CN112745772A - High-elasticity hot melt adhesive material made of pure TPU (thermoplastic polyurethane) material and preparation process thereof - Google Patents
High-elasticity hot melt adhesive material made of pure TPU (thermoplastic polyurethane) material and preparation process thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/35—Heat-activated
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention relates to the technical field of high-molecular adhesives, in particular to a high-elasticity hot melt adhesive material made of a pure TPU material. The modified cross-linked TPU film layer is prepared from modified cross-linked TPU raw materials, and has the following gain effects: the invention adopts a material crosslinking modification method to form a pure TPU high-elasticity adhesive material with a 3-layer structure, obtains a plurality of high-elasticity adhesive materials with different properties by adjusting the crosslinking degree of a TPU intermediate layer material and matching the modified material, can be widely applied to the seams of underpants, underwear and the like, has wide application range, and can overcome the defects of poor hygroscopicity, poor heat resistance and poor flexibility of the existing seamless high-elasticity adhesive products; the pure TPU hot melt adhesive material is completely processed by using the TPU material, and the components of the pure TPU hot melt adhesive material are completely environment-friendly and recyclable.
Description
Technical Field
The invention relates to the technical field of high-molecular adhesives, in particular to a high-elasticity hot melt adhesive material made of a pure TPU material and a preparation process thereof.
Background
The high-elasticity rubber band is an indispensable material in the manufacturing process of underwear and underpants, and can meet the requirements of high elasticity and repeated stretching and recovery of the lower hem of the underwear and the waist of the underpants. However, the high-elasticity rubber band can generate seam edge bone bulges after being processed, and the appearance and the use comfort of the product are influenced.
The waist and the lower hem of the existing underpants are supported by rubber bands at places needing high elasticity, and can generate seam edge bones after being processed by a sewing process, the seam edge bones can influence the attractiveness of the underpants and the underwear, and the raised shape of the seam edge bones can also cause discomfort to a wearer. The seamless high-elastic glue products which are gradually emerging in recent years can partially replace the sewing process, the best product is the imported Baimei paste product, but the Baimei paste product belongs to a high import dependence product, the price rapidly rises in the recent years, and the wider application of the Baimei paste product in the underwear and underpants industry is limited. Secondly, the spandex fabric in the existing seamless high-elasticity rubber has the problem of poor hygroscopicity, and can cause discomfort to skin when used in summer.
In view of the above, a novel high-elastic hot-melt adhesive material is urgently needed to replace spandex fabrics in the existing high-elastic adhesive, so that the defect of dependence on Baimei adhesive in China is overcome, and the problems of poor hygroscopicity and heat resistance of Baimei adhesive are solved.
Disclosure of Invention
The invention aims to solve the defects of the existing high-elasticity hot melt adhesive material and provides the high-elasticity hot melt adhesive material which is made of pure TPU material, has high elasticity, high hygroscopicity, high heat resistance, wide application range and environmental protection.
In order to solve the technical problems, the invention adopts the following technical scheme:
a high-elastic hot-melt adhesive material made of pure TPU material comprises an upper layer, a middle layer and a lower layer, wherein the upper layer and the lower layer are TPU adhesive film layers, the middle layer is a modified cross-linked TPU layer,
the TPU film layer is prepared from TPU film raw materials, the modified cross-linked TPU layer is prepared from modified cross-linked TPU raw materials,
the modified cross-linked TPU raw material comprises the following components in percentage by mass: 97-99% of thermoplastic polyurethane elastomer, 0.1-0.8% of cross-linking agent, 0.1-0.5% of hydrolysis stabilizer, 0.2-0.5% of antioxidant, 0.5-1% of ultraviolet absorbent and 0.2-1% of silane coupling agent;
the TPU adhesive film comprises the following raw materials in percentage by mass: 50-55% of Thermoplastic Polyurethane (TPU), 13-26% of Thermoplastic Polyester (TPE), 5-16% of tackifier, 3-13% of functional filler and 3-16% of functional auxiliary agent, wherein the functional filler comprises organic filler and inorganic filler, and the functional auxiliary agent is one or a mixture of more of antioxidant, ultraviolet absorbent, antistatic agent, light stabilizer and hydrolysis stabilizer.
Preferably, the crosslinking agent in the modified crosslinked TPU layer is one or more of dicumyl peroxide (DCP), t-butyl cumyl peroxide (TBCP), dibenzoyl peroxide (BPO), di-t-butylperoxydiisopropylbenzene (BIPB);
the hydrolysis stabilizer is one or more of carbodiimide, liquid carbodiimide and epoxy compound;
the antioxidant is one or more of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl alcohol ester (antioxidant 1076), triisotridecyl phosphite or 4, 4' -para-isopropyldiphenyl C12-15-alcohol phosphite ester (antioxidant 1500), tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (antioxidant 1010);
the ultraviolet absorbent is one or more of 2- (2-hydroxy-3, 5-di-tert-amylphenyl) benzotriazole (ultraviolet absorbent UV-328), 2- [ 2-hydroxy-5- (1, 1, 3, 3-tetramethylbutyl) phenyl ] benzotriazole (ultraviolet absorbent UV-329), 2- (2H-benzotriazole-2-yl) -4, 6-di (1-methyl-1-phenylethyl) -phenol (ultraviolet absorbent UV-234);
the silane coupling agent is one or more of gamma-aminopropyltriethoxysilane (KH-550), gamma- (2, 3-glycidoxy) propyltrimethoxysilane (KH-560), N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane (KH-792), N-beta-aminoethyl) -gamma-aminopropyltriethoxysilane (KH-901), and N-beta- (aminoethyl) -gamma-aminopropylmethyldiethoxysilane (KH-602).
Preferably, the tackifier in the TPU film layer is one or a mixture of at least two of petroleum resin, rosin resin, maleated rosin, acrylic modified rosin, terpene resin, phenolic resin, terpene-phenolic resin or terpene-phenolic resin;
the inorganic filler is selected from any one or a mixture of at least two of calcium carbonate, kaolin, talcum powder, mica, powder, titanium dioxide, graphite powder, white carbon black or carbon black;
the organic filler is selected from any one or a mixture of at least two of polytetrafluoroethylene powder, polyphenylene sulfide powder or polyether sulfone powder;
the antioxidant is selected from one or more of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate, triisotridecyl phosphite or 4, 4' -p-isopropyldiphenyl C12-15-alcohol phosphite, and tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester;
the ultraviolet absorbent is one or more selected from 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate, 2- (2-hydroxy-3, 5-di-tert-amylphenyl) benzotriazole), 2- (2H-benzotriazole-2-yl) -4, 6-di (1-methyl-1-phenylethyl) -phenol;
the antistatic agent is selected from one or more of nonionic antistatic agents and composite antistatic agents;
the light stabilizer is selected from one or more of 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazole, 2- (2 ' -hydroxy-3 ', 5 ' -di-tert-pentylphenyl) benzotriazole, bis (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) sebacate or bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate.
Preferably, the preparation of the modified cross-linked TPU feedstock comprises the steps of: uniformly mixing the thermoplastic polyurethane elastomer, a crosslinking agent, a hydrolysis stabilizer, an antioxidant, an ultraviolet absorbent and a silane coupling agent in a mixer, pumping the mixture into a hopper of a double-screw extruder through a vacuum pump, extruding the mixture by the double-screw extruder to obtain modified crosslinked TPU particles, and drying the modified crosslinked TPU particles in a 60 ℃ drying oven for 6 hours;
the preparation of the TPU adhesive film raw material comprises the following steps: the thermoplastic polyurethane, the thermoplastic polyester, the tackifier and the functional filler are uniformly mixed in a mixer, and then are pumped into a hopper of a double-screw extruder through a vacuum pump, and are extruded by the double-screw extruder to obtain TPU adhesive film particles, and the TPU adhesive film particles are dried in a 60 ℃ oven for 6 hours.
A preparation process of a high-elasticity hot melt adhesive material made of pure TPU materials comprises the following steps: step 1:
sucking TPU glue film particles into a hopper of a No. 2 single-screw extruder of a composite extrusion casting machine through a vacuum pump, forming an ultrathin TPU glue film layer through a gap pressing agent, spraying the ultrathin TPU glue film layer on release base paper, pressing and cooling the TPU glue film layer by a composite roller and a conveying roller, conveying the TPU glue film layer to the tail end, cutting edges and winding to prepare a TPU glue film layer substrate;
step 2:
and (2) sucking the crosslinked TPU particles into a hopper of a No. 1 single-screw extruder of the composite extrusion casting machine through a vacuum pump, sucking the TPU adhesive film particles into a hopper of a No. 2 single-screw extruder of the composite extrusion casting machine through the vacuum pump, conveying the TPU adhesive film particles through a conveying roller, respectively spraying the TPU adhesive film particles on the TPU adhesive film layer of the TPU adhesive film layer substrate prepared in the step 1 through the No. 1 and No. 2 extruders in sequence, pressing and cooling the TPU adhesive film layer by a composite roller and the conveying roller to form an ultrathin TPU hot-melt adhesive material, conveying the TPU hot-melt adhesive material to the tail end to separate from a release base paper, cutting edges and rolling, and finishing the high.
Preferably, the temperatures of the barrel 1-6 sections of the No. 2 single-screw extruder in the step 1 are sequentially as follows: 135 deg.C, 140 deg.C, 145 deg.C, 150 deg.C, 155 deg.C and 160 deg.C, the temperatures of the die head 1-7 zones are set at 160 deg.C, 160 deg.C and 160 deg.C, and the die head is heated to 180 deg.C.
Preferably, the temperatures of the barrel 1-6 sections of the No. 1 single-screw extruder in the step 2 are sequentially as follows: 145 ℃, 150 ℃, 160 ℃, 180 ℃ and 180 ℃, the temperatures of the 1-7 areas of the die head are set as 165 ℃, 170 ℃, 180 ℃ and 180 ℃, and the die head is heated to 190 ℃; the temperature of the machine barrel 1-6 area of the No. 2 single screw extruder is as follows in sequence: 135 deg.C, 140 deg.C, 145 deg.C, 150 deg.C, 155 deg.C and 160 deg.C, the temperatures of the die head 1-7 zones are set at 160 deg.C, 160 deg.C and 160 deg.C, and the die head is heated to 180 deg.C.
Preferably, the thickness of the high-elasticity hot melt adhesive material made of the pure TPU material is 0.05-0.3 mm.
Preferably, the release liner is one of PP release paper or PE release paper.
Compared with the prior art, the invention has the following gain effects:
1. the high-elastic hot melt adhesive material made of the pure TPU material can overcome the defects that the edge seam is not attractive and uncomfortable to wear after the old underwear hem and the underwear waistband are sewn;
2. compared with the hot melt adhesive films made of other materials, the TPU hot melt adhesive film adopted by the high-elasticity hot melt adhesive material made of the pure TPU material is softer in hand feeling under the same thickness, and is more suitable for compounding and bonding of textile fabrics in the field of clothing. The cloth adhered by the TPU hot melt adhesive film does not have plastic feeling or foreign body feeling, and is comfortable to wear;
3. the invention adopts a material crosslinking modification method to form a pure TPU high-elastic adhesive material with a 3-layer structure, and obtains a plurality of high-elastic adhesive materials with different properties by adjusting the crosslinking degree of a TPU intermediate layer material and matching the modified material, so that the TPU high-elastic adhesive material can be widely applied to the sewing positions of underpants, underwear and the like, and has wide application range;
4. the invention can overcome the defects of poor hygroscopicity, poor heat resistance and poor flexibility of the existing seamless high-elasticity rubber product;
5. the existing seamless high elastic glue product mainly comprises a TPU surface layer and a spandex fabric layer, wherein the spandex fabric layer is mainly composed of polyurethane, but 10% -30% of other fabrics are required to be added for blending, so that the material cannot achieve the aim of complete environmental protection; the pure TPU hot melt adhesive material is completely processed by using the TPU material, and the components of the pure TPU hot melt adhesive material are completely environment-friendly and recyclable.
Drawings
FIG. 1 is a flow chart of the preparation process of the present invention.
Fig. 2 is a schematic structural diagram of the present invention.
Detailed Description
The invention relates to a high-elastic hot melt adhesive material made of pure TPU material, which comprises an upper layer, a middle layer and a lower layer, wherein the upper layer and the lower layer are TPU adhesive film layers, the middle layer is a modified cross-linked TPU layer,
the TPU film layer is prepared from TPU film raw materials, the modified cross-linked TPU layer is prepared from modified cross-linked TPU raw materials,
the modified cross-linked TPU raw material comprises the following components in percentage by mass: 97-99% of thermoplastic polyurethane elastomer, 0.1-0.8% of cross-linking agent, 0.1-0.5% of hydrolysis stabilizer, 0.2-0.5% of antioxidant, 0.5-1% of ultraviolet absorbent and 0.2-1% of silane coupling agent;
the TPU adhesive film comprises the following raw materials in percentage by mass: 50-55% of Thermoplastic Polyurethane (TPU), 13-26% of Thermoplastic Polyester (TPE), 5-16% of tackifier, 3-13% of functional filler and 3-16% of functional auxiliary agent, wherein the functional filler comprises organic filler and inorganic filler, and the functional auxiliary agent is one or a mixture of more of antioxidant, ultraviolet absorbent, antistatic agent, light stabilizer and hydrolysis stabilizer.
Preferably, the crosslinking agent in the modified crosslinked TPU layer is one or more of dicumyl peroxide (DCP), t-butyl cumyl peroxide (TBCP), dibenzoyl peroxide (BPO), di-t-butylperoxydiisopropylbenzene (BIPB);
the hydrolysis stabilizer is one or more of carbodiimide, liquid carbodiimide and epoxy compound;
the antioxidant is one or more of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl alcohol ester (antioxidant 1076), triisotridecyl phosphite or 4, 4' -para-isopropyldiphenyl C12-15-alcohol phosphite ester (antioxidant 1500), tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (antioxidant 1010);
the ultraviolet absorbent is one or more of 2- (2-hydroxy-3, 5-di-tert-amylphenyl) benzotriazole (ultraviolet absorbent UV-328), 2- [ 2-hydroxy-5- (1, 1, 3, 3-tetramethylbutyl) phenyl ] benzotriazole (ultraviolet absorbent UV-329), 2- (2H-benzotriazole-2-yl) -4, 6-di (1-methyl-1-phenylethyl) -phenol (ultraviolet absorbent UV-234);
the silane coupling agent is one or more of gamma-aminopropyltriethoxysilane (KH-550), gamma- (2, 3-glycidoxy) propyltrimethoxysilane (KH-560), N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane (KH-792), N-beta-aminoethyl) -gamma-aminopropyltriethoxysilane (KH-901), and N-beta- (aminoethyl) -gamma-aminopropylmethyldiethoxysilane (KH-602).
Preferably, the tackifier in the TPU film layer is one or a mixture of at least two of petroleum resin, rosin resin, maleated rosin, acrylic modified rosin, terpene resin, phenolic resin, terpene-phenolic resin or terpene-phenolic resin;
the inorganic filler is selected from any one or a mixture of at least two of calcium carbonate, kaolin, talcum powder, mica, powder, titanium dioxide, graphite powder, white carbon black or carbon black;
the organic filler is selected from any one or a mixture of at least two of polytetrafluoroethylene powder, polyphenylene sulfide powder or polyether sulfone powder;
the antioxidant is selected from one or more of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate, triisotridecyl phosphite or 4, 4' -p-isopropyldiphenyl C12-15-alcohol phosphite, and tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester;
the ultraviolet absorbent is one or more selected from 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate, 2- (2-hydroxy-3, 5-di-tert-amylphenyl) benzotriazole), 2- (2H-benzotriazole-2-yl) -4, 6-di (1-methyl-1-phenylethyl) -phenol;
the antistatic agent is selected from one or more of nonionic antistatic agents and composite antistatic agents;
the light stabilizer is selected from one or more of 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazole, 2- (2 ' -hydroxy-3 ', 5 ' -di-tert-pentylphenyl) benzotriazole, bis (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) sebacate or bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate.
Preferably, the preparation of the modified cross-linked TPU feedstock comprises the steps of: uniformly mixing the thermoplastic polyurethane elastomer, a crosslinking agent, a hydrolysis stabilizer, an antioxidant, an ultraviolet absorbent and a silane coupling agent in a mixer, pumping the mixture into a hopper of a double-screw extruder through a vacuum pump, extruding the mixture by the double-screw extruder to obtain modified crosslinked TPU particles, and drying the modified crosslinked TPU particles in a 60 ℃ drying oven for 6 hours;
the preparation of the TPU adhesive film raw material comprises the following steps: the thermoplastic polyurethane, the thermoplastic polyester, the tackifier and the functional filler are uniformly mixed in a mixer, and then are pumped into a hopper of a double-screw extruder through a vacuum pump, and are extruded by the double-screw extruder to obtain TPU adhesive film particles, and the TPU adhesive film particles are dried in a 60 ℃ oven for 6 hours.
A preparation process of a high-elasticity hot melt adhesive material made of pure TPU materials comprises the following steps: step 1:
sucking TPU glue film particles into a hopper of a No. 2 single-screw extruder of a composite extrusion casting machine through a vacuum pump, forming an ultrathin TPU glue film layer through a gap pressing agent, spraying the ultrathin TPU glue film layer on release base paper, pressing and cooling the TPU glue film layer by a composite roller and a conveying roller, conveying the TPU glue film layer to the tail end, cutting edges and winding to prepare a TPU glue film layer substrate;
step 2:
and (2) sucking the crosslinked TPU particles into a hopper of a No. 1 single-screw extruder of the composite extrusion casting machine through a vacuum pump, sucking the TPU adhesive film particles into a hopper of a No. 2 single-screw extruder of the composite extrusion casting machine through the vacuum pump, conveying the TPU adhesive film particles through a conveying roller, respectively spraying the TPU adhesive film particles on the TPU adhesive film layer of the TPU adhesive film layer substrate prepared in the step 1 through the No. 1 and No. 2 extruders in sequence, pressing and cooling the TPU adhesive film layer by a composite roller and the conveying roller to form an ultrathin TPU hot-melt adhesive material, conveying the TPU hot-melt adhesive material to the tail end to separate from a release base paper, cutting edges and rolling, and finishing the high.
Preferably, the temperatures of the barrel 1-6 sections of the No. 2 single-screw extruder in the step 1 are sequentially as follows: 135 deg.C, 140 deg.C, 145 deg.C, 150 deg.C, 155 deg.C and 160 deg.C, the temperatures of the die head 1-7 zones are set at 160 deg.C, 160 deg.C and 160 deg.C, and the die head is heated to 180 deg.C.
Preferably, the temperatures of the barrel 1-6 sections of the No. 1 single-screw extruder in the step 2 are sequentially as follows: 145 ℃, 150 ℃, 160 ℃, 180 ℃ and 180 ℃, the temperatures of the 1-7 areas of the die head are set as 165 ℃, 170 ℃, 180 ℃ and 180 ℃, and the die head is heated to 190 ℃; the temperature of the machine barrel 1-6 area of the No. 2 single screw extruder is as follows in sequence: 135 deg.C, 140 deg.C, 145 deg.C, 150 deg.C, 155 deg.C and 160 deg.C, the temperatures of the die head 1-7 zones are set at 160 deg.C, 160 deg.C and 160 deg.C, and the die head is heated to 180 deg.C.
Preferably, the thickness of the high-elasticity hot melt adhesive material made of the pure TPU material is 0.05-0.3 mm.
Preferably, the release liner is one of PP release paper or PE release paper.
Example 1
The formula is as follows: crosslinking of the TPU: 98% of thermoplastic polyurethane elastomer and 60A of hardness; the cross-linking agent is DCP, 0.2%; 0.2 percent of hydrolysis stabilizer liquid carbodiimide; the antioxidant is 1010, 0.4%; 328 percent of ultraviolet absorbent, 0.2 percent of ultraviolet absorbent and 0.8 percent of silane coupling agent, which are KH-550 percent.
TPU glue film: 60% of Thermoplastic Polyurethane (TPU) elastomer, 12% of Thermoplastic Polyester Elastomer (TPE), 12% of tackifier which is a mixture of petroleum resin and phenolic resin, 10% of functional filler which is inorganic filler kaolin and 6% of functional auxiliary agent.
After all the ingredients are mixed by a mixer according to the mass parts, the ingredients are extruded, laminated, cooled, separated, trimmed and rolled, and a novel TPU adhesive film is obtained after packaging, and the performance of the novel TPU adhesive film is shown in table 1 together with the partial performance of the underwear adhesive film on the market.
TABLE 1 comparison of the product Properties of the underwear adhesive film
Example 2
The formula is as follows: crosslinking of the TPU: 98% of thermoplastic polyurethane elastomer, and the hardness of the thermoplastic polyurethane elastomer is 65A; the cross-linking agent is BIPB, 0.3%; 0.3 percent of hydrolysis stabilizer liquid carbodiimide; 1076, 0.3% of antioxidant; 329 percent and 0.4 percent of ultraviolet absorbent and 0.6 percent of silane coupling agent.
TPU glue film: 60% of Thermoplastic Polyurethane (TPU) elastomer, 18% of Thermoplastic Polyester Elastomer (TPE), 6% of a mixture of petroleum resin, phenolic resin, acrylic acid modified rosin and terpene resin as a tackifier, 11% of organic filler polytetrafluoroethylene powder as a functional filler and 5% of a functional assistant.
After all the ingredients are mixed by a mixing machine according to the mass parts, the ingredients are extruded, laminated, cooled, separated, trimmed and rolled, and a novel TPU adhesive film is obtained after packaging, and the performance of the TPU adhesive film is shown in table 2.
TABLE 2 comparison of the product Properties of the underwear adhesive film
Embodiment 3
The formula is as follows: crosslinking of the TPU: 97% of thermoplastic polyurethane elastomer and 60A of hardness; the cross-linking agent is a mixture of DCP and BIPB, and is 0.6 percent; 0.6 percent of carbodiimide serving as a hydrolysis stabilizer; 0.6 percent of antioxidant which is a mixture of 1010 and 1076 percent; the ultraviolet absorbent is a mixture of 234 and 328, 0.4 percent, and the silane coupling agent is KH-560, 0.4 percent.
TPU glue film: 60% of Thermoplastic Polyurethane (TPU) elastomer, 10% of Thermoplastic Polyester Elastomer (TPE), 12% of petroleum resin, phenolic resin and terpene resin mixture as tackifier, 11% of inorganic filler and organic filler mixture as functional filler, and 7% of functional assistant.
After all the ingredients are mixed by a mixing machine according to the mass parts, the ingredients are extruded, laminated, cooled, separated, trimmed and rolled, and the novel TPU adhesive film and the performance and appearance of the underwear adhesive film on the market are obtained after packaging, such as table 3 and table 4.
TABLE 3 comparison of the product Properties of the underwear adhesive film
TABLE 4 comparison of appearance of underwear glue film after testing
Example 4
The formula is as follows: crosslinking of the TPU: 97% of thermoplastic polyurethane elastomer and 60A of hardness; the cross-linking agent is BIPB, 0.6%; hydrolysis stabilizer hydrolysis diimine 0.6%; 0.5 percent of antioxidant which is a mixture of 1010 and 1500; the ultraviolet absorbent is a mixture of 328 and 329, 0.4%, and the silane coupling agent is a mixture of KH-550 and KH-560, 1%.
TPU glue film: 55% of Thermoplastic Polyurethane (TPU) elastomer, 20% of Thermoplastic Polyester Elastomer (TPE), 10% of phenolic resin tackifier, 10% of terpene-phenolic resin and terpene resin mixture, and 6% of functional filler, wherein the inorganic filler is talcum powder, 9% of organic filler polyether sulfone powder mixture and 6% of functional auxiliary agent.
After all the ingredients are mixed by a mixer according to the mass parts, the ingredients are extruded, laminated, cooled, separated, trimmed and rolled, and a novel TPU adhesive film and a hot melt adhesive film pair on the market are obtained after packaging, wherein the ratio is shown in Table 5.
TABLE 5 comparison of the Properties of Hot-melt adhesive films
In the above embodiment, the tensile spring back test standard: ASTM D2594-2006 test method for elastic recovery properties of low stretch fabrics; water washing test standard: ISO 6330 shrinkage performance test; tensile strength test standard: ASTM-D638 Standard test method for tensile Properties of plastics; peel strength test standard: GB-T2792-2014 adhesive tape peeling strength test method.
It can be seen from the above embodiment that the blending modified TPU adhesive film produced by the invention, simultaneously, the self-crosslinking TPU of the invention is introduced as a substrate layer to form a hot melt adhesive film with a three-layer composite structure; the structure ensures that the product not only has excellent bonding performance index, excellent water resistance, good tensile property and excellent elastic recovery performance, but also has excellent performances of low tensile deformation rate and the like, and also has faster production efficiency compared with the middle layer added spandex fabric in the market, is more fit with the human body when being worn, and has higher comfort level.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (9)
1. The high-elasticity hot melt adhesive material is characterized by comprising an upper layer, a middle layer and a lower layer, wherein the upper layer and the lower layer are respectively a TPU adhesive film layer, the middle layer is a modified cross-linked TPU layer, the TPU adhesive film layer is prepared from a TPU adhesive film raw material, the modified cross-linked TPU layer is prepared from a modified cross-linked TPU raw material, and the modified cross-linked TPU raw material comprises the following components in percentage by mass: 97-99% of thermoplastic polyurethane elastomer, 0.1-0.8% of cross-linking agent, 0.1-0.5% of hydrolysis stabilizer, 0.2-0.5% of antioxidant, 0.5-1% of ultraviolet absorbent and 0.2-1% of silane coupling agent; the TPU adhesive film comprises the following raw materials in percentage by mass: 50-55% of Thermoplastic Polyurethane (TPU), 13-26% of Thermoplastic Polyester (TPE), 5-16% of tackifier, 3-13% of functional filler and 3-16% of functional auxiliary agent, wherein the functional filler comprises organic filler and inorganic filler, and the functional auxiliary agent is one or a mixture of more of antioxidant, ultraviolet absorbent, antistatic agent, light stabilizer and hydrolysis stabilizer.
2. The high elastic hot melt adhesive material of pure TPU material as claimed in claim 1, wherein the crosslinking agent in the modified crosslinked TPU layer is one or more of dicumyl peroxide (DCP), t-butyl cumyl peroxide (TBCP), dibenzoyl peroxide (BPO), di-t-butylperoxydiisopropylbenzene (BIPB);
the hydrolysis stabilizer is one or more of carbodiimide, liquid carbodiimide and epoxy compound;
the antioxidant is one or more of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl alcohol ester (antioxidant 1076), triisotridecyl phosphite or 4, 4' -para-isopropyldiphenyl C12-15-alcohol phosphite ester (antioxidant 1500), tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (antioxidant 1010);
the ultraviolet absorbent is one or more of 2- (2-hydroxy-3, 5-di-tert-amylphenyl) benzotriazole (ultraviolet absorbent UV-328), 2- [ 2-hydroxy-5- (1, 1, 3, 3-tetramethylbutyl) phenyl ] benzotriazole (ultraviolet absorbent UV-329), 2- (2H-benzotriazole-2-yl) -4, 6-di (1-methyl-1-phenylethyl) -phenol (ultraviolet absorbent UV-234);
the silane coupling agent is one or more of gamma-aminopropyltriethoxysilane (KH-550), gamma- (2, 3-glycidoxy) propyltrimethoxysilane (KH-560), N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane (KH-792), N-beta-aminoethyl) -gamma-aminopropyltriethoxysilane (KH-901), and N-beta- (aminoethyl) -gamma-aminopropylmethyldiethoxysilane (KH-602).
3. The highly elastic hot melt adhesive material of pure TPU material as claimed in claim 1, wherein the tackifier in the TPU adhesive film layer is one or a mixture of at least two of petroleum resin, rosin resin, maleic rosin, acrylic modified rosin, terpene resin, phenolic resin, terpene-phenolic resin or terpene-phenolic resin;
the inorganic filler is selected from any one or a mixture of at least two of calcium carbonate, kaolin, talcum powder, mica, powder, titanium dioxide, graphite powder, white carbon black or carbon black;
the organic filler is selected from any one or a mixture of at least two of polytetrafluoroethylene powder, polyphenylene sulfide powder or polyether sulfone powder;
the antioxidant is selected from one or more of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate, triisotridecyl phosphite or 4, 4' -p-isopropyldiphenyl C12-15-alcohol phosphite, and tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester;
the ultraviolet absorbent is one or more selected from 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate, 2- (2-hydroxy-3, 5-di-tert-amylphenyl) benzotriazole), 2- (2H-benzotriazole-2-yl) -4, 6-di (1-methyl-1-phenylethyl) -phenol;
the antistatic agent is selected from one or more of nonionic antistatic agents and composite antistatic agents;
the light stabilizer is selected from one or more of 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazole, 2- (2 ' -hydroxy-3 ', 5 ' -di-tert-pentylphenyl) benzotriazole, bis (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) sebacate or bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate.
4. The highly elastic hot melt adhesive material of pure TPU material as claimed in claim 1, wherein the preparation of the modified cross-linked TPU raw material comprises the following steps: uniformly mixing the thermoplastic polyurethane elastomer, a crosslinking agent, a hydrolysis stabilizer, an antioxidant, an ultraviolet absorbent and a silane coupling agent in a mixer, pumping the mixture into a hopper of a double-screw extruder through a vacuum pump, extruding the mixture by the double-screw extruder to obtain modified crosslinked TPU particles, and drying the modified crosslinked TPU particles in a 60 ℃ drying oven for 6 hours;
the preparation of the TPU adhesive film raw material comprises the following steps: the thermoplastic polyurethane, the thermoplastic polyester, the tackifier and the functional filler are uniformly mixed in a mixer, and then are pumped into a hopper of a double-screw extruder through a vacuum pump, and are extruded by the double-screw extruder to obtain TPU adhesive film particles, and the TPU adhesive film particles are dried in a 60 ℃ oven for 6 hours.
5. A preparation process of a high-elasticity hot melt adhesive material made of pure TPU (thermoplastic polyurethane), which is characterized by comprising the following steps of:
step 1:
sucking TPU glue film particles into a hopper of a No. 2 single-screw extruder of a composite extrusion casting machine through a vacuum pump, forming an ultrathin TPU glue film layer through a gap pressing agent, spraying the ultrathin TPU glue film layer on release base paper, pressing and cooling the TPU glue film layer by a composite roller and a conveying roller, conveying the TPU glue film layer to the tail end, cutting edges and winding to prepare a TPU glue film layer substrate;
step 2:
and (2) sucking the crosslinked TPU particles into a hopper of a No. 1 single-screw extruder of the composite extrusion casting machine through a vacuum pump, sucking the TPU adhesive film particles into a hopper of a No. 2 single-screw extruder of the composite extrusion casting machine through the vacuum pump, conveying the TPU adhesive film particles through a conveying roller, respectively spraying the TPU adhesive film particles on the TPU adhesive film layer of the TPU adhesive film layer substrate prepared in the step 1 through the No. 1 and No. 2 extruders in sequence, pressing and cooling the TPU adhesive film layer by a composite roller and the conveying roller to form an ultrathin TPU hot-melt adhesive material, conveying the TPU hot-melt adhesive material to the tail end to separate from a release base paper, cutting edges and rolling, and finishing the high.
6. The process for preparing a pure TPU high-elasticity hot melt adhesive material according to claim 5, wherein the temperatures in the barrel 1-6 of the single screw extruder No. 2 in the step 1 are as follows: 135 deg.C, 140 deg.C, 145 deg.C, 150 deg.C, 155 deg.C and 160 deg.C, the temperatures of the die head 1-7 zones are set at 160 deg.C, 160 deg.C and 160 deg.C, and the die head is heated to 180 deg.C.
7. The process for preparing a pure TPU high-elasticity hot melt adhesive material according to claim 5, wherein the temperatures in the barrel 1-6 of the single screw extruder No. 1 in the step 2 are as follows: 145 ℃, 150 ℃, 160 ℃, 180 ℃ and 180 ℃, the temperatures of the 1-7 areas of the die head are set as 165 ℃, 170 ℃, 180 ℃ and 180 ℃, and the die head is heated to 190 ℃; the temperature of the machine barrel 1-6 area of the No. 2 single screw extruder is as follows in sequence: 135 deg.C, 140 deg.C, 145 deg.C, 150 deg.C, 155 deg.C and 160 deg.C, the temperatures of the die head 1-7 zones are set at 160 deg.C, 160 deg.C and 160 deg.C, and the die head is heated to 180 deg.C.
8. The process for preparing the high-elasticity hot melt adhesive material made of the pure TPU according to claim 5, wherein the thickness of the high-elasticity hot melt adhesive material made of the pure TPU is 0.05 to 0.3 mm.
9. The process for preparing a high elastic hot melt adhesive material of pure TPU material according to claim 5, wherein the release liner is one of PP release paper or PE release paper.
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| CN115260966A (en) * | 2022-07-25 | 2022-11-01 | 广东汇齐新材料有限公司 | Hot-melt adhesive film with thermosetting crosslinking function and preparation method thereof |
| WO2023123607A1 (en) * | 2021-12-30 | 2023-07-06 | 广东汇齐新材料有限公司 | High adhesion-strength tpu hot melt adhesive film and preparation method therefor |
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