CN108300383A - A kind of special anti-self-adhesion hot melt adhesive film of auto industry production - Google Patents
A kind of special anti-self-adhesion hot melt adhesive film of auto industry production Download PDFInfo
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- CN108300383A CN108300383A CN201810199126.4A CN201810199126A CN108300383A CN 108300383 A CN108300383 A CN 108300383A CN 201810199126 A CN201810199126 A CN 201810199126A CN 108300383 A CN108300383 A CN 108300383A
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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
- C09J123/08—Copolymers of ethene
- C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09J123/0853—Vinylacetate
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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
- C09J7/00—Adhesives in the form of films or foils
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- 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
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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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- 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
- C09J2423/00—Presence of polyolefin
- C09J2423/04—Presence of homo or copolymers of ethene
Abstract
The invention discloses a kind of auto industrys to produce special anti-self-adhesion hot melt adhesive film, belongs to technical field of polymer materials.It includes matrix resin that the auto industry that the present invention develops, which produces special anti-self-adhesion hot melt adhesive film, tackifying resin, antitack agent, antioxidant and filler, wherein, antitack agent is by nano magnesia, coupling agent, metal salt, isocyanates and linoleic acid composition, and filler is then to have biomass filler and polymer carrier to constitute, in configuration process, first by matrix resin, after tackifying resin and the melting of antioxidant heating stirring, add filler and antitack agent, continue after being stirred, calendering film forming, cutting, after constant temperature and humidity is stood, winding, storage, special anti-self-adhesion hot melt adhesive film is produced up to auto industry.Auto industry prepared by technical solution of the present invention produces the characteristics of special anti-self-adhesion hot melt adhesive film is with excellent mechanical property, adhesion strength and heat resistance.
Description
Technical field
The invention discloses a kind of auto industrys to produce special anti-self-adhesion hot melt adhesive film, belongs to high polymer material technology neck
Domain.
Background technology
Filminess is made in hot melt adhesive, to meet splicing needs, recently, is more and more received by big industrial production.Cause
For this adhesive material for being referred to as hot melt adhesive film has its distinctive strong point：（1）Process of Applying Glue easy to operate, not loaded down with trivial details,
As long as by hot melt adhesive film laying in splicing connection place.（2）Hot melt adhesion, complete one be glued part bonding need only several seconds,
Tens seconds, it is greatly improved work efficiency.（3）Production, the use of hot melt adhesive film are not polluted in the process.In recent years, domestic automobile
Quickly, new automobile constantly appears on the market rate of industrial development.With the continuous development of auto industry, automotive interior material is also constantly more
New to regenerate, required adhesive kind is also more and more.The interior design of some vehicles selected polyethylene or polypropylene hard and
Soft material, the difficult viscous material of these materials, in addition to being difficult to be bonded with other adhesive other than hot melt adhesive.Just because of such as
This has used hot melt adhesive film in large quantities in auto industry production of introduction.To keep relatively good seating environment, automobile it is interior
Portion's roof needs outside adiabatic, sound insulation, must also have certain rigidity（In order to install, keep dimensionally stable）, so form vehicle
Very useful composite material.But hot melt adhesive available on the market is very poor to the adhesive strength and heat resistance of PE and PP, when temperature reaches
At 60~70 DEG C, this kind of glue soon melts, non-binding intensity, will produce degumming phenomenon in practical applications so that automobile gold
Belong to material to be exposed in air, lose to its protective effect.
Therefore, how to improve conventional hot melt glued membrane adhesive property and heat resistance is poor, the bad disadvantage of mechanical property, to obtain
The hot melt adhesive film for taking more high combination property is that it is promoted and applies, meets industrial production demand urgent problem to be solved.
Invention content
The present invention solves the technical problem of：Poor, the mechanics for conventional hot melt glued membrane adhesive property and heat resistance
The bad disadvantage of performance provides a kind of special anti-self-adhesion hot melt adhesive film of auto industry production.
In order to solve the above-mentioned technical problem, the technical solution adopted in the present invention is：
A kind of special anti-self-adhesion hot melt adhesive film of auto industry production, includes the raw material of following parts by weight：
60~80 parts of matrix resin
50~60 parts of tackifying resin
10~20 parts of antitack agent
3~5 parts of antioxidant
10~20 parts of filler
The antitack agent is made of the raw material of following parts by weight：4~8 parts of nano magnesias, 8~10 parts of coupling agents, 6~10
Part metal salt, 8~10 parts of isocyanates, 30~40 parts of linoleic acid；
The filler is made of the raw material of following parts by weight：8~10 parts of biomass fillers, 20~30 parts of polymer carriers；
The configuration process that the auto industry produces special anti-self-adhesion hot melt adhesive film is：
（1）It is formed by raw material and weighs each component；
（2）After first melting matrix resin, tackifying resin and antioxidant heating stirring, filler and antitack agent are added, continues to stir
After mixing mixing, calendering film forming, cutting, after constant temperature and humidity is stood, winding, storage is to get the special anti-self-adhesion heat of auto industry production
Melten gel film.
Described matrix resin is any one in EVA resin or TPU resins.
It is 1 in mass ratio that the tackifying resin, which is by hydrogenated petroleum resin and rosin,：1~3：1 compounds.
The antioxidant is modified L-AA；The L-AA preparation process is：Chlorobenzoyl chloride and L- are resisted
Bad hematic acid is 0.6 in mass ratio：1~0.8：After 1 mixing, heating stirring reaction is anti-to get modified L- under nitrogen protection state
Bad hematic acid.
The coupling agent is silane coupling agent, any one in titanate coupling agent or aluminate coupling agent.
It is 1 in mass ratio that the metal salt, which is by calcium stearate and zinc stearate,：1~1：3 compound.
The isocyanates is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate or trimethyl cyclohexane diisocyanate
Any one in ester.
The biomass filler is any one in chitosan, casein or gelatin.
The polymer carrier is cross-linking type hydroxyethyl cellulose graft acrylamide polymer or cross-linked carboxymethyl fiber
Any one in plain graft acrylamide.
The beneficial effects of the invention are as follows：
（1）The present invention is antitack agent by using nano magnesia, coupling agent, metal salt, isocyanates and linoleic acid, is being processed
In the process, under heating condition, metal salt melts, and under lightweight and the diffusion of the lower isocyanates of boiling point,
Molten metal salt floats up to film surface, and with follow-up cooling, molten metal salt is cured again, and in film surface
Metal salt film layer is formed, during constant temperature and humidity is stood, metal salt absorbs moisture in air, and moisture is fixed on metal salt
In film layer, to effectively play the effect for preventing glued membrane self-adhesion, and in use, melting is reheated in glued membrane, at this time
Moisture evaporation in metal salt film layer will not cause harmful effect to glued membrane adhesion strength, in addition, the presence of metal salt, it can be to gold
Belong to substrate surface and form micro- rotten activation, to effectively improve adhesion strength of the glued membrane to metallic substrate surface；
（2）The present invention is antioxidant ingredient by using modified L-AA, and first, it is anti-that modified L-AA inherits L-
The excellent oxidation resistance of bad hematic acid, secondly, after the modification of chlorobenzoyl chloride, obtained benzoic acid acid ascorbyl ester after
The aromatic structure in chlorobenzoyl chloride has been held, in use, has passed through the pi bond in molecule, it is easier to adsorb, carry in metal surface
The adhesive property of high glued membrane and metallic substrate surface, and due to the complexing of hydroxyl in molecule, metal anode dissolving is made to generate
Metal ion and benzoic acid ascorbic acid molecule form insoluble complex, inhibit the anodic solution behavior of metal, avoid producing
Further erosion of the component to metallic substrate surface, effective protection metal base in product.
Specific implementation mode
It is 0.6 in mass ratio：1~0.8：Chlorobenzoyl chloride and L-AA are mixed and are poured into three-necked flask by 1, and by three
Mouthful flask moves into digital display and tests the speed constant temperature blender with magnetic force, nitrogen is passed through into three-necked flask with 30~50mL/min rates, in nitrogen
It it is 45~50 DEG C in temperature, under the conditions of rotating speed is 300~500r/min, constant temperature is stirred to react 6~8h, goes out under gas shielded state
Material, obtains modified L-AA, as antioxidant；It counts in parts by weight, takes 4~8 parts of nano magnesias, 8~10 parts of idols successively
Join agent, 6~10 parts of metal salts, 8~10 parts of isocyanates, 30~40 parts of linoleic acid, first by nano magnesia and metal salt in baking
Drying to constant weight in case, then nano magnesia and metal salt and coupling agent, the isocyanates and linoleic acid after drying are added
In ball grinder, discharges after 3~5h of ball milling mixing, obtain antitack agent；It counts in parts by weight, takes 8~10 parts of biomass fillers successively, 20
~30 parts of polymer carriers, after 45~60min of ball milling mixing, discharging obtains filler；It counts in parts by weight, takes 60~80 parts successively
Matrix resin, 50~60 parts of tackifying resins, 10~20 antitack agents, 3~5 parts of antioxidant, 10~20 parts of fillers, first by matrix tree
Fat, tackifying resin and antioxidant are heated to 180~200 DEG C, under the conditions of rotating speed is 300~500r/min after stirring melting, then
Filler and antitack agent is added, continues after being stirred 2~4h, obtains fused materials, and gained fused materials are transferred in film-forming machine,
Calendering film forming after, cooled to room temperature, then after cutting after, be transferred in greenhouse, in temperature be 30~35 DEG C, relative air humidity
Under the conditions of 65~70%, after constant temperature and humidity stands 8~12h, winding, storage is to get the special anti-self-adhesion hot melt of auto industry production
Glued membrane.Described matrix resin is any one in EVA resin or TPU resins.The tackifying resin is by hydrogenated petroleum resin
It is 1 in mass ratio with rosin：1~3：1 compounds.The coupling agent is silane coupling agent, titanate coupling agent or Aluminate
Any one in coupling agent.It is 1 in mass ratio that the metal salt, which is by calcium stearate and zinc stearate,：1~1：3 compounding and
At.The isocyanates is toluene di-isocyanate(TDI), in methyl diphenylene diisocyanate or trimethylhexane diisocyanate
Any one.The biomass filler is any one in chitosan, casein or gelatin.The polymer carrier is crosslinking
Any one in type hydroxyethyl cellulose graft acrylamide polymer or cross-linked carboxymethyl cellulose graft acrylamide.
Example 1
It is 0.8 in mass ratio：1 pours into chlorobenzoyl chloride and L-AA mixing in three-necked flask, and three-necked flask is moved into
Digital display tests the speed constant temperature blender with magnetic force, and nitrogen is passed through into three-necked flask with 50mL/min rates, under nitrogen protection state, in
Temperature is 50 DEG C, and under the conditions of rotating speed is 500r/min, constant temperature is stirred to react 8h, and discharging obtains modified L-AA, as antioxygen
Agent；It counts in parts by weight, takes 8 parts of nano magnesias, 10 parts of coupling agents, 10 parts of metal salts, 10 parts of isocyanates, 40 parts of Asias successively
Oleic acid, first by nano magnesia and metal salt, drying to constant weight in baking oven, then by the nano magnesia and metal salt after drying,
And coupling agent, isocyanates and linoleic acid are added in ball grinder, discharge after ball milling mixing 5h, obtain antitack agent；In parts by weight
Meter, takes 10 parts of biomass fillers successively, 30 parts of polymer carriers, and after ball milling mixing 60min, discharging obtains filler；In parts by weight
Meter, takes 80 parts of matrix resins successively, 60 parts of tackifying resins, 20 antitack agents, 5 parts of antioxidant, 20 parts of fillers, first by matrix resin,
Tackifying resin and antioxidant are heated to 200 DEG C, under the conditions of rotating speed is 500r/min after stirring melting, add filler and anti-sticking
Agent continues after being stirred 4h, obtains fused materials, and gained fused materials are transferred in film-forming machine, naturally cold after calendering film forming
But to room temperature, then after cutting after, be transferred in greenhouse, in temperature be 35 DEG C, relative air humidity be 70% under the conditions of, constant temperature and humidity
After standing 12h, winding, storage produces special anti-self-adhesion hot melt adhesive film to get auto industry.Described matrix resin is EVA resin.
It is 3 in mass ratio that the tackifying resin, which is by hydrogenated petroleum resin and rosin,：1 compounds.The coupling agent is silane coupled
Agent.It is 1 in mass ratio that the metal salt, which is by calcium stearate and zinc stearate,：3 compound.The isocyanates is toluene two
Isocyanates.The biomass filler is chitosan.The polymer carrier is cross-linking type hydroxyethyl cellulose grafted propylene acyl
Amine polymer.
Example 2
It is 0.8 in mass ratio：1 pours into chlorobenzoyl chloride and L-AA mixing in three-necked flask, and three-necked flask is moved into
Digital display tests the speed constant temperature blender with magnetic force, and nitrogen is passed through into three-necked flask with 50mL/min rates, under nitrogen protection state, in
Temperature is 50 DEG C, and under the conditions of rotating speed is 500r/min, constant temperature is stirred to react 8h, and discharging obtains modified L-AA, as antioxygen
Agent；It counts in parts by weight, takes 10 parts of coupling agents, 10 parts of metal salts, 10 parts of isocyanates, 40 parts of linoleic acid, first by metal successively
Drying to constant weight in baking oven for salt, then ball grinder is added in metal salt and coupling agent, the isocyanates and linoleic acid after drying
In, it discharges after ball milling mixing 5h, obtains antitack agent；It counts in parts by weight, 10 parts of biomass fillers, 30 parts of macromolecules is taken to fill out successively
Expect, after ball milling mixing 60min, discharging obtains filler；It counts in parts by weight, takes 80 parts of matrix resins successively, 60 parts of tackifying resins,
Matrix resin, tackifying resin and antioxidant are first heated to 200 DEG C, are in rotating speed by 20 antitack agents, 5 parts of antioxidant, 20 parts of fillers
Under the conditions of 500r/min after stirring melting, filler and antitack agent are added, is continued after being stirred 4h, obtains fused materials, and will
Gained fused materials are transferred in film-forming machine, calendering film forming after, cooled to room temperature, then after cutting after, be transferred in greenhouse, Yu Wen
Degree is 35 DEG C, and under the conditions of relative air humidity is 70%, after constant temperature and humidity stands 12h, winding, storage produces to get auto industry
Special anti-self-adhesion hot melt adhesive film.Described matrix resin is EVA resin.The tackifying resin be by hydrogenated petroleum resin and rosin by
Mass ratio is 3：1 compounds.The coupling agent is silane coupling agent.The metal salt be by calcium stearate and zinc stearate by
Mass ratio is 1：3 compound.The isocyanates is toluene di-isocyanate(TDI).The biomass filler is chitosan.It is described
Polymer carrier is cross-linking type hydroxyethyl cellulose graft acrylamide polymer.
Example 3
It is 0.8 in mass ratio：1 pours into chlorobenzoyl chloride and L-AA mixing in three-necked flask, and three-necked flask is moved into
Digital display tests the speed constant temperature blender with magnetic force, and nitrogen is passed through into three-necked flask with 50mL/min rates, under nitrogen protection state, in
Temperature is 50 DEG C, and under the conditions of rotating speed is 500r/min, constant temperature is stirred to react 8h, and discharging obtains modified L-AA, as antioxygen
Agent；It counts in parts by weight, takes 8 parts of nano magnesias successively, 10 parts of coupling agents, 10 parts of isocyanates, 40 parts of linoleic acid will first receive
Drying to constant weight in baking oven for rice magnesia, then by nano magnesia and coupling agent, the isocyanates and linoleic acid after drying
It is added in ball grinder, discharges after ball milling mixing 5h, obtain antitack agent；It counts in parts by weight, takes 10 parts of biomass fillers successively, 30 parts
Polymer carrier, after ball milling mixing 60min, discharging obtains filler；It counts in parts by weight, takes 80 parts of matrix resins, 60 parts of increasings successively
Matrix resin, tackifying resin and antioxidant are first heated to 200 DEG C by viscosity resin, 20 antitack agents, 5 parts of antioxidant, 20 parts of fillers,
Under the conditions of rotating speed is 500r/min after stirring melting, filler and antitack agent are added, continues after being stirred 4h, obtains fusant
Material, and gained fused materials is transferred in film-forming machine, after calendering film forming, cooled to room temperature, then after cutting after, be transferred to greenhouse
In, it is 35 DEG C in temperature, under the conditions of relative air humidity is 70%, after constant temperature and humidity stands 12h, winding is put in storage to get automobile
The special anti-self-adhesion hot melt adhesive film of industrial production.Described matrix resin is EVA resin.The tackifying resin is by hydrogenated petroleum resin
It is 3 in mass ratio with rosin：1 compounds.The coupling agent is silane coupling agent.The isocyanates is toluene diisocynate
Ester.The biomass filler is chitosan.The polymer carrier polymerize for cross-linking type hydroxyethyl cellulose graft acrylamide
Object.
Example 4
It is 0.8 in mass ratio：1 pours into chlorobenzoyl chloride and L-AA mixing in three-necked flask, and three-necked flask is moved into
Digital display tests the speed constant temperature blender with magnetic force, and nitrogen is passed through into three-necked flask with 50mL/min rates, under nitrogen protection state, in
Temperature is 50 DEG C, and under the conditions of rotating speed is 500r/min, constant temperature is stirred to react 8h, and discharging obtains modified L-AA, as antioxygen
Agent；It counts in parts by weight, takes 8 parts of nano magnesias, 10 parts of coupling agents, 10 parts of metal salts, 40 parts of linoleic acid, first by nanometer successively
Drying to constant weight in baking oven for magnesia and metal salt, then by after drying nano magnesia and metal salt and coupling agent and
Linoleic acid is added in ball grinder, discharges after ball milling mixing 5h, obtains antitack agent；It counts in parts by weight, 10 parts of biomass is taken to fill out successively
Expect, 30 parts of polymer carriers, after ball milling mixing 60min, discharging obtains filler；It counts in parts by weight, takes 80 parts of matrix trees successively
Fat, 60 parts of tackifying resins, 20 antitack agents, 5 parts of antioxidant, 20 parts of fillers first heat matrix resin, tackifying resin and antioxidant
To 200 DEG C, under the conditions of rotating speed is 500r/min after stirring melting, filler and antitack agent is added, is continued after being stirred 4h,
Fused materials, and gained fused materials are transferred in film-forming machine, after calendering film forming, cooled to room temperature, then after cutting after,
It is transferred in greenhouse, is 35 DEG C in temperature, under the conditions of relative air humidity is 70%, after constant temperature and humidity stands 12h, winds, storage,
Special anti-self-adhesion hot melt adhesive film is produced up to auto industry.Described matrix resin is EVA resin.The tackifying resin is by hydrogenating
Petropols and rosin are 3 in mass ratio：1 compounds.The coupling agent is silane coupling agent.The metal salt is by tristearin
Sour calcium and zinc stearate are 1 in mass ratio：3 compound.The biomass filler is chitosan.The polymer carrier is to hand over
Connection type hydroxyethyl cellulose graft acrylamide polymer.
Example 5
It is 0.8 in mass ratio：1 pours into chlorobenzoyl chloride and L-AA mixing in three-necked flask, and three-necked flask is moved into
Digital display tests the speed constant temperature blender with magnetic force, and nitrogen is passed through into three-necked flask with 50mL/min rates, under nitrogen protection state, in
Temperature is 50 DEG C, and under the conditions of rotating speed is 500r/min, constant temperature is stirred to react 8h, and discharging obtains modified L-AA, as antioxygen
Agent；It counts in parts by weight, takes 8 parts of nano magnesias successively, 10 parts of coupling agents, 10 parts of metal salts, 10 parts of isocyanates will first receive
Drying to constant weight in baking oven for rice magnesia and metal salt, then by after drying nano magnesia and metal salt and coupling agent,
Isocyanates is added in ball grinder, discharges after ball milling mixing 5h, obtains antitack agent；It counts in parts by weight, takes 10 parts of biomass successively
Filler, 30 parts of polymer carriers, after ball milling mixing 60min, discharging obtains filler；It counts in parts by weight, takes 80 parts of matrix trees successively
Fat, 60 parts of tackifying resins, 20 antitack agents, 5 parts of antioxidant, 20 parts of fillers first heat matrix resin, tackifying resin and antioxidant
To 200 DEG C, under the conditions of rotating speed is 500r/min after stirring melting, filler and antitack agent is added, is continued after being stirred 4h,
Fused materials, and gained fused materials are transferred in film-forming machine, after calendering film forming, cooled to room temperature, then after cutting after,
It is transferred in greenhouse, is 35 DEG C in temperature, under the conditions of relative air humidity is 70%, after constant temperature and humidity stands 12h, winds, storage,
Special anti-self-adhesion hot melt adhesive film is produced up to auto industry.Described matrix resin is EVA resin.The tackifying resin is by hydrogenating
Petropols and rosin are 3 in mass ratio：1 compounds.The coupling agent is silane coupling agent.The metal salt is by tristearin
Sour calcium and zinc stearate are 1 in mass ratio：3 compound.The isocyanates is toluene di-isocyanate(TDI).The biomass is filled out
Material is chitosan.The polymer carrier is cross-linking type hydroxyethyl cellulose graft acrylamide polymer.
Example 6
It is 0.8 in mass ratio：1 pours into chlorobenzoyl chloride and L-AA mixing in three-necked flask, and three-necked flask is moved into
Digital display tests the speed constant temperature blender with magnetic force, and nitrogen is passed through into three-necked flask with 50mL/min rates, under nitrogen protection state, in
Temperature is 50 DEG C, and under the conditions of rotating speed is 500r/min, constant temperature is stirred to react 8h, and discharging obtains modified L-AA, as antioxygen
Agent；It counts in parts by weight, takes 8 parts of nano magnesias, 10 parts of coupling agents, 10 parts of metal salts, 10 parts of isocyanates, 40 parts of Asias successively
Oleic acid, first by nano magnesia and metal salt, drying to constant weight in baking oven, then by the nano magnesia and metal salt after drying,
And coupling agent, isocyanates and linoleic acid are added in ball grinder, discharge after ball milling mixing 5h, obtain antitack agent；In parts by weight
Meter, takes 30 parts of polymer carriers successively, and after ball milling mixing 60min, discharging obtains filler；It counts in parts by weight, takes 80 parts of bases successively
Body resin, 60 parts of tackifying resins, 20 antitack agents, 5 parts of antioxidant, 20 parts of fillers, first by matrix resin, tackifying resin and antioxidant
200 DEG C are heated to, under the conditions of rotating speed is 500r/min after stirring melting, filler and antitack agent is added, continues to be stirred
After 4h, fused materials are obtained, and gained fused materials are transferred in film-forming machine, after calendering film forming, cooled to room temperature, then through cutting
It after cutting, is transferred in greenhouse, is 35 DEG C in temperature, under the conditions of relative air humidity is 70%, after constant temperature and humidity stands 12h, winds,
Storage produces special anti-self-adhesion hot melt adhesive film to get auto industry.Described matrix resin is EVA resin.The tackifying resin is
It is 3 in mass ratio by hydrogenated petroleum resin and rosin：1 compounds.The coupling agent is silane coupling agent.The metal salt is
It is 1 in mass ratio by calcium stearate and zinc stearate：3 compound.The isocyanates is toluene di-isocyanate(TDI).The height
Molecular stuffing is cross-linking type hydroxyethyl cellulose graft acrylamide polymer.
Example 7
It is 0.8 in mass ratio：1 pours into chlorobenzoyl chloride and L-AA mixing in three-necked flask, and three-necked flask is moved into
Digital display tests the speed constant temperature blender with magnetic force, and nitrogen is passed through into three-necked flask with 50mL/min rates, under nitrogen protection state, in
Temperature is 50 DEG C, and under the conditions of rotating speed is 500r/min, constant temperature is stirred to react 8h, and discharging obtains modified L-AA, as antioxygen
Agent；It counts in parts by weight, takes 8 parts of nano magnesias, 10 parts of coupling agents, 10 parts of metal salts, 10 parts of isocyanates, 40 parts of Asias successively
Oleic acid, first by nano magnesia and metal salt, drying to constant weight in baking oven, then by the nano magnesia and metal salt after drying,
And coupling agent, isocyanates and linoleic acid are added in ball grinder, discharge after ball milling mixing 5h, obtain antitack agent；In parts by weight
Meter, takes 10 parts of biomass fillers successively, and after ball milling mixing 60min, discharging obtains filler；It counts in parts by weight, takes 80 parts of bases successively
Body resin, 60 parts of tackifying resins, 20 antitack agents, 5 parts of antioxidant, 20 parts of fillers, first by matrix resin, tackifying resin and antioxidant
200 DEG C are heated to, under the conditions of rotating speed is 500r/min after stirring melting, filler and antitack agent is added, continues to be stirred
After 4h, fused materials are obtained, and gained fused materials are transferred in film-forming machine, after calendering film forming, cooled to room temperature, then through cutting
It after cutting, is transferred in greenhouse, is 35 DEG C in temperature, under the conditions of relative air humidity is 70%, after constant temperature and humidity stands 12h, winds,
Storage produces special anti-self-adhesion hot melt adhesive film to get auto industry.Described matrix resin is EVA resin.The tackifying resin is
It is 3 in mass ratio by hydrogenated petroleum resin and rosin：1 compounds.The coupling agent is silane coupling agent.The metal salt is
It is 1 in mass ratio by calcium stearate and zinc stearate：3 compound.The isocyanates is toluene di-isocyanate(TDI).The life
Substance filler is chitosan.
Example 8
It counts in parts by weight, takes 8 parts of nano magnesias successively, 10 parts of coupling agents, 10 parts of metal salts, 10 parts of isocyanates, 40 parts
Linoleic acid, first by nano magnesia and metal salt, drying to constant weight in baking oven, then by the nano magnesia and metal after drying
Salt and coupling agent, isocyanates and linoleic acid are added in ball grinder, discharge after ball milling mixing 5h, obtain antitack agent；By weight
Number meter, takes 10 parts of biomass fillers successively, 30 parts of polymer carriers, and after ball milling mixing 60min, discharging obtains filler；By weight
Number meter, takes 80 parts of matrix resins, 60 parts of tackifying resins, 20 antitack agents, 5 parts of L-AAs, 20 parts of fillers, first by matrix successively
Resin, tackifying resin and L-AA are heated to 200 DEG C, under the conditions of rotating speed is 500r/min after stirring melting, add
Filler and antitack agent continue after being stirred 4h, obtain fused materials, and gained fused materials are transferred in film-forming machine, are rolled into
After film, cooled to room temperature, then after cutting after, be transferred in greenhouse, in temperature be 35 DEG C, relative air humidity be 70% condition
Under, after constant temperature and humidity stands 12h, winding, storage produces special anti-self-adhesion hot melt adhesive film to get auto industry.Described matrix tree
Fat is EVA resin.It is 3 in mass ratio that the tackifying resin, which is by hydrogenated petroleum resin and rosin,：1 compounds.The coupling
Agent is silane coupling agent.It is 1 in mass ratio that the metal salt, which is by calcium stearate and zinc stearate,：3 compound.The isocyanide
Acid esters is toluene di-isocyanate(TDI).The biomass filler is chitosan.The polymer carrier is cross-linking type hydroxy ethyl fiber
Plain graft acrylamide polymer.
Comparative example：The hot melt adhesive film of Dongguan City new material Science and Technology Ltd. production.
The auto industry of 1 to 8 gained of example is produced into special anti-self-adhesion hot melt adhesive film and comparative example product carries out performance inspection
It surveys, specific detection method is as follows：
1. mechanical property：Test specimen tensile strength is detected according to by GB/T 6329；
2. adhesive property：According to GB 2791 to test specimen and metal testing plate（Aluminium flake）Peel strength is detected.
Specific testing result is as shown in table 1：
Table 1：Mechanical property and the specific testing result of adhesive property
| Detection project | Tensile strength/MPa | Peel strength Nian Jie with aluminium flake/（kN/m） |
| Example 1 | 27.1 | 9.3 |
| Example 2 | 25.4 | 8.7 |
| Example 3 | 20.8 | 6.6 |
| Example 4 | 21.7 | 7.2 |
| Example 5 | 14.1 | 5.4 |
| Example 6 | 16.9 | 5.9 |
| Example 7 | 15.2 | 5.7 |
| Example 8 | 13.6 | 4.3 |
| Comparative example | 9.3 | 3.1 |
By 1 testing result of table it is found that the special anti-self-adhesion hot melt adhesive film of auto industry production prepared by technical solution of the present invention has
The characteristics of mechanical property and adhesive property, has broad prospects in the development of hot melt adhesive film industry.
Claims (9)
1. a kind of auto industry produces special anti-self-adhesion hot melt adhesive film, include the raw material of following parts by weight：
60~80 parts of matrix resin
50~60 parts of tackifying resin
10~20 parts of antitack agent
3~5 parts of antioxidant
10~20 parts of filler
It is characterized in that：
The antitack agent is made of the raw material of following parts by weight：4~8 parts of nano magnesias, 8~10 parts of coupling agents, 6~10
Part metal salt, 8~10 parts of isocyanates, 30~40 parts of linoleic acid；
The filler is made of the raw material of following parts by weight：8~10 parts of biomass fillers, 20~30 parts of polymer carriers；
The configuration process that the auto industry produces special anti-self-adhesion hot melt adhesive film is：
（1）It is formed by raw material and weighs each component；
（2）After first melting matrix resin, tackifying resin and antioxidant heating stirring, filler and antitack agent are added, continues to stir
After mixing mixing, calendering film forming, cutting, after constant temperature and humidity is stood, winding, storage is to get the special anti-self-adhesion heat of auto industry production
Melten gel film.
2. a kind of auto industry according to claim 1 produces special anti-self-adhesion hot melt adhesive film, it is characterised in that：The base
Body resin is any one in EVA resin or TPU resins.
3. a kind of auto industry according to claim 1 produces special anti-self-adhesion hot melt adhesive film, it is characterised in that：The increasing
It is 1 in mass ratio that viscosity resin, which is by hydrogenated petroleum resin and rosin,：1~3：1 compounds.
4. a kind of auto industry according to claim 1 produces special anti-self-adhesion hot melt adhesive film, it is characterised in that：It is described anti-
Oxygen agent is modified L-AA；The L-AA preparation process is：In mass ratio by chlorobenzoyl chloride and L-AA
It is 0.6：1~0.8：After 1 mixing, heating stirring reaction is to get modified L-AA under nitrogen protection state.
5. a kind of auto industry according to claim 1 produces special anti-self-adhesion hot melt adhesive film, it is characterised in that：The idol
Connection agent is silane coupling agent, any one in titanate coupling agent or aluminate coupling agent.
6. a kind of auto industry according to claim 1 produces special anti-self-adhesion hot melt adhesive film, it is characterised in that：The gold
It is 1 in mass ratio that category salt, which is by calcium stearate and zinc stearate,：1~1：3 compound.
7. a kind of auto industry according to claim 1 produces special anti-self-adhesion hot melt adhesive film, it is characterised in that：It is described different
Cyanate is toluene di-isocyanate(TDI), any one in methyl diphenylene diisocyanate or trimethylhexane diisocyanate
Kind.
8. a kind of auto industry according to claim 1 produces special anti-self-adhesion hot melt adhesive film, it is characterised in that：The life
Substance filler is any one in chitosan, casein or gelatin.
9. a kind of auto industry according to claim 1 produces special anti-self-adhesion hot melt adhesive film, it is characterised in that：The height
Molecular stuffing is cross-linking type hydroxyethyl cellulose graft acrylamide polymer or cross-linked carboxymethyl cellulose graft acrylamide
In any one.
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| CN114350280A (en) * | 2022-01-18 | 2022-04-15 | 鑫序高分子材料(苏州)有限公司 | High-temperature-resistant hot-melt adhesive film and preparation method thereof |
| WO2024021204A1 (en) * | 2022-07-28 | 2024-02-01 | 广东汇齐新材料有限公司 | Biomass tpu hot melt adhesive film and preparation method therefor |
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