CN114369426B - Hot melt adhesive film composition and preparation method and application thereof - Google Patents

Hot melt adhesive film composition and preparation method and application thereof Download PDF

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CN114369426B
CN114369426B CN202210014446.4A CN202210014446A CN114369426B CN 114369426 B CN114369426 B CN 114369426B CN 202210014446 A CN202210014446 A CN 202210014446A CN 114369426 B CN114369426 B CN 114369426B
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parts
hot melt
melt adhesive
adhesive film
film composition
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CN114369426A (en
Inventor
周光远
丁忠洋
姜国伟
陈勇
张庆雨
李秀洁
白玮
安玉贤
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Shenghong Petrochemical Group Shanghai New Material Co ltd
Jiangsu Sailboat Petrochemical Co ltd
Dalian Institute of Chemical Physics of CAS
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Shenghong Petrochemical Group Shanghai New Material Co ltd
Jiangsu Sailboat Petrochemical Co ltd
Dalian Institute of Chemical Physics of CAS
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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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/06—Polyethene
    • 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
    • C09J11/08—Macromolecular additives
    • 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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09J123/0853—Vinylacetate
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Abstract

The invention relates to a hot melt adhesive film composition, a preparation method and application thereof, wherein the hot melt adhesive film comprises, by weight, 32-175 parts of matrix resin, 5-15 parts of tackifying resin and 1-15 parts of lamellar barrier material; the matrix resin comprises the following components in parts by weight: 10-50 parts of ethylene-vinyl acetate copolymer, 0-40 parts of high-density polyethylene, 10-40 parts of linear low-density polyethylene, 2-20 parts of maleic anhydride grafted polyethylene and 0-15 parts of thermoplastic elastomer. The sheet barrier material adopted by the hot melt adhesive film composition can obviously reduce the release amount of organic volatile matters (VOC) in the hot melt adhesive formula, and can better maintain the bonding strength of the hot melt adhesive.

Description

Hot melt adhesive film composition and preparation method and application thereof
Technical Field
The invention relates to the technical field of hot melt adhesive films, in particular to a hot melt adhesive film composition, a preparation method and application thereof.
Background
In recent years, with the vigorous development of the industries of electronic products, building industry, clothes decoration, shoe industry, automobiles, household products and the like, a hot melt adhesive film is used as a novel adhesive, and has the advantages of strong adhesive force, no pollution, convenient operation and convenient storage, so that the hot melt adhesive film is widely applied. Hot melt adhesive films are generally prepared from saturated polyolefin materials such as Polyethylene (PE), ethylene-vinyl acetate copolymer (EVA), polyolefin elastomer (POE), and the like as a base material. The hot melt adhesive film belongs to one kind of hot melt adhesive. The preparation method generally comprises the steps of carrying out melt blending and extrusion granulation on polyolefin materials and auxiliary agents in a double-screw extruder, and finally forming a film in film-forming equipment. In order to increase the adhesive property of the hot melt adhesive film, an auxiliary agent for facilitating the adhesion is generally added. However, most of the adhesion aids contain polar functional groups such as ester functional groups, acid functional groups, and residual acidic substances. Under high temperature conditions, a large amount of toxic and harmful gases may be released, and the standard of VOC (such as NESM0402 standard of Japanese patent Co., ltd.) of the automobile material is not met. VOC (Volatile Organic Compound) refers to volatile organic compounds below 250 ℃. Formaldehyde and acetaldehyde are common VOC components. According to the development requirements of the automobile industry, it is necessary to develop hot melt adhesive film products with low VOC release and high adhesive properties.
CN108034368A discloses a VOC-free hot melt adhesive film for automobiles and a preparation method thereof, belonging to the technical field of hot melt adhesive films. Solves the problem of high VOC content in the prior hot melt adhesive film. The method firstly utilizes a spray drying method to generate porous materials with core-shell structures in situ by starch, white carbon black, a compound thermoplastic elastomer and a surfactant; the porous composite material, polyolefin material, bonding auxiliary agent, antioxidant and stabilizer are melted and blended in a double screw extruder, extruded and granulated, and finally formed into a film in film-forming equipment. Compared with the prior art, the disclosed material has higher structural degree and better adsorption effect on VOC, and as the latex and the auxiliary agent are compounded and spray-dried to form a porous structural material, the porous material has the characteristics of large specific surface area, strong adsorption capacity and high activity, can reduce or eliminate the VOC of the material, and simultaneously improves the physical and mechanical properties, heat resistance, ageing resistance and flame retardance of the product, but the components and the preparation process of the disclosed hot melt adhesive film are relatively complex.
In view of the above, it is important to develop a hot melt adhesive film which has both low VOC emissions and high adhesive strength, and which is simple in composition and preparation.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a hot melt adhesive film composition, a preparation method and application thereof, wherein a sheet barrier material adopted by the hot melt adhesive film composition can obviously reduce the release amount of organic volatile matters (VOC) in a hot melt adhesive formula, and meanwhile, the adhesive strength of the hot melt adhesive can be better maintained, and the components and the process are simple.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a hot melt adhesive film composition comprising, by weight, 32-175 parts of a matrix resin, 5-15 parts of a tackifying resin, and 1-15 parts of a sheet barrier material;
the matrix resin comprises the following components in parts by weight:
Figure BDA0003454490170000021
the invention adopts the sheet barrier material to obviously reduce the release amount of organic volatile matters (VOC) in the hot melt adhesive formulation, and simultaneously can better maintain the bonding strength of the hot melt adhesive with simple components. And the addition amount of the sheet barrier material is adjusted to be in the range of 1-15 parts, but when the content of the sheet barrier material is too high, the adhesion fails.
In the invention, the weight parts of the matrix resin are 32-175 parts, such as 40 parts, 50 parts, 60 parts, 80 parts, 100 parts, 120 parts, 140 parts, 160 parts and the like;
wherein the ethylene-vinyl acetate copolymer is 10 to 50 parts by weight, for example, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, etc.
The weight parts of the high-density polyethylene are 10 to 40 parts, for example, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, etc.
The linear low density polyethylene is 10 to 40 parts by weight, for example 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, etc.
The weight parts of the maleic anhydride grafted polyethylene are 2 to 20 parts, for example 4 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, etc.
The thermoplastic elastomer is 0 to 15 parts by weight, for example 1 part, 2 parts, 4 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, etc.
The weight parts of the tackifying resin are 5-15 parts, for example 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, etc.
The sheet barrier material is 1-15 parts by weight, for example 2 parts, 4 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, etc.
Preferably, the tackifying resin comprises any one or a combination of at least two of a hydrogenated petroleum resin, a phenolic terpene resin, or a carbon five petroleum resin, wherein typical but non-limiting combinations include: a combination of a hydrogenated petroleum resin and a phenolic terpene resin, a combination of a phenolic terpene resin and a carbon five petroleum resin, a combination of a hydrogenated petroleum resin, a phenolic terpene resin and a carbon five petroleum resin, and the like.
The tackifying resin selected by the hot melt adhesive film is one or more of hydrogenated carbon nine petroleum resin, phenolic terpene resin and carbon five petroleum resin, has good tackifying effect, is easy to form a hydrogen bond network, and improves the wettability and the cohesiveness of the hot melt adhesive film.
Preferably, the sheet barrier material comprises surface-activated potassium aluminum silicate, preferably surface-activated potassium aluminum silicate.
Preferably, the platelet barrier material is a two-dimensional nanolaminate structure.
Preferably, the platelet thickness of the platelet barrier material is 30-60nm, such as 35nm, 40nm, 45nm, 50nm, 55nm, etc.
Preferably, the sheet barrier material has a sheet diameter size of 0.5-10 μm, e.g. 1 μm, 2 μm, 4 μm, 6 μm, 8 μm, etc.
The sheet barrier material is preferably aluminum potassium silicate after surface activation treatment, and the aluminum potassium silicate is the sheet barrier material, and the morphological characteristics of the sheet barrier material are shown in figure 1. The molecular formula of the aluminum potassium silicate is SiO 2 ·Al 2 O 3 ·K 2 The structure of O is a two-dimensional nano lamellar structure, the thickness of the lamellar layer is 30-60nm, and the size of the lamellar diameter is 0.5-10 mu m. The sheet aluminum potassium silicate has the characteristics of large specific surface area and good barrier effect, and can obviously reduce the release amount of VOC in the hot melt adhesive formula.
Preferably, in the aluminum potassium silicate after the surface activation treatment, the surface-treated material includes a coupling agent.
Preferably, the maleic anhydride grafted polyethylene (PE-g-MAH) has a grafting ratio in weight percent of 0.1% to 1.5%, such as 0.2%, 0.4%, 0.6%, 0.8%, 1.0%, 1.2%, 1.4%, etc. The PE-g-MAH selected in the hot melt adhesive film composition of the invention is used as a compatilizer.
Preferably, the ethylene vinyl acetate copolymer (EVA) has a melt index of 2.0-30g/10min (e.g., 5g/10min, 10g/10min, 15g/10min, 20g/10min, 25g/10min, etc.), and a VA content of 17% -40% (e.g., 18%, 20%, 25%, 30%, 35%, etc.) by weight. EVA selected by the hot melt adhesive film composition has good mechanical property and processing stability.
Preferably, the High Density Polyethylene (HDPE) has a melt index of 2-20g/10min, such as 4g/10min, 6g/10min, 8g/10min, 10g/10min, 12g/10min, 14g/10min, 16g/10min, 18g/10min, etc. The HDPE selected by the hot melt adhesive film of the invention has good heat resistance and mechanical property.
Preferably, the Linear Low Density Polyethylene (LLDPE) has a melt index of 1 to 10g/10min, such as 2g/10min, 4g/10min, 6g/10min, 8g/10min, etc. LLDPE selected by the hot melt adhesive film composition has a melt index of 1-10g/10min and good processability.
Preferably, the thermoplastic elastomer comprises any one or a combination of at least two of a styrene-butadiene-styrene block copolymer, a hydrogenated styrene copolymer, or a styrene-isoprene copolymer, wherein typical but non-limiting combinations include: a combination of a block copolymer of styrene-butadiene-styrene and a hydrogenated styrene copolymer, a combination of a hydrogenated styrene copolymer and a styrene-isoprene copolymer, a combination of a block copolymer of styrene-butadiene-styrene, a hydrogenated styrene copolymer and a styrene-isoprene copolymer, and the like.
Preferably, the styrene content in the thermoplastic elastomer is not more than 60% by weight, such as 50%, 45%, 40%, 35%, etc.
The SBS (styrene-butadiene-styrene) selected for the hot melt adhesive film of the present invention can improve the viscoelasticity of the hot melt adhesive film. SBS is a thermoplastic elastomer with better elasticity, and the styrene content of the SBS is not more than 60 percent by weight. Too high a styrene content will lose its elasticity. Hydrogenated styrene copolymers (SEBS) having a styrene-like content and styrene-isoprene copolymers (SIS) can also be used.
Preferably, the hot melt adhesive film composition further comprises an auxiliary agent.
Preferably, the auxiliary agent comprises a lubricant and/or an antioxidant.
The antioxidant selected by the hot melt adhesive film composition of the invention is a general antioxidant which can be used for polyolefin materials, such as hindered phenols, phosphites, hindered amines and the like. One or more of antioxidant 1010, antioxidant 168 and the like are used for improving the ageing resistance of the material.
Preferably, the lubricant is present in an amount of 0.5 to 5 parts by weight, such as 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, etc.
Preferably, the antioxidant is present in an amount of 0 to 1.5 parts by weight, for example 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts, 1.0 parts, 1.2 parts, 1.4 parts, etc.
Preferably, the lubricant comprises any one or a combination of at least two of polyethylene wax, methyl silicone oil or silicone resin, wherein typical but non-limiting combinations include: a combination of polyethylene wax and methyl silicone oil, a combination of methyl silicone oil and silicone resin, a combination of polyethylene wax, methyl silicone oil and silicone resin, and the like, and polyethylene wax is further preferable.
In a second aspect, the present invention provides a method for preparing the hot melt adhesive film composition according to the first aspect, the method comprising the steps of:
mixing matrix resin, tackifying resin and lamellar barrier material according to the formula amount, and processing to obtain the hot melt adhesive film composition.
Preferably, the preparation method of the sheet barrier material comprises the following steps: and introducing aluminum potassium silicate into a coupling agent, performing surface activation treatment, and drying to obtain the sheet barrier material.
Preferably, the surface activation treatment includes stirring and ultrasonic vibration.
Preferably, the stirring is carried out at a speed of 5000-7000 rpm, for example 5200 rpm, 5400 rpm, 5600 rpm, 5800 rpm, 6000 rpm, 6200 rpm, 6400 rpm, 6600 rpm, 6800 rpm, etc.
Preferably, the stirring time is 1-5 minutes, such as 1.5 minutes, 2 minutes, 3 minutes, 4 minutes, etc.
Preferably, the frequency of the ultrasonic oscillation is 20-60KHz, such as 25KHz, 30KHz, 35KHz, 40KHz, 45KHz, 50KHz, 55KHz, etc.
Preferably, the time of the ultrasonic oscillation is 1-5 minutes, such as 1.5 minutes, 2 minutes, 3 minutes, 4 minutes, etc.
Preferably, the drying means comprises spray drying.
Preferably, the preparation method further comprises adding an auxiliary agent during mixing.
Preferably, the method of mixing comprises melt blending.
Preferably, the processing mode sequentially comprises extrusion granulation, casting and shaping.
Illustratively, the process parameters of the extrusion granulation are:
in a twin screw extruder, the screw feed section temperature is 115 ℃ (zone 1), the processing section is 155 ℃ (zone 2-4), the processing section is 160 ℃ (zone 5-7), the last section is 165 ℃ (zone 8 and die head); the screw speed was 650rpm.
Illustratively, the process parameters of casting are:
the extruder temperature was 135℃in zone one, 155℃in zone two, 175℃in zone three-six, and 175℃in roll two.
As a preferable technical scheme, the preparation method comprises the following steps:
step one: introducing aluminum potassium silicate into a coupling agent, performing surface activation treatment in a stirring and ultrasonic vibration mode, and then performing spray drying to obtain a lamellar barrier material;
step two: putting the sheet barrier material obtained in the step one, matrix resin, tackifying resin and auxiliary agent into a high-speed mixer, and uniformly mixing;
step three: putting the mixture obtained in the second step into an extruder for melt blending, performing vacuum devolatilization, extruding and granulating to obtain granules;
step four: and (3) putting the granules obtained in the step (III) into a casting machine, and carrying out casting, cooling and shaping to obtain the hot melt adhesive film.
In a third aspect, the present invention provides a use of the hot melt adhesive film composition of the first aspect in metal or fabric bonding.
Compared with the prior art, the invention has the following beneficial effects:
(1) The sheet barrier material adopted by the invention can obviously reduce the release amount of organic volatile compounds (VOC) at 250+/-5 ℃ in the hot melt adhesive formula, and can better maintain the bonding strength of the hot melt adhesive.
(2) When the sheet layer blocking material is preferably aluminum potassium silicate, the adhesive film has certain adhesive property to fabrics and metals, the formaldehyde content of the hot melt adhesive film composition is less than 83ppm, the acetaldehyde content is less than 89ppm, the adhesive strength with the fabrics is between 25 and 32N/2.5cm, the adhesive strength with the metals is between 51 and 58N/2.5cm, and the effect is more obvious along with the increase of the content of the sheet layer aluminum potassium silicate.
Drawings
FIG. 1 is a scanning electron micrograph (magnification 50000) of the morphology of a lamellar aluminum potassium silicate according to the present invention;
FIG. 2 is a schematic flow chart of the production process according to example 1 of the present invention.
Detailed Description
To facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Experimental raw material information
Sheet aluminum potassium silicate: average sheet diameters were 3 μm and 5. Mu.m.
Lamellar talc powder: the average sheet diameter was 6. Mu.m.
EVA: melt index 6g/10min, VA content 28%, available from Siterbang under the brand UF0628.
HDPE: the melt index is 10g/10min, and is purchased from LG and has the brand ME9180.
LLDPE: the melt index is 2g/10min, and is purchased from Daqing petrochemical industry and has the brand of DFDA7042.
PE-g-MAH: the melt index was 1.5g/10min, the grafting ratio was 0.7%, and the grade was MC218D, which was obtained from a commercially available light source.
SBS: styrene content 30%, commercially available from Yue Hua under the trade name 791.
Polyethylene wax: molecular weight 2750, commercially available from SCG under the trade designation LP1040P.
Hydrogenated carbon nine petroleum resin: the solid content is more than 95%, and the brand of the product is FP125.
Phenolic terpene resin: the solids were greater than 95% and were purchased from Koteng under the trademark Kraton1160.
Carbon five petroleum resin: the solid content is more than 95 percent, and is purchased from Jitian chemical industry with the brand number of No. 6.
An antioxidant: the brand is antioxidant 168 and antioxidant 1010.
Coupling agent: the brand is KH 550, and the purity is more than 98%.
Example 1
The embodiment provides a hot melt adhesive film, and a specific production flow chart is shown in fig. 2, and the preparation method of the hot melt adhesive film comprises the following steps:
(1) Introducing a coupling agent into an inorganic powder material of aluminum potassium silicate, performing surface activation treatment by high-speed stirring (6000 rpm, 2 minutes) and ultrasonic vibration (40 KHz,2 minutes), and then performing spray drying to obtain activated lamellar aluminum potassium silicate;
(2) 2 parts by weight of potassium aluminum silicate (average sheet diameter of 3 mu m), EVA, HDPE, LLDPE, PE grafted maleic anhydride, SBS, polyethylene wax, hydrogenated carbon nine resin, terpene phenolic resin, carbon five petroleum resin, antioxidant 168, antioxidant 1010, 37.5 parts by weight, 10 parts by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 0.25 parts by weight, and adding into a double screw extruder, wherein the temperature of a screw feeding stage is 115 ℃ (zone 1), a processing stage 155 ℃ (zone 2-4), a processing stage 160 ℃ (zone 5-7), and a final stage 165 ℃ (zone 8) and a die head; the screw speed was 650rpm. And (3) selecting the temperature of a casting machine: the extruder temperature was 135℃in zone one, 155℃in zone two, 175℃in zone three-six, and 175℃in roll two.
Example 2
The embodiment provides a hot melt adhesive film, and the preparation method of the hot melt adhesive film comprises the following steps:
(1) Introducing a coupling agent into an inorganic powder material of aluminum potassium silicate, performing surface activation treatment by high-speed stirring (6000 rpm, 2 minutes) and ultrasonic vibration (40 KHz,2 minutes), and then performing spray drying to obtain activated lamellar aluminum potassium silicate;
(2) The hot melt adhesive film was obtained by the same operation as in example 1, except that the silane coupling agent-activated sheet aluminum potassium silicate (average sheet diameter 3 μm), EVA, HDPE, LLDPE, PE grafted maleic anhydride, SBS, polyethylene wax, hydrogenated carbon nine resin, terpene phenolic resin, carbon five petroleum resin, antioxidant 168, antioxidant 1010 were used in the same amount of 5 parts by weight, 30 parts by weight, 34.5 parts by weight, 10 parts by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 0.25 parts by weight.
Example 3
The embodiment provides a hot melt adhesive film, and the preparation method of the hot melt adhesive film comprises the following steps:
(1) Introducing a coupling agent into an inorganic powder material of aluminum potassium silicate, performing surface activation treatment by high-speed stirring (6000 rpm, 2 minutes) and ultrasonic vibration (40 KHz,2 minutes), and then performing spray drying to obtain activated lamellar aluminum potassium silicate;
(2) The hot melt adhesive film was obtained by the same operation as in example 1, except that the silane coupling agent-activated sheet aluminum potassium silicate (average sheet diameter 3 μm), EVA, HDPE, LLDPE, PE grafted maleic anhydride, SBS, polyethylene wax, hydrogenated carbon nine resin, terpene phenolic resin, carbon five petroleum resin, antioxidant 168, antioxidant 1010, in parts by weight, was 10 parts, 30 parts, 29.5 parts, 10 parts, 1 part, 2 parts, 3 parts, 0.25 part.
Example 4
The embodiment provides a hot melt adhesive film, and the preparation method of the hot melt adhesive film comprises the following steps:
(1) Introducing a coupling agent into an inorganic powder material of aluminum potassium silicate, performing surface activation treatment by high-speed stirring (6000 rpm, 2 minutes) and ultrasonic vibration (40 KHz,2 minutes), and then performing spray drying to obtain activated lamellar aluminum potassium silicate;
(3) The hot melt adhesive film was obtained by the same operation as in example 1, except that 15 parts by weight of potassium aluminum silicate (average sheet diameter: 3 μm), EVA, HDPE, LLDPE, PE grafted maleic anhydride, SBS, polyethylene wax, hydrogenated carbon nine resin, terpene phenolic resin, carbon five petroleum resin, antioxidant 168, antioxidant 1010, which was activated with a silane coupling agent, 30 parts by weight, 24.5 parts by weight, 10 parts by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 0.25 parts by weight.
Example 5
The embodiment provides a hot melt adhesive film, and the preparation method of the hot melt adhesive film comprises the following steps:
(1) Introducing a coupling agent into an inorganic powder material of aluminum potassium silicate, performing surface activation treatment by high-speed stirring (6000 rpm, 2 minutes) and ultrasonic vibration (40 KHz,2 minutes), and then performing spray drying to obtain activated lamellar aluminum potassium silicate;
(2) The hot melt adhesive film was obtained by the same operation as in example 1, except that the silane coupling agent-activated sheet aluminum potassium silicate (average sheet diameter 5 μm), EVA, HDPE, LLDPE, PE grafted maleic anhydride, SBS, polyethylene wax, hydrogenated carbon nine resin, terpene phenolic resin, carbon five petroleum resin, antioxidant 168, antioxidant 1010, in parts by weight, was 2 parts, 30 parts, 37.5 parts, 10 parts, 1 part, 2 parts, 3 parts, 0.25 part.
Example 6
The embodiment provides a hot melt adhesive film, and the preparation method of the hot melt adhesive film comprises the following steps:
(1) Introducing a coupling agent into an inorganic powder material of aluminum potassium silicate, performing surface activation treatment by high-speed stirring (6000 rpm, 2 minutes) and ultrasonic vibration (40 KHz,2 minutes), and then performing spray drying to obtain activated lamellar aluminum potassium silicate;
(2) The hot melt adhesive film was obtained by the same operation as in example 1, except that the silane coupling agent-activated sheet aluminum potassium silicate (average sheet diameter 5 μm), EVA, HDPE, LLDPE, PE grafted maleic anhydride, SBS, polyethylene wax, hydrogenated carbon nine resin, terpene phenolic resin, carbon five petroleum resin, antioxidant 168, antioxidant 1010, in parts by weight, was 5 parts, 30 parts, 34.5 parts, 10 parts, 1 part, 2 parts, 3 parts, 0.25 part.
Example 7
The embodiment provides a hot melt adhesive film, and the preparation method of the hot melt adhesive film comprises the following steps:
(1) Introducing a coupling agent into an inorganic powder material of aluminum potassium silicate, performing surface activation treatment by high-speed stirring (6000 rpm, 2 minutes) and ultrasonic vibration (40 KHz,2 minutes), and then performing spray drying to obtain activated lamellar aluminum potassium silicate;
(2) The hot melt adhesive film was obtained by the same operation as in example 1, except that the silane coupling agent-activated sheet aluminum potassium silicate (average sheet diameter 5 μm), EVA, HDPE, LLDPE, PE grafted maleic anhydride, SBS, polyethylene wax, hydrogenated carbon nine resin, terpene phenolic resin, carbon five petroleum resin, antioxidant 168, antioxidant 1010, in parts by weight, was 10 parts, 30 parts, 29.5 parts, 10 parts, 1 part, 2 parts, 3 parts, 0.25 part.
Example 8
The embodiment provides a hot melt adhesive film, and the preparation method of the hot melt adhesive film comprises the following steps:
(1) Introducing a coupling agent into an inorganic powder material of aluminum potassium silicate, performing surface activation treatment by high-speed stirring (6000 rpm, 2 minutes) and ultrasonic vibration (40 KHz,2 minutes), and then performing spray drying to obtain activated lamellar aluminum potassium silicate;
(2) The hot melt adhesive film was obtained by the same operation as in example 1, except that 15 parts by weight of potassium aluminum silicate (average sheet diameter 5 μm), EVA, HDPE, LLDPE, PE grafted maleic anhydride, SBS, polyethylene wax, hydrogenated carbon nine resin, terpene phenolic resin, carbon five petroleum resin, antioxidant 168, antioxidant 1010, which were activated with a silane coupling agent, were used in the same amount as in example 1.
Example 9
This example differs from example 1 in that the surface-treated potassium aluminum silicate flakes were replaced with surface-treated talc flakes, and the remainder were the same as in example 1.
Comparative example 1
The comparative example provides a hot melt adhesive film, the preparation method of which comprises the following steps:
the EVA, HDPE, LLDPE, PE grafted maleic anhydride, SBS, polyethylene wax, hydrogenated carbon nine resin, terpene phenolic resin, carbon five petroleum resin, antioxidant 168 and antioxidant 1010 are prepared into hot melt adhesive films according to the same operation process as in example 1, wherein the weight parts of the hot melt adhesive films are 30 parts, 40 parts, 10 parts, 9.5 parts, 1 part, 2 parts, 3 parts, 0.25 part and 0.25 part.
Comparative example 2
The comparative example provides a hot melt adhesive film, the preparation method of which comprises the following steps:
(1) Introducing a coupling agent into an inorganic powder material of aluminum potassium silicate, performing surface activation treatment by high-speed stirring (6000 rpm, 2 minutes) and ultrasonic vibration (40 KHz,2 minutes), and then performing spray drying to obtain activated lamellar aluminum potassium silicate;
(2) The hot melt adhesive film was obtained by the same operation as in example 1, except that the silane coupling agent-activated sheet aluminum potassium silicate (average sheet diameter 3 μm), EVA, HDPE, LLDPE, PE grafted maleic anhydride, SBS, polyethylene wax, hydrogenated carbon nine resin, terpene phenolic resin, carbon five petroleum resin, antioxidant 168, antioxidant 1010, in parts by weight, was 16 parts, 30 parts, 23.5 parts, 10 parts, 1 part, 2 parts, 3 parts, 0.25 part.
Comparative example 3
(1) Introducing a coupling agent into an inorganic powder material of aluminum potassium silicate, performing surface activation treatment by high-speed stirring (6000 rpm, 2 minutes) and ultrasonic vibration (40 KHz,2 minutes), and then performing spray drying to obtain activated lamellar aluminum potassium silicate;
(2) The hot melt adhesive film was obtained by the same operation as in example 1, except that 16 parts by weight of potassium aluminum silicate (average sheet diameter 5 μm), EVA, HDPE, LLDPE, PE grafted maleic anhydride, SBS, polyethylene wax, hydrogenated carbon nine resin, terpene phenolic resin, carbon five petroleum resin, antioxidant 168, antioxidant 1010, 23.5 parts by weight, 10 parts by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 0.25 parts by weight, and the like were subjected to activation with a silane coupling agent.
Performance testing
The hot melt adhesive films described in examples 1 to 8 and comparative examples 1 to 3 were subjected to the following test:
(1) VOC content: the detection was carried out according to the NESM0402 standard of Japanese production. Formaldehyde, acetaldehyde content is required to be less than or equal to 100ppm.
(2) Adhesive strength: detection is carried out according to GB/T2790-1995. The stripping force between the hot melt adhesive film and the metal is required to be more than or equal to 50N/2.5cm; the adhesive peel strength with the fabric is required to be more than or equal to 25N/2.5cm.
The test results are summarized in table 1.
TABLE 1
Figure BDA0003454490170000141
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Figure BDA0003454490170000151
As can be seen from the data of Table 1, in examples 1-8, when the sheet barrier material is preferably aluminum potassium silicate, the formaldehyde content of the hot melt adhesive film composition of the invention is less than 83ppm, the acetaldehyde content is less than 89ppm, the bonding strength with fabrics is between 25 and 32N/2.5cm, the bonding strength with metals is between 51 and 58N/2.5cm, and the effect is more obvious as the content of the aluminum potassium silicate of the sheet is increased. At this time, the adhesive strength of the adhesive film to the fabric and the metal is reduced, but the adhesive film still meets the requirements. The sheet barrier material adopted by the invention can obviously reduce the release amount of organic volatile matters (VOC) in the hot melt adhesive formula, and can better maintain the bonding strength of the hot melt adhesive.
Analysis of comparative example 1 and example 1 shows that the formaldehyde and acetaldehyde contents of the hot melt adhesive film composition of comparative example 1 are significantly higher than those of example 1, demonstrating that the hot melt adhesive film composition of the invention with the addition of the sheet barrier material performs better.
Analysis of comparative examples 2-3 and examples 1 and 4 revealed that comparative examples 2-3 exhibited adhesive failure, demonstrating that the hot melt adhesive film compositions formed with the addition amounts of the sheet barrier materials in the range of 1-15 exhibited better performance.
Analysis of example 9 and example 1 shows that example 9 performs less well than example 1, demonstrating that the hot melt adhesive film composition formed with the surface-activated aluminum potassium silicate as the sheet barrier material performs better.
The applicant states that the detailed method of the present invention is illustrated by the above examples, but the present invention is not limited to the detailed method described above, i.e. it does not mean that the present invention must be practiced in dependence upon the detailed method described above. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims (21)

1. The hot melt adhesive film composition is characterized by comprising, by weight, 32-175 parts of a matrix resin, 5-15 parts of a tackifying resin and 1-15 parts of a sheet barrier material;
the matrix resin comprises the following components in parts by weight:
Figure FDA0004164844200000011
the sheet barrier material comprises aluminum potassium silicate after surface activation treatment;
the lamellar barrier material is of a two-dimensional nano lamellar structure;
the thickness of the sheet layer barrier material is 30-60nm;
the sheet diameter of the sheet barrier material is 0.5-10 mu m;
in the aluminum potassium silicate subjected to the surface activation treatment, the surface-treated material comprises a coupling agent.
2. The hot melt adhesive film composition according to claim 1, wherein the tackifying resin comprises any one or a combination of at least two of a hydrogenated petroleum resin, a phenolic terpene resin, or a carbon five petroleum resin.
3. The hot melt adhesive film composition according to claim 1, wherein the grafting ratio of the maleic anhydride grafted polyethylene is 0.1% to 1.5% by weight.
4. The hot melt adhesive film composition according to claim 1, wherein the ethylene-vinyl acetate copolymer has a melt index of 2.0 to 30g/10min and a va content of 17 to 40% by weight.
5. The hot melt adhesive film composition according to claim 1, wherein the high density polyethylene has a melt index of 2 to 20g/10min.
6. The hot melt adhesive film composition according to claim 1, wherein the linear low density polyethylene has a melt index of 1 to 10g/10min.
7. The hot melt adhesive film composition according to claim 1, wherein the thermoplastic elastomer comprises any one or a combination of at least two of a styrene-butadiene-styrene block copolymer, a hydrogenated styrene copolymer, or a styrene-isoprene copolymer.
8. The hot melt adhesive film composition according to claim 1, wherein the styrene content in the thermoplastic elastomer is not more than 60% by weight.
9. The hot melt adhesive film composition according to claim 1, wherein the hot melt adhesive film composition further comprises an auxiliary agent.
10. The hot melt adhesive film composition according to claim 9, wherein the auxiliary agent comprises a lubricant and/or an antioxidant.
11. The hot melt adhesive film composition according to claim 10, wherein the lubricant is 0.5 to 5 parts by weight.
12. The hot melt adhesive film composition according to claim 10, wherein the antioxidant is 0 to 1.5 parts by weight.
13. The hot melt adhesive film composition according to claim 10, wherein the lubricant comprises any one or a combination of at least two of polyethylene wax, methyl silicone oil, or silicone resin.
14. A process for preparing a hot melt adhesive film composition according to any one of claims 1 to 13, characterized in that the process comprises the steps of:
mixing matrix resin, tackifying resin and lamellar barrier material according to the formula amount, and processing to obtain the hot melt adhesive film composition;
the preparation method of the sheet barrier material comprises the following steps: and introducing aluminum potassium silicate into a coupling agent, performing surface activation treatment, and drying to obtain the sheet barrier material.
15. The method of claim 14, wherein the surface activation treatment comprises stirring and ultrasonic agitation.
16. The method of claim 14, wherein the drying comprises spray drying.
17. The method of claim 14, further comprising adding an auxiliary agent during mixing.
18. The method of making according to claim 17, wherein the method of mixing comprises melt blending.
19. The method of claim 14, wherein the processing comprises extrusion granulation, casting, and sizing in that order.
20. The preparation method according to claim 14, characterized in that the preparation method comprises the steps of:
step one: introducing aluminum potassium silicate into a coupling agent, performing surface activation treatment in a stirring and ultrasonic vibration mode, and then performing spray drying to obtain a lamellar barrier material;
step two: putting the sheet barrier material obtained in the step one, matrix resin, tackifying resin and auxiliary agent into a high-speed mixer, and uniformly mixing;
step three: putting the mixture obtained in the second step into an extruder for melt blending, performing vacuum devolatilization, extruding and granulating to obtain granules;
step four: and (3) putting the granules obtained in the step (III) into a casting machine, and carrying out casting, cooling and shaping to obtain the hot melt adhesive film.
21. Use of a hot melt adhesive film composition according to any one of claims 1 to 13 in metal or fabric bonding.
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Publication number Priority date Publication date Assignee Title
CN111171750A (en) * 2020-03-21 2020-05-19 烟台正海合泰科技股份有限公司 Hot melt adhesive film for automotive interior ceiling and production method thereof
CN112226180A (en) * 2020-10-10 2021-01-15 厦门联合信诺新材料有限公司 Hot melt adhesive film for composite shoe sole and preparation method thereof

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CN111635706A (en) * 2020-06-12 2020-09-08 常州斯威克光伏新材料有限公司 PID (potential induced degradation) resistant packaging adhesive film for double-sided PREC (pre-positive electrode contact) battery and preparation method thereof
CN112778938A (en) * 2020-12-25 2021-05-11 上海邦中新材料有限公司 Adhesive resin for pesticide barrier bottle and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111171750A (en) * 2020-03-21 2020-05-19 烟台正海合泰科技股份有限公司 Hot melt adhesive film for automotive interior ceiling and production method thereof
CN112226180A (en) * 2020-10-10 2021-01-15 厦门联合信诺新材料有限公司 Hot melt adhesive film for composite shoe sole and preparation method thereof

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