[0036] (4) The epoxy resin used in the application can improve the bonding crosslinking density and rigidity, increase the bonding strength and rigidity of the hot melt adhesive and the fabric, and make the bonding performance of the composite material excellent, thereby having better wash resistance.

[0037] (5) Compared with the prior art, the wash-resistant reactive polyurethane hot melt adhesive for fabric provided by the application has the characteristics of high initial adhesion, large bonding strength, strong wash resistance and easy industrial production.

[0038] As can be seen from the above, the embodiment of the application has the characteristics of wash resistance and strong adhesion at the same time, and improves the service life of the composite material.

[0039] In order to more clearly show the technical solutions provided by the application and the technical effects generated, the wash-resistant reactive polyurethane hot melt adhesive for fabric provided by the application and the preparation method and application thereof are described in detail below with specific embodiments.

[0040] All raw materials of the embodiment of the application are described as follows, but are not limited to these materials:

[0041] Isocyanate: MDI100, 4,4'-diphenyl methane diisocyanate;

[0042] Polyether polyol: PPG-2000, polypropylene glycol, hydroxyl value is 56.1 mgKOH / g, number average molecular weight is 2000;

[0043] Polyester polyol 1: PNA-2000, polyneopentyl glycol phthalate diol, hydroxyl value is 56.1 mgKOH / g, acid value is 0.5 mgKOH / g, number average molecular weight is 4000;

[0044] Polyester polyol 2: PAA-3000, polyhexamethylene adipate diol, hydroxyl value is 37.4 mgKOH / g, acid value is 0.1 mgKOH / g, number average molecular weight is 2000;

[0045] Polyester polyol 3: PNH-5000 refers to polybutanedioic acid-neopentyl glycol-1,6 hexanediol diol, hydroxyl value is 22.44 mgKOH / g, acid value is 0.2 mgKOH / g, number average molecular weight is 5000;

[0046] Tackifying resin: petroleum resin;

[0047] Epoxy resin: bisphenol A type liquid epoxy resin E-51 (0164);

[0048] Thermoplastic acrylic resin: Mitsubishi thermoplastic acrylic resin (BR106);

[0049] Stabilizer: phosphoric acid;

[0050] Catalyst: 2,2-dimorpholinyl diethyl ether (DMDEE);

[0051] The preparation method of the polyurethane hot melt adhesive of Examples 1-3 is as follows:

[0052] According to the proportions in Table 1, polyester polyol, polyether diol, epoxy resin, acrylic resin, tackifying resin were added to the reaction vessel, the temperature was controlled between 130℃, the pressure was maintained between-0.09MPa, melting and dehydrating for 1h, then cooling to 80℃, catalyst, stabilizer and isocyanate were added to the reaction kettle, the temperature was maintained at 90℃, the vacuum degree was maintained at-0.09MPa, stirring for 1h; after the reaction was completed, the stirring was stopped, and the bubble was removed for 20min, filtered, discharged, and the water-washing resistant reactive polyurethane hot melt adhesive for fabric was prepared.

[0053] The water-washing resistant reactive polyurethane hot melt adhesive for fabric prepared by Examples 1-3 and the water-washing resistant reactive polyurethane hot melt adhesive for fabric commercially available in Comparative Examples 1-2 were subjected to the following parallel comparison under the same conditions.

[0054] Performance detection:

[0055] (1) Rotational viscosity: CAP2000 cone and plate viscometer was used to test the rotational viscosity at 110℃, and the flowability was characterized.

[0056] (2) Peel strength: the prepared hot melt adhesive was used to bond any long 25cm, wide 1.5cm long strip of textile fabric in the environment of (RT: 25℃, RH: 50%), the interlayer T-type peel strength after bonding for 24h was tested, and the average value was obtained by testing 5 samples.

[0057] (3) Washing performance: in the washing machine, the water temperature was 20-30℃, and the continuous washing was 100 times, the drying was half an hour at 40℃, and the delamination of the adhesive bonding was checked.

[0058] The performance detection results are shown in Table 1.

[0059] Table 1

[0060] Item Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Isocyanate 25 20 15 / / Polyether polyol 15 20 25 / / Polyester polyol 1 7 15 10 / / Polyester polyol 2 6 10 14 / Polyester polyol 3 7 10 10 / / Epoxy resin 10 5 3 / / Thermoplastic acrylic resin 10 5 3 / / Tackifying resin 20 15 20 / / Stabilizer 0.01 0.05 0.1 / / Catalyst 0.05 0.1 0.5 / / Rotational viscosity / mpa.s 8500 8350 8750 8550 8800 Water washing times >100 >100 >100 60 80 Peeling strength N / 15mm 8.95 8.32 8.66 8.74 8.90

[0061] As can be seen from Table 1, compared with the comparative examples, the adhesive of the examples of the application uses specific isocyanate, polyether polyol, epoxy resin and thermoplastic acrylic resin and tackifying resin, and the polyester polyol with different hydroxyl value, acid value and number average molecular weight, which has a carbon chain of more than six or an aromatic ring, is used, the viscosity of the water-washing resistant reactive polyurethane hot melt adhesive for fabric obtained is moderate, has good hot melt fluidity and bonding strength, and the washing resistance is more excellent.

[0062] From the above, it can be seen that the washable reactive polyurethane hot melt adhesive for fabric described in the embodiment of the present application can be used for bonding of textile fabrics, has high bonding strength, and has excellent washability, and can be applied and popularized to bonding of various washable fabrics.

[0063] The above description is merely preferred specific embodiments of the present application, but the protection scope of the present application is not limited thereto, and any changes or replacements within the technical scope disclosed by the present application can be easily thought of by those skilled in the art, and should be covered within the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.

Claims

1. A wash-resistant reactive polyurethane hot melt adhesive for fabrics, characterized in that, It is made from raw materials containing the following components in parts by weight: 15-25 parts isocyanate, 15-25 parts polyether polyol, 15-35 parts high molecular weight polyester polyol, 1-10 parts epoxy resin, 1-10 parts thermoplastic acrylic resin, 10-20 parts tackifying resin, 0.01-0.1 parts stabilizer, and 0.1-1 parts catalyst.

2. The wash-resistant reactive polyurethane hot melt adhesive for fabrics according to claim 1, characterized in that, The polyether polyol is obtained by polymerization of one or more of ethylene oxide, propylene oxide, and butane oxide.

3. The wash-resistant reactive polyurethane hot melt adhesive for fabrics according to claim 2, characterized in that, The polymer molecular weight range of the polyether polyol is 400 to 3000, and the functionality is 2.

4. The wash-resistant reactive polyurethane hot melt adhesive for fabrics according to claim 1, characterized in that, The high molecular weight polyester polyol is an alkyd polyester polyol prepared by polycondensation reaction of diol and diacid and its derivatives. The alkyd polyester polyol has an acid value of less than 1.2 mgKOH / g, a hydroxyl value of 20 to 100 mgKOH / g, a number average molecular weight range of 1000 to 5000, and a functionality of 2.

5. The wash-resistant reactive polyurethane hot melt adhesive for fabrics according to claim 4, characterized in that, The dicarboxylic acid and its derivatives are one or more of terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, adipic acid, and succinic acid; and / or the diol is one or more of ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, and hexanediol.

6. The wash-resistant reactive polyurethane hot melt adhesive for fabrics according to claim 1, characterized in that, The epoxy resin is prepared by polycondensation reaction of one of the following: polyamine, polyphenol, polyacid, or polyol, with epichlorohydrin.

7. The wash-resistant reactive polyurethane hot melt adhesive for fabrics according to claim 1, characterized in that, The thermoplastic acrylic resin is one or both of amino acrylic resin and hydroxy acrylic resin; and / or, the tackifying resin is one or both of petroleum resin and phenolic resin.

8. The wash-resistant reactive polyurethane hot melt adhesive for fabrics according to claim 1, characterized in that, The isocyanate is at least one selected from 4,4'-diphenylmethane diisocyanate, diphenylmethane-2,4-diisocyanate, 1,5-naphthalene diisocyanate, p-toluenesulfonyl isocyanate, and 4,4'-dicyclohexylmethane diisocyanate; and / or, the stabilizer is one or more selected from erucic acid, phosphoric acid, and oxalic acid; and / or, the catalyst is 2,2-dimorpholinodiethyl ether (DMDEE).

9. A method for preparing a wash-resistant reactive polyurethane hot melt adhesive for fabrics according to any one of claims 1 to 8, characterized in that, Includes the following steps: Step 1: Weigh out the polyether polyol, polyester polyol, epoxy resin, thermoplastic acrylic resin and tackifying resin by weight and add them to the reaction vessel. Step 2: Control the temperature of the reactor at 100-150℃ and maintain the pressure between -0.06 and -0.095 MPa, and stir to melt and dehydrate for 1-2 hours; Step 3: After dehydration, cool down to 60-85℃, add catalyst, stabilizer and isocyanate to the reaction vessel, maintain the temperature of the reaction vessel at 80-100℃, maintain the vacuum degree between -0.06 and -0.095 MPa, and stir the reaction for 1-3 hours. Step 4: Stop stirring, degas for 10-20 minutes, filter, and discharge to obtain a water-resistant reactive polyurethane hot melt adhesive for fabrics. Step 5: Place the fabric in a sealed package using a water-resistant reactive polyurethane hot melt adhesive and fill it with inert gas for protection.

10. The application of the wash-resistant reactive polyurethane hot melt adhesive for fabrics according to any one of claims 1-8, characterized in that, Used for bonding various textile fabrics that require washing.