CN115216263B - Hot melt adhesive for clothing cloth bonding and preparation method thereof - Google Patents
Hot melt adhesive for clothing cloth bonding and preparation method thereof Download PDFInfo
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- CN115216263B CN115216263B CN202211026554.XA CN202211026554A CN115216263B CN 115216263 B CN115216263 B CN 115216263B CN 202211026554 A CN202211026554 A CN 202211026554A CN 115216263 B CN115216263 B CN 115216263B
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- melt adhesive
- polyamide resin
- clothing
- cloth bonding
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- 239000004831 Hot glue Substances 0.000 title claims abstract description 54
- 239000004744 fabric Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 74
- 239000000945 filler Substances 0.000 claims abstract description 24
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 21
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 21
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 15
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 239000004034 viscosity adjusting agent Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 30
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 23
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 15
- 239000004952 Polyamide Substances 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 239000000395 magnesium oxide Substances 0.000 claims description 12
- 229920002647 polyamide Polymers 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 239000004200 microcrystalline wax Substances 0.000 claims description 5
- 235000019808 microcrystalline wax Nutrition 0.000 claims description 5
- 235000007586 terpenes Nutrition 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 125000002298 terpene group Chemical group 0.000 claims description 2
- YKYJSUGMSFMGHC-UHFFFAOYSA-N n,n,n',n'-tetraphenylmethanediamine Chemical group C=1C=CC=CC=1N(C=1C=CC=CC=1)CN(C=1C=CC=CC=1)C1=CC=CC=C1 YKYJSUGMSFMGHC-UHFFFAOYSA-N 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 abstract description 14
- 239000000853 adhesive Substances 0.000 abstract description 13
- 230000000052 comparative effect Effects 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 description 4
- 239000012279 sodium borohydride Substances 0.000 description 4
- HCUZVMHXDRSBKX-UHFFFAOYSA-N 2-decylpropanedioic acid Chemical compound CCCCCCCCCCC(C(O)=O)C(O)=O HCUZVMHXDRSBKX-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229920000592 inorganic polymer Polymers 0.000 description 3
- 150000003505 terpenes Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- -1 aluminum ions Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
-
- 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
- C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The application relates to the field of adhesives, and particularly discloses a hot melt adhesive for clothing and cloth bonding and a preparation method thereof. The hot melt adhesive for clothing cloth bonding comprises 100 parts of modified polyamide resin; 10-18 parts of viscosity modifier; 20-30 parts of tackifier; 7-13 parts of inorganic metal oxide filler; 0.1-0.5 part of antioxidant; the preparation method comprises the following steps: s1: mixing the modified polyamide resin, the viscosity modifier, the tackifier, the inorganic metal oxide filler and the antioxidant, and uniformly stirring under the condition of inert gas; s2: reacting at 270-300 deg.c and 1.5-2.0MPa to obtain the hot melt adhesive. The heat-resistant polyamide resin has the advantages of improving the heat resistance of the polyamide resin and further reducing the occurrence of the condition that the hot melt adhesive oozes out of the lining cloth.
Description
Technical Field
The application relates to the field of adhesives, in particular to a hot melt adhesive for clothing and cloth bonding and a preparation method thereof.
Background
Hot melt adhesive refers to an adhesive that adheres in a heated, molten state. The adhesive is characterized by being free of solvent, being solid at room temperature, being liquid when heated to the melting point temperature, having fluidity, and exhibiting excellent adhesive property, being capable of being adhered with other objects quickly, and forming high-strength adhesion after cooling.
The adhesive does not need to volatilize solvent in the use process, does not pollute the environment, and is beneficial to the regeneration of resources and the protection of the environment; but also can be made into blocks, films, strips or grains, so that the packaging, the storage and the use are very convenient; in addition, the hot melt adhesive is convenient to use and high in bonding speed, and meets the requirements of automation and high efficiency of industrial production. Because the hot melt adhesive has the characteristics, the hot melt adhesive becomes one of the fastest-developing varieties in the adhesive and is widely applied in various industries.
At present, an adhesive lining is often used in the clothing field, and the adhesive lining is a lining coated with hot melt adhesive and is one of auxiliary materials frequently used for fabric manufacture. The adhesive interlining is adhered to the back of the cloth by heating and ironing, and the adhesive interlining can be added to embody when the cloth needs to express stiffness and thickness. In bonding an adhesive backing to a cloth, polyamide hot melt adhesives are often used to coat the cloth.
With respect to the related art in the above, the inventors consider that there are the following drawbacks: the polyamide resin, which is the main raw material of the polyamide hot melt adhesive, has an excessively high sensitivity to temperature, and when the temperature is excessively high, the phenomenon that the polyamide resin bleeds out of the lining cloth occurs.
Disclosure of Invention
In order to improve the heat resistance of polyamide resin and further reduce the occurrence of exudation of hot melt adhesive from lining cloth, the application provides hot melt adhesive for clothing cloth bonding and a preparation method thereof.
In a first aspect, the present application provides a hot melt adhesive for clothing and cloth bonding, which adopts the following technical scheme:
a hot melt adhesive for clothing cloth bonding is prepared from the following raw materials in parts by weight:
100 parts of modified polyamide resin;
10-18 parts of viscosity modifier;
20-30 parts of tackifier;
7-13 parts of inorganic metal oxide filler;
0.1-0.5 part of antioxidant;
the modified polyamide resin is prepared by grafting dicarboxylic acid on the polyamide resin and then reducing carbonyl of the dicarboxylic acid into hydroxyl in a reducing atmosphere.
According to the technical scheme, the cloth-attached hot melt adhesive is prepared from the modified polyamide resin serving as the base material, the modified polyamide resin is prepared by grafting dicarboxylic acid onto the polyamide resin, and the toughness of the polyamide resin can be improved by grafting dicarboxylic acid onto the polyamide resin. The heat resistance of the polyamide resin is improved by combining the obtained product with an inorganic metal oxide filler after reducing the carbonyl group on the polyamide resin to a hydroxyl group. Meanwhile, the viscosity of the polyamide resin is adjusted through the tackifier and the viscosity regulator, so that the polyamide hot melt adhesive is adhered to the lining cloth faster and better, the application and mixing of the polyamide hot melt adhesive in a molten state are protected by adding the antioxidant, and the hot melt adhesive is also protected from oxidation with the passage of time. The modified polyamide resin is prepared by modifying the polyamide resin by dicarboxylic acid and then reducing carbonyl groups on the dicarboxylic acid, and after the modified polyamide resin is compounded with the inorganic metal oxide filler, the sensitivity of the polyamide hot melt adhesive to temperature is reduced, and the heat resistance of the polyamide hot melt adhesive is improved.
Preferably, the specific preparation method of the modified polyamide comprises the following steps:
s1: polyamide resin and dicarboxylic acid according to (1-3): 1, dropwise adding phosphoric acid, stirring and heating to react in a vacuum environment, and cooling to obtain an intermediate;
s2: and introducing hydrogen and a catalyst into the intermediate, and cooling after the reaction to obtain the modified polyamide resin.
By adopting the technical scheme, in S1, the carboxyl in dicarboxylic acid and the amide bond of polyamide resin are subjected to dehydration condensation reaction; in this reaction, hydrogen bonds originally existing between hydrogens of amide bonds are broken, and carbonyl groups formed after the carboxyl groups are dehydroxylated are connected with nitrogen after the amide bonds are dehydrogenated, so that the intermolecular distance is increased, the toughness of the polyamide resin is further improved, and in S2, carbonyl groups on the grafted polyamide resin are reduced to hydroxyl groups: by adding hydrogen and then adding a catalyst, under certain conditions, the reducibility of the hydrogen can reduce carbonyl into hydroxyl, and the heat resistance of the polyamide can be improved by matching the hydroxyl with the inorganic metal oxide filler in the raw material.
Preferably, the inorganic metal oxide filler is selected from at least one of alumina and magnesia.
By adopting the technical scheme, aluminum oxide and magnesium oxide are both in crystal structures, and when the inorganic metal oxide filler is mixed with the modified polyamide resin at high temperature for reaction, hydroxyl groups on the modified polyamide resin and aluminum ions in the aluminum oxide and the magnesium oxide can undergo inorganic polymerization reaction to generate an inorganic polymer with a three-dimensional structure, so that the heat resistance of the polyamide hot melt adhesive is improved.
Preferably, the inorganic metal oxide filler is alumina and magnesia, and the mass ratio of the alumina to the magnesia is (0.5-1.5): 1.
by adopting the technical scheme, the mass ratio of the alumina to the magnesia is (0.5-1.5): 1, under the heating condition, the effect of combining hydroxyl groups in the modified polyamide resin with aluminum ions and magnesium ions is most obvious, and the content of the generated inorganic polymer with a three-dimensional structure is the greatest, so that the modified polyamide resin shows more excellent heat resistance.
Preferably, the phosphoric acid concentration in S1 is 83-87%.
By adopting the technical scheme, the phosphoric acid with the concentration of 83-87% is a viscous solution and is easy to crystallize, meanwhile, the phosphoric acid is a ternary medium strong acid, is ionized in three steps, has acid universality, and can combine with water generated by condensation to generate hemihydrate crystals in the dehydration condensation process of the polyamide resin and the dicarboxylic acid, so that the effect of promoting the condensation reaction is achieved.
Preferably, in S1, the temperature is raised to 250-270 ℃ firstly, and then the temperature is lowered to 160-200 ℃.
By adopting the technical scheme, when the temperature is raised to the temperature range of 250-270 ℃, the efficiency of the phosphoric acid to combine water is highest, and the dehydration reaction of polyamide and dicarboxylic acid is more sufficient. After the reaction is completed, the temperature is reduced to 160-200 ℃, hydrogen is introduced to carry out reduction reaction, and under the temperature range, the catalyst sodium borohydride can carry out catalytic reduction reaction on the intermediate prepared in the S1 process most efficiently, so that carbonyl on carboxyl grafted on polyamide resin is changed into hydroxyl to the greatest extent.
Preferably, the viscosity modifier is microcrystalline wax; the tackifier is terpene resin; the antioxidant is N, N, N ', N' -tetraphenylamino methane.
By adopting the technical scheme, the N, N, N ', N' -tetraphenylamino methane is used as an antioxidant, and has high antioxidant base and antioxidant performance and small pollution and colorability. The preparation method has the outstanding advantages of small mobility, low pollution, low toxicity and good heat resistance and oxidation resistance; the microcrystalline wax is mainly branched saturated hydrocarbon of C31-70, contains a small amount of cyclic and straight hydrocarbon, has ash content below 0.05%, has high viscosity and ductility, is not fragile at low temperature, and has the characteristic of preventing separation and precipitation of molten resin when being mixed with the molten resin; the terpene resin has the advantages of light color, low odor, high hardness, high adhesive force, good oxidation resistance and thermal stability, good compatibility and solubility, and the like.
In a second aspect, the present application provides a method for preparing a hot melt adhesive for bonding clothing and fabric, which adopts the following technical scheme:
the preparation method of the hot melt adhesive for clothing cloth bonding comprises the following preparation steps:
s1: mixing the modified polyamide resin, the viscosity modifier, the tackifier, the filler and the antioxidant, and uniformly stirring under the condition of inert gas;
s2: reacting at 270-300 deg.c and 1.5-2.0MPa to obtain the hot melt adhesive.
By adopting the technical scheme, all raw materials are mixed and heated for reaction, so that the raw materials can be fused together more fully, the inert gas is used for replacing the gas in the reaction kettle, so that some inflammable and explosive gases in the reaction kettle can be prevented from being exploded, and secondly, stirring and vacuum pressurizing reactions are carried out to enable the reaction to take place more fully, the finally obtained hot melt adhesive has optimal performance, heat resistance and toughness.
In summary, the present application has the following beneficial effects:
1. as the cloth-attached hot melt adhesive is prepared from the modified polyamide resin as the base material, the modified polyamide resin is prepared by grafting dicarboxylic acid onto the polyamide resin and reducing carbonyl groups on the polyamide resin into hydroxyl groups, so that the toughness of the polyamide resin is improved. The resulting modified polyamide resin is combined with an metal oxide filler free of metal oxide to improve the heat resistance of the polyamide resin.
2. Phosphoric acid is preferably used in the present application in a concentration of 83-87%, and in this concentration range, phosphoric acid is a viscous solution and is easily crystallized. Phosphoric acid has acid universality, and in the dehydration condensation process of polyamide resin and dicarboxylic acid, 83-87% concentration phosphoric acid can combine with water generated by condensation to form hemihydrate crystals, so that the effect of promoting the condensation reaction is achieved.
3. The method has the advantages that the N, N, N ', N' -tetraphenylamino methane is used as an antioxidant, the antioxidant effect of the antioxidant is high, and the pollution and the colorability are small. The preparation method has the outstanding advantages of small mobility, low pollution, low toxicity and good heat resistance and oxidation resistance; the microcrystalline wax is mainly branched saturated hydrocarbon of C31-70, contains a small amount of cyclic and straight hydrocarbon, has ash content below 0.05%, has high viscosity and ductility, is not fragile at low temperature, and has the characteristic of preventing separation and precipitation of molten resin when being mixed with the molten resin; the terpene resin has the advantages of light color, low odor, high hardness, high adhesive force, good oxidation resistance and thermal stability, good compatibility and solubility, and the like.
Detailed Description
The present application is described in further detail below with reference to examples.
Preparation example of hot melt adhesive for clothing cloth bonding
The polyamide resin is 011 resin;
the dicarboxylic acid is undecane dicarboxylic acid;
preparation example 1
The preparation method of the modified polyamide resin comprises the following steps:
s1: mixing 25kg of polyamide resin with 15kg of dicarboxylic acid, adding the mixture into a reactor with a vacuumizing and condensing system, dropwise adding 0.02kg of phosphoric acid with the concentration of 85% and the vacuum degree of 670mmHg, heating to 260 ℃ under stirring for reacting for 1h, and cooling to 180 ℃ to obtain an intermediate;
s2: hydrogen is introduced into the intermediate, 0.7kg of sodium borohydride is added, and after 1 hour of reaction, the reaction product is cooled to room temperature, and the modified polyamide resin is obtained.
Preparation example 2
The preparation method of the modified polyamide resin comprises the following steps:
s1: mixing 20kg of polyamide resin with 20kg of dicarboxylic acid, adding the mixture into a reactor with a vacuumizing and condensing system, dropwise adding 0.03kg of phosphoric acid with the concentration of 85% under the vacuum degree of 670mmHg, heating to 260 ℃ under stirring for reacting for 1h, and cooling to 180 ℃ to obtain an intermediate;
s2: hydrogen is introduced into the intermediate, 0.5kg of sodium borohydride is added, and after 1 hour of reaction, the reaction product is cooled to room temperature, and the modified polyamide resin is obtained.
Preparation example 3
The preparation method of the modified polyamide resin comprises the following steps:
s1: mixing 30kg of polyamide resin with 10kg of dicarboxylic acid, adding the mixture into a reactor with a vacuumizing and condensing system, dropwise adding 0.01kg of phosphoric acid with the concentration of 85% and the vacuum degree of 670mmHg, heating to 260 ℃ under stirring for reacting for 1h, and cooling to 180 ℃ to obtain an intermediate;
s2: hydrogen is introduced into the intermediate, 0.9kg of sodium borohydride is added, and after 1 hour of reaction, the reaction product is cooled to room temperature, and the modified polyamide resin is obtained.
Preparation example 4
The preparation method of the modified polyamide resin comprises the following steps:
s1: 25kg of polyamide resin and 15kg of dicarboxylic acid are mixed, the mixture is added into a reactor with a vacuumizing and condensing system, the vacuum degree is 670mmHg, 0.02kg of phosphoric acid with the concentration of 85% is dropwise added, the temperature is raised to 260 ℃ under stirring for reaction for 1h, and then the mixture is cooled to obtain the modified polyamide resin.
Examples
Example 1
The preparation method of the hot melt adhesive for cloth bonding comprises the following steps:
(1): 100kg of modified polyamide resin, 14kg of microcrystalline wax, 25kg of terpene resin, 10kg of alumina and 0.3kg of N, N' -tetraphenylamino methane are heated to 200 ℃, nitrogen is introduced into the mixture for gas replacement, and the mixture is stirred at a temperature to obtain the modified polyamide resin;
(2): heating the product prepared in the step (1), keeping the temperature at 270-300 ℃ for continuous reaction for 1h when the temperature is increased to 280 ℃, keeping the pressure at 1.5-2.0MPa, continuing the reaction for 2h, and cooling to obtain the hot melt adhesive.
The modified polyamide resin in preparation example 1 is used as a raw material.
Examples 2 to 3
The hot melt adhesive for bonding clothing and cloth is different from example 1 in that the raw materials and the corresponding parts by weight are shown in table 2.
TABLE 2 weight (kg) of the raw materials in examples 1 to 3
Example 4
The hot melt adhesive for bonding clothing fabric was different from example 1 in that the modified polyamide resin in preparation example 2 was selected as the raw material.
Example 5
The hot melt adhesive for bonding clothing fabric was different from example 1 in that the modified polyamide resin in preparation example 3 was selected as the raw material.
Example 6
A hot melt adhesive for clothing material bonding, which is different from example 1 in that only magnesium oxide is selected as the inorganic metal oxide filler.
Example 7
A hot melt adhesive for clothing material bonding, which is different from example 1 in that only alumina is selected as the inorganic metal oxide filler.
Comparative example
Comparative example 1
The hot melt adhesive for clothing and cloth bonding is different from example 1 in that the modified polyamide resin is replaced with a common polyamide resin (011 resin).
Comparative example 2
The hot melt adhesive for bonding clothing fabric is different from example 1 in that the inorganic metal oxide filler is replaced with a clay filler.
Comparative example 3
The hot melt adhesive for bonding clothing fabric was different from example 1 in that the modified polyamide resin in preparation example 4 was selected as the raw material.
Performance test
1. The method for detecting the heat resistance of the hot melt adhesive comprises the following steps:
the hot melt adhesive is pressed into a sample strip, the sample strip is loaded with 200g in an oven at 80 ℃, and the complete stripping time and the heat resistance data unit min are compared.
2. The method for detecting the low-temperature flexibility of the hot melt adhesive comprises the following steps:
low temperature test chamber: the temperature fluctuation is not more than + -1C, and the temperature range is recommended to be between room temperature and-80 ℃.
Flexibility test device: the device consists of a mandrel support and a mandrel, wherein the diameters of the mandrel are 3.2mm, 6.4mm, 12.8mm and 25.6mm respectively, and the effective length is 125mm, and the device is made of stainless steel or brass materials. The diameter and length of the mandrel required may also be determined according to particular requirements.
Sample: the test specimens should be cut from molded or extruded sheets or films without visible obvious cracking, blistering of the surface. The use of several laminated specimens is not allowed.
The size of the sample may vary according to the requirements of use. The recommended sample size is 75mm X10 mm (length X width) and thickness 1.25mm ± 0.01mm. The thickness dimension is critical and must be precisely controlled and measured.
The testing method comprises the following steps:
and placing the mandrel, the mandrel support and the test sample together in a low-temperature test chamber. Stored for 24h under experimental conditions.
The spindle with the largest diameter is arranged on the wedge-shaped notch of the spindle support, and the flat surface of the sample is tangentially placed at right angles to the horizontal axis of the test spindle by hand.
The sample was folded 180 ° over 1s, forming an inverted "U" shape on the mandrel, and maintained in intimate contact with the mandrel.
The test pieces were observed for breakage and recorded. If no fracture occurs, a new sample is taken and bent over the next smaller diameter mandrel. Until breaking.
The test was repeated five times on a mandrel of the smallest diameter, in which no fracture occurred, with 5 new samples, and the presence or absence of fracture of the samples was observed and recorded.
If the sample of four fifths of the repeated test is not broken, taking 5 new samples to test around a mandrel with smaller diameter; otherwise, 5 new samples are taken and wound on a mandrel with larger diameter for testing. The test pieces were observed for breakage and recorded.
TABLE 3 Table 3
It can be seen from the combination of example 1, comparative example 3 and comparative example 1 and the combination of table 3 that, first, the difference between comparative example 1 and comparative example 3 is that example 1 is further reduced by one step, the effect achieved by the reduction process is that the carbonyl group of the intermediate obtained in S1 is reduced to hydroxyl group, and a three-dimensional inorganic polymer can be formed between the hydroxyl group and the metal ion in the inorganic metal oxide filler, which can improve the heat resistance of the polyamide resin; secondly, in both the embodiment 1 and the comparative example 3, the step of grafting dicarboxylic acid to the polyamide resin is carried out, the carboxyl in the dicarboxylic acid is combined with the hydrogen in the amide bond, so that the hydrogen bond formed between the hydrogen in the original amide bond in the polyamide resin is broken, the dicarboxylic acid is undecane dicarboxylic acid, and the long carbon chain in the undecane dicarboxylic acid can increase the molecular distance between the polyamide resin, so that the toughness of the polyamide resin is improved, and the high temperature resistance is affected; in comparative example 1, a hot melt adhesive prepared from a common polyamide resin was used, so that the total peeling time of comparative example 1 was lower than that of examples 1 and 3, but was close to that of comparative example 3; at low temperature flexibility, neither example 1 nor comparative example 3 had cracks, and comparative example 1 failed.
As can be seen from the combination of example 1 and comparative example 2 and the combination of table 3, comparative example 2 changes the inorganic metal oxide filler to the clay-based filler, and the inorganic metal oxide filler is selected from aluminum oxide and magnesium oxide, and the aluminum oxide and magnesium oxide ionize inorganic metal ions in a molten state, and there is a reaction between the inorganic metal ions and the modified polyamide, but the clay-based filler in comparative example 2 does not ionize inorganic metal ions, and thus is shorter in total peeling time than in example 1.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (8)
1. The hot melt adhesive for clothing cloth bonding is characterized by being prepared from the following raw materials in parts by weight: 100 parts of modified polyamide resin;
10-18 parts of viscosity modifier;
20-30 parts of tackifier;
7-13 parts of inorganic metal oxide filler;
0.1-0.5 part of antioxidant;
the modified polyamide resin is prepared by grafting dicarboxylic acid on the polyamide resin and then reducing carbonyl of the dicarboxylic acid into hydroxyl in a reducing atmosphere.
2. The hot melt adhesive for clothing and cloth bonding according to claim 1, wherein: the specific preparation method of the modified polyamide comprises the following steps:
s1: polyamide resin and dicarboxylic acid according to (1-3): 1, dropwise adding phosphoric acid, stirring, heating, reacting and cooling in a vacuum environment to obtain an intermediate;
s2: and introducing hydrogen and a catalyst into the intermediate, and cooling after the reaction to obtain the modified polyamide resin.
3. The hot melt adhesive for clothing and cloth bonding according to claim 1, wherein: the inorganic metal oxide filler is at least one selected from the group consisting of alumina and magnesia.
4. The hot melt adhesive for clothing and cloth bonding according to claim 1, wherein: the inorganic metal oxide filler is alumina and magnesia, and the mass ratio of the alumina to the magnesia is (0.5-1.5): 1.
5. the hot melt adhesive for clothing and cloth bonding according to claim 2, wherein: the phosphoric acid concentration in S1 is 83-87%.
6. The hot melt adhesive for clothing and cloth bonding according to claim 2, wherein: in S1, the temperature is firstly increased to 250-270 ℃, and then the temperature is reduced to 160-200 ℃.
7. The hot melt adhesive for clothing and cloth bonding according to claim 1, wherein:
the viscosity modifier is microcrystalline wax; the tackifier is terpene resin; the antioxidant is N, N, N ', N' -tetraphenyldiaminomethane.
8. A method for preparing a hot melt adhesive for bonding clothing materials according to any one of claims 1 to 7, characterized in that: the preparation method comprises the following preparation steps:
(1): mixing the modified polyamide resin, the viscosity modifier, the tackifier, the inorganic metal oxide filler and the antioxidant, and uniformly stirring under the condition of inert gas;
(2): reacting at 270-300 deg.c and 1.5-2.0MPa to obtain the hot melt adhesive.
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| CN1191316C (en) * | 2000-12-12 | 2005-03-02 | 梁子材 | Multi-purpose polyamide hot melt adhesive and its prepn |
| JP2013087172A (en) * | 2011-10-17 | 2013-05-13 | Asahi Kagaku Gosei Kk | Reactive hot-melt adhesive composition |
| CN103254868B (en) * | 2013-05-17 | 2014-12-10 | 上海凯赛生物技术研发中心有限公司 | Hot melt adhesive |
| JP7263640B2 (en) * | 2017-04-10 | 2023-04-25 | コンチネンタル・ライフェン・ドイチュラント・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング | Functionalized resin with polar linkers |
| CN107674632A (en) * | 2017-09-22 | 2018-02-09 | 安庆市虹泰新材料有限责任公司 | A kind of preparation method of modified polyamide thermosol |
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