CN112409963A - Environment-friendly hot melt adhesive, adhesive tape and preparation method thereof - Google Patents
Environment-friendly hot melt adhesive, adhesive tape and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J145/00—Adhesives based on homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic system; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/35—Heat-activated
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
- C09J2453/00—Presence of block copolymer
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Abstract
The invention relates to an environment-friendly hot melt adhesive which comprises the following raw materials in percentage by mass: 30-55% of polystyrene block copolymer, 26-55% of tackifying resin, 5-15% of plasticizer, 3-10% of heat conducting particles and 0.5-1.0% of antioxidant 1010; the polystyrene block copolymer is a mixture of a styrene-isoprene-styrene copolymer and a styrene-butadiene-styrene copolymer. The invention also relates to an adhesive tape using the environment-friendly hot melt adhesive and a preparation method thereof. The hot melt adhesive tape can be activated by laser, the adhesive film is uniformly heated, the laser bonding processing speed is high, the adhesive tape has good adaptability and high bonding strength for bonding a transparent panel/frame body in a display screen, the bonded product has excellent performances of water resistance, cold resistance, impact resistance and the like, and the reworking performance of the adhesive tape is good. The invention reduces the melt viscosity of the hot melt adhesive, can perform hot melt coating of the hot melt adhesive, replaces the traditional solvent coating, and realizes the solvent-free production of the hot melt adhesive and the adhesive tape thereof.
Description
Technical Field
The invention relates to the field of adhesive tapes, in particular to an environment-friendly hot melt adhesive, an adhesive tape and a preparation method thereof.
Background
Modern consumer electronics products such as mobile phones, tablet terminals, liquid crystal televisions, digital camera devices, portable game consoles and the like all have visual display systems to display the operating status of the device, or other information, often using Liquid Crystal (LCD) or Organic Light Emitting Diode (OLED) based display modules to implement the display function. These apparatuses include a transparent panel such as a glass plate or acrylic plate for displaying a screen, in addition to a frame for accommodating a substrate or the like. Since the peripheral portion of the display screen has the connection terminals, the peripheral portion of the transparent panel needs to be formed with a black printed portion, a so-called frame portion, so that the terminals are not visible from the surface side of the transparent panel at the outermost layer of the display screen. Generally, the transparent panels of the display screen are bonded to the frame body by an adhesive hidden under the bezel. In recent years, to reduce the appearance of the screen of the electronic device and to increase the display screen to become a popular trend of the consumer electronic screen, the width of the frame part of the transparent panel becomes narrower (narrow frame), and thus the width of the adhesive agent covered under the frame becomes narrower (the width is required to be less than or equal to 2mm, or less than or equal to 1mm, or less than or equal to 0.8mm, or even less than or equal to 0.5mm), and thus the requirement for the adhesive property of the adhesive agent is more severe.
Although the liquid adhesive can meet the requirements, the problems of unclean operation of finished products caused by extrusion of the adhesive, migration of a solvent from the adhesive to a formed product, harmful organic volatile substances (VOC) and odor brought by the adhesive and the like exist; the pressure-sensitive adhesive tape has a problem of insufficient adhesive strength. The hot melt adhesive tape has the advantages of reliable bonding strength, good push-out resistance, good anti-seismic performance and the like, so that the hot melt adhesive tape has wide application space in the consumer electronics industry, but the hot melt adhesive has no bonding property in a solid state, and how to activate the performance of the hot melt adhesive and achieve the optimal bonding process always hinders the application of the hot melt adhesive in the consumer electronics industry.
The hot melt adhesive tape usually adopts a hot-pressing laminating mode, and the instability of batch production caused by poor double-layer temperature control precision and nonuniform heating exists in the mode; the pressure is not uniform, so that transparent panels such as glass and the like are damaged; the parallax error is monitored visually, and the positioning cannot be accurate; compatibility is poor, and various products cannot be considered; long heating time, greatly increased processing cost and the like. Because the laser has the excellent performances of high energy density, good coherence, good monochromaticity, strong directivity and the like, the hot melt adhesive can be thermally activated by the laser to have viscosity, so that the bonding of an upper layer material and a lower layer material is realized, and the processing technology has the advantages of uniform and controllable temperature of an adhesive film, observable bonding parts, high processing speed, (capability of meeting materials to be bonded with different sizes and shapes) and high flexibility, so the hot melt adhesive activated by the laser has higher application value.
Further, when the product inspection finds that there is a defect in the transparent panel, the substrate, or the like, or the bonding operation fails, or the screen removal maintenance is performed, the transparent panel may be temporarily detached from the housing, and usable components may be reused. However, if the adhesive remains on the transparent panel or the frame, the adhesive becomes an obstacle to reuse, and therefore, there is a problem that the adhesive must be gradually peeled off by using a solvent, heating, or the like.
Patent document CN103781869B discloses a solvent-based adhesive containing a styrene-butadiene-styrene copolymer and a terpene tackifier, which can be prepared in the form of a tape sandwiched between a first member and a second member having light transmittance, and which can be bonded to each other by heating the patterned layer of the first member by laser irradiation to soften the tape and thereby cause tackiness, and which can also be heated by laser irradiation to reduce tackiness and cause peeling of the two members, and which has good room-temperature bonding strength and reworkability (low reworking peeling force and no residue on the two members). However, the laser heats the pattern layer to soften the adhesive film adjacent to the pattern layer in an indirect heat transfer mode, which affects the processing speed of laser bonding and still has the problem of uneven heating; in addition, the problems of VOC, adhesive tape production environment, human health, solvent recovery cost and the like caused by solvent volatilization when the solvent-based adhesive is prepared into the adhesive tape.
Patent document CN108531114A discloses a solvent-based laser-activated adhesive, which is mainly composed of styrene-butadiene-styrene (SBS)/hydrogenated styrene-butadiene block copolymer (SEBS)/styrene-isoprene-styrene block copolymer (SIS), can be applied to inclined, corner, and curved surfaces by a dispensing head without flowing randomly, and is very suitable for bonding between components in a non-planar form. However, the above two defects of patent CN103781869B also exist.
Due to different actual use environments of consumer electronics products and narrow frames of display screens, the bonding strength of the adhesive capable of being activated by laser to the transparent panel and the frame body is high, and the performance requirements of the products on impact resistance, cold resistance, water resistance and the like are met. The reworking of the transparent panel and the frame adhesive member requires that the adhesive tape does not remain on the transparent panel and the frame. In addition, the problems of solvent generated by the solvent type hot melt adhesive and the adhesive tape thereof and uneven laser bonding processing speed and heating are solved. Therefore, there is a need to develop an environmentally friendly hot melt adhesive tape having high bonding strength between the transparent panel and the frame, good reworkability (low reworking peel force and no residue on the two members), and rapid and uniform laser activation heating rate.
Disclosure of Invention
The invention aims to solve the problems and provides a laser-activated environment-friendly hot melt adhesive, an adhesive tape and a preparation method thereof.
In order to solve the technical problems, the invention provides an environment-friendly hot melt adhesive which comprises the following raw materials in percentage by mass: 30-55% of polystyrene block copolymer, 26-55% of tackifying resin, 5-15% of plasticizer, 3-10% of heat conducting particles and 0.5-1.0% of antioxidant 1010; the polystyrene block copolymer is a mixture of a styrene-isoprene-styrene copolymer and a styrene-butadiene-styrene copolymer, and when the content of the styrene-isoprene-styrene copolymer is 100 parts by weight, the content of the styrene-butadiene-styrene copolymer is 10-40 parts by weight, namely the mass ratio of the styrene-isoprene-styrene copolymer to the styrene-butadiene-styrene copolymer is 2.5: 1-10: 1; the tackifying resin is one of rosin resin, terpene resin and petroleum resin; the plasticizer is aliphatic mineral oil or mineral oil with aromatic ring content less than 5 percent which is compatible with the diene block of the polystyrene block copolymer and the tackifying resin; the heat conducting particles are nano-scale heat conducting particles with heat conductivity coefficient more than 200W/(m.K) and average particle size of 40-60 nm.
Furthermore, the mass content of styrene in the styrene-isoprene-styrene copolymer is 10-40%, and the mass content of the styrene-isoprene diblock component is 0-40%.
Furthermore, the mass content of styrene in the styrene-butadiene-styrene copolymer is 10-35%, and the mass content of the styrene-butadiene diblock component is 0-20%.
Further, the styrene-butadiene-styrene copolymer is one or more of D-1102JS, DX-405JOP, D1116, D1192, D1153 and D4153 of KRATON company.
The tackifying resin is preferably a terpene resin having a softening point of 80-120 ℃ and YS (Ys of YASUHARA CHEMICAL Co.)T80、YST100、YST115, or ARIZNA CHEMICALTP95、TP105、One of the TPs 115.
Further, the heat conducting particles are one of silicon carbide, titanium carbide or boron carbide of KAIER NANO company.
The invention also provides an environment-friendly hot melt adhesive tape, which uses the environment-friendly hot melt adhesive in the proportion, is arranged between the first part of the light-transmitting transparent panel and the second part of the light-proof frame body, absorbs the energy of laser irradiated on the first part, is heated and softened to be sticky, and realizes effective bonding of the first part and the second part.
Furthermore, the first component of the light-transmitting transparent panel is a transparent panel of which the upper surface is light-transmitting and the lower surface facing the frame is also light-transmitting or contains a black narrow frame, the panel is made of polyacrylate (organic glass), Polycarbonate (PC), glass and the like, and the second component of the light-proof frame is made of plastic such as ABS, PC and the like or metal such as aluminum Al and the like.
The use method of the environment-friendly hot melt adhesive tape comprises the following steps:
(1) when the adhesive tape is used, the adhesive tape is placed between the first part of the light-transmitting transparent panel and the second part of the light-proof frame body, the first part is irradiated by laser, the adhesive tape quickly absorbs laser energy and is heated to be softened to form viscosity, and effective bonding of the first part and the second part is achieved.
(2) When the adhesive tape is used for heavy work, a workpiece for bonding the first component and the second component by the adhesive tape needs to be peeled off again, the adhesive tape is activated for the second time by laser or heated to 80-100 ℃ for softening, the first component and the second component can be easily separated, the adhesive tape is damaged by interface peeling, and the adhesive tape cannot remain on related components.
The invention also provides a preparation method of the environment-friendly hot melt adhesive tape, which comprises the following steps:
first, preparation stage of hot melt adhesive
S1: weighing a plasticizer, tackifying resin and an antioxidant 1010 according to a formula, putting into a reaction kettle, introducing nitrogen into the reaction kettle, heating to 120-140 ℃ while stirring, adding heat conducting particles weighed according to the formula after all solids are melted and uniformly mixed, and stirring for 10-30 min;
s2: then adding the weighed polystyrene block copolymer, heating to 170-180 ℃, and stirring for 1-2 hours;
s3: stopping heating, stopping introducing nitrogen, vacuumizing the reaction kettle under the condition of continuously stirring, and keeping the vacuum pressure at-0.08 MPa for 30 min;
s4: evacuating, introducing 0.1MPa compressed air into the reaction kettle, discharging, cooling the hot melt adhesive into a glue block, and packaging to obtain the environment-friendly hot melt adhesive;
(II) Hot melt adhesive coating stage
S5: and melting the hot melt adhesive block at 170-180 ℃, wherein the melt viscosity is 10000-20000 mPa.s, and coating the hot melt adhesive block on glassine paper or a PET release film to obtain the environment-friendly hot melt adhesive tape containing the release carrier.
According to the invention, by adjusting the proportion of the styrene-isoprene-styrene copolymer with viscoelasticity and the styrene-butadiene-styrene copolymer with high cohesive force in the main polymer resin of the hot melt adhesive, the hot melt adhesive can be ensured to permeate and conform to the shapes of the concave and convex steps after being softened under the condition that the concave and convex steps exist on the bonding surface, and can be tightly bonded with the bonding surface without gaps and the bonding strength, so that the requirements of the product on the performances such as water resistance, cold resistance and impact resistance are met; the softening points of the main polymer resin and the tackifying resin are adjusted, so that the hot melt adhesive has high peel strength at normal temperature and low peel strength at 80-100 ℃, the bonded product is firm under the application environment of less than 60 ℃, the bonded product is easy to peel at high temperature, and sufficient strength can be ensured after the peeled hot melt adhesive is cooled, so that the hot melt adhesive can be easily peeled off from the bonding surface, and the reworkability is good; by adjusting the proportion of the styrene content and the diblock in the main polymer resin and the type and the amount of the plasticizer, the hot melt adhesive has lower melt viscosity at 170-180 ℃, can be easily coated to form a film to prepare an adhesive tape, realizes solvent-free coating, and has the advantage of environmental protection in production; by introducing the nanoscale heat-conducting particles with high heat conductivity into the hot melt adhesive, the hot melt adhesive tape is high in heating rate and uniform in heating during laser activation, and the bonding stability of the product and the laser processing speed are improved.
Compared with the prior art, the invention has the advantages that:
(1) the hot melt adhesive tape can be activated by laser, a more efficient laser bonding process is adopted, the adaptability to bonding of a transparent panel/frame body in a display screen is good, the bonding strength is high, the bonded product has excellent waterproof, cold-resistant and impact-resistant performances, meanwhile, the bonding piece can be easily peeled off at 80-100 ℃, the hot melt adhesive is easily peeled off from the bonding surface, and the reworking performance of the adhesive tape is good.
(2) The invention solves the problems of uneven heating of the adhesive film and improvement of the processing speed of laser bonding when the hot melt adhesive is subjected to laser bonding through the action of the nano heat-conducting particles with high heat conductivity.
(3) The invention reduces the melt viscosity of the hot melt adhesive, can perform hot melt coating of the hot melt adhesive, replaces the traditional solvent coating, and realizes the solvent-free production of the hot melt adhesive and the adhesive tape thereof.
Detailed Description
The environment-friendly hot melt adhesive comprises the following raw materials in percentage by mass: 30-55% of polystyrene block copolymer, 26-55% of tackifying resin, 5-15% of plasticizer, 3-10% of heat conducting particles and 0.5-1.0% of antioxidant 1010; the polystyrene block copolymer is a mixture of a styrene-isoprene-styrene copolymer and a styrene-butadiene-styrene copolymer, and when the content of the styrene-isoprene-styrene copolymer is 100 parts by weight, the content of the styrene-butadiene-styrene copolymer is 10-40 parts by weight; the tackifying resin is one of rosin resin, terpene resin and petroleum resin; the plasticizer is aliphatic mineral oil or mineral oil with aromatic ring content less than 5 percent which is compatible with the diene block of the polystyrene block copolymer and the tackifying resin; the heat conducting particles are nano-scale heat conducting particles with heat conductivity coefficient more than 200W/(m.K) and average particle size of 40-60 nm. The styrene-isoprene-styrene copolymer contains 10-40% by mass of styrene and 0-40% by mass of a styrene-isoprene diblock component; preferably, the mass content of the styrene is 10-30%, and the mass content of the styrene-isoprene diblock component is 0-25%. The styrene-isoprene-styrene copolymer is prepared from DEXCO POLYMER4111A、4113A、4211A、4215A. The mass content of styrene in the styrene-butadiene-styrene copolymer is 10-35%, and the mass content of the styrene-butadiene diblock component isThe mass content is 0-20%. The styrene-butadiene-styrene copolymer is one or more of D-1102JS, DX-405JOP, D1116, D1192, D1153 and D4153 of KRATON company. The tackifying resin is preferably a terpene resin, the softening point of the terpene resin is 80-120 ℃, and the terpene resin is YS (Ys of YASUHARA CHEMICAL Co.)T80、YS T100、YST115, or ARIZNA CHEMICALTP95、TP105、One of the TPs 115. The plasticizer is Shell company371、451、956、6204, a naphthenic oil. The thermally conductive particles are one of silicon carbide, titanium carbide or boron carbide from KAIER NANO corporation.
Example 1
The environment-friendly hot melt adhesive comprises the following raw materials in percentage by mass: 30% of polystyrene block copolymer, 55% of tackifying resin, 5% of plasticizer, 9.5% of heat conducting particles and 0.5% of antioxidant 1010; the polystyrene block copolymer is a mixture of a styrene-isoprene-styrene copolymer and a styrene-butadiene-styrene copolymer, and the mass ratio of the styrene-isoprene-styrene copolymer to the styrene-butadiene-styrene copolymer is 2.5: 1.
In this embodiment, the styrene-isoprene-styrene copolymer is prepared by mixing 18% of styrene by mass and 18% of styrene-isoprene diblock component by mass<1% of4111A and styrene in an amount of 15% by mass, the styrene-isoprene diblock component being in an amount of 18% by mass4113A。
In this embodiment, the styrene-butadiene-styrene copolymer is preferably DX-405JOP having a styrene mass content of 24% and a styrene mass content of DX-405JOP having a styrene mass content of 0% and D1116 having a styrene mass content of 16% in the styrene-butadiene diblock component, all of which are manufactured by KRATON corporation.
In the embodiment, the tackifying resin is preferably a terpene resin with a softening point of 80-120 ℃, and the terpene resin is YS (Ys of YASUHARA CHEMICAL Co.)T80。
Preferably, the plasticizer in this embodiment is an aliphatic mineral oil or a mineral oil having an aromatic ring content of < 5% that is compatible with both the diene block of the polystyrene block copolymer and the tackifying resin; the plasticizer is Shell company371。
The heat conducting particles are silicon carbide of KAIER NANO company, and the heat conducting particles are NANO-scale heat conducting particles with heat conductivity coefficient more than 200W/(m.K) and average particle size of 40-60 nm.
The environment-friendly hot melt adhesive tape of this embodiment has used the environment-friendly hot melt adhesive like aforementioned ratio, and environment-friendly hot melt adhesive tape sets up between the first part of light transmissivity transparent panel and the second part of light tight frame body, absorbs the energy of the laser that shines first part and is heated and softened viscidity, realizes effectively bonding to first part and second part, and its preparation method includes following step:
first, preparation stage of hot melt adhesive
S1: putting 5% by mass of plasticizer, 55% by mass of tackifying resin and 0.5% by mass of antioxidant 1010 into a reaction kettle, introducing nitrogen into the reaction kettle, heating to 120-140 ℃ while stirring, adding 9.5% by mass of silicon carbide after the solids are completely melted and uniformly mixed, and stirring for 10-30 min;
s2: then adding 30 mass percent of polystyrene block copolymer, heating to 170-180 ℃, and stirring for 1-2 hours;
s3: stopping heating, stopping introducing nitrogen, vacuumizing the reaction kettle under the condition of continuously stirring, and keeping the vacuum pressure at-0.08 MPa for 30 min;
s4: evacuating, introducing 0.1MPa compressed air into the reaction kettle, discharging, cooling the hot melt adhesive into a glue block, and packaging to obtain the environment-friendly hot melt adhesive;
(II) Hot melt adhesive coating stage
S5: and melting the hot melt adhesive block at 170-180 ℃, wherein the melt viscosity is 10000-20000 mPa.s, and coating the hot melt adhesive block on glassine paper or a PET release film to obtain the environment-friendly hot melt adhesive tape containing the release carrier.
In the preferred embodiment, the thickness of the environmentally friendly hot melt adhesive tape is 40-300 um.
Example 2
The environment-friendly hot melt adhesive comprises the following raw materials in percentage by mass: 35% of a polystyrene block copolymer, 45% of a tackifying resin, 10% of a plasticizer, 9.2% of thermally conductive particles, and 0.8% of an antioxidant 1010; the polystyrene block copolymer is a mixture of a styrene-isoprene-styrene copolymer and a styrene-butadiene-styrene copolymer, and the mass ratio of the styrene-isoprene-styrene copolymer to the styrene-butadiene-styrene copolymer is 4: 1.
In this embodiment, the styrene-isoprene-styrene copolymer is prepared by mixing 18% of styrene by mass and 18% of styrene-isoprene diblock component by mass<1% of4111A and styrene in an amount of 30% by mass, the styrene-isoprene diblock component being in an amount of 18% by mass4215A。
In this embodiment, the styrene-butadiene-styrene copolymer is preferably D-1102JS with a styrene mass content of 28%, a styrene-butadiene diblock component mass content of 16%, and DX-405JOP with a styrene mass content of 24%, and a styrene-butadiene diblock component mass content of 0%, manufactured by KRATON.
In the embodiment, the tackifying resin is preferably a terpene resin with a softening point of 80-120 ℃, and the terpene resin is prepared by ARIZNA CHEMICAL companyTP95。
Preferably, the plasticizer in this embodiment is an aliphatic mineral oil or a mineral oil having an aromatic ring content of < 5% that is compatible with both the diene block of the polystyrene block copolymer and the tackifying resin; the plasticizer is Shell company451。
The heat conducting particles are silicon carbide of KAIER NANO company, and the heat conducting particles are NANO-scale heat conducting particles with heat conductivity coefficient more than 200W/(m.K) and average particle size of 40-60 nm.
The environment-friendly hot melt adhesive tape of this embodiment has used the environment-friendly hot melt adhesive like aforementioned ratio, and environment-friendly hot melt adhesive tape sets up between the first part of light transmissivity transparent panel and the second part of light tight frame body, absorbs the energy of the laser that shines first part and is heated and softened viscidity, realizes effectively bonding to first part and second part, and its preparation method includes following step:
first, preparation stage of hot melt adhesive
S1: putting 10% by mass of plasticizer, 45% by mass of tackifying resin and 0.8% by mass of antioxidant 1010 into a reaction kettle, introducing nitrogen into the reaction kettle, heating to 120-140 ℃ while stirring, adding 9.2% by mass of silicon carbide after the solids are completely melted and uniformly mixed, and stirring for 10-30 min;
s2: adding 35% by mass of polystyrene block copolymer, heating to 170-180 ℃, and stirring for 1-2 hours;
s3: stopping heating, stopping introducing nitrogen, vacuumizing the reaction kettle under the condition of continuously stirring, and keeping the vacuum pressure at-0.08 MPa for 30 min;
s4: evacuating, introducing 0.1MPa compressed air into the reaction kettle, discharging, cooling the hot melt adhesive into a glue block, and packaging to obtain the environment-friendly hot melt adhesive;
(II) Hot melt adhesive coating stage
S5: and melting the hot melt adhesive block at 170-180 ℃, wherein the melt viscosity is 10000-20000 mPa.s, and coating the hot melt adhesive block on glassine paper or a PET release film to obtain the environment-friendly hot melt adhesive tape containing the release carrier.
In the preferred embodiment, the thickness of the environmentally friendly hot melt adhesive tape is 40-300 um.
Example 3
The environment-friendly hot melt adhesive comprises the following raw materials in percentage by mass: 40% of a polystyrene block copolymer, 40% of a tackifying resin, 9.3% of a plasticizer, 10% of thermally conductive particles, and 0.7% of an antioxidant 1010; the polystyrene block copolymer is a mixture of a styrene-isoprene-styrene copolymer and a styrene-butadiene-styrene copolymer, and the mass ratio of the styrene-isoprene-styrene copolymer to the styrene-butadiene-styrene copolymer is 5: 1.
In this embodiment, the styrene-isoprene-styrene copolymer is prepared by mixing 18% of styrene by mass and 18% of styrene-isoprene diblock component by mass<1% of4111A and styrene content of 30% by mass, styrene-isoprene diblock component<1% of4211A。
In this embodiment, the styrene-butadiene-styrene copolymer is preferably DX-405JOP having a styrene mass content of 24% and a styrene mass content of DX-405JOP having a styrene mass content of 0% and D1153 having a styrene mass content of 29% and a styrene mass content of 5% in KRATON.
In the embodiment, the tackifying resin is preferably a terpene resin with a softening point of 80-120 ℃, and the terpene resin is YS (Ys of YASUHARA CHEMICAL Co.)T100。
Preferably, the plasticizer in this embodiment is an aliphatic mineral oil or a mineral oil having an aromatic ring content of < 5% that is compatible with both the diene block of the polystyrene block copolymer and the tackifying resin; the plasticizer is of Shell company956。
The heat conducting particles are titanium carbide of KAIER NANO company, and the heat conducting particles are NANO-scale heat conducting particles with heat conductivity coefficient more than 200W/(m.K) and average particle size of 40-60 nm.
The environment-friendly hot melt adhesive tape of this embodiment has used the environment-friendly hot melt adhesive like aforementioned ratio, and environment-friendly hot melt adhesive tape sets up between the first part of light transmissivity transparent panel and the second part of light tight frame body, absorbs the energy of the laser that shines first part and is heated and softened viscidity, realizes effectively bonding to first part and second part, and its preparation method includes following step:
first, preparation stage of hot melt adhesive
S1: putting 9.3% of plasticizer, 40% of tackifying resin and 0.7% of antioxidant 1010 in mass ratio into a reaction kettle, introducing nitrogen into the reaction kettle, heating to 120-140 ℃ while stirring, adding 10% of titanium carbide after the solids are completely melted and uniformly mixed, and stirring for 10-30 min;
s2: then adding 40 mass percent of polystyrene block copolymer, heating to 170-180 ℃, and stirring for 1-2 hours;
s3: stopping heating, stopping introducing nitrogen, vacuumizing the reaction kettle under the condition of continuously stirring, and keeping the vacuum pressure at-0.08 MPa for 30 min;
s4: evacuating, introducing 0.1MPa compressed air into the reaction kettle, discharging, cooling the hot melt adhesive into a glue block, and packaging to obtain the environment-friendly hot melt adhesive;
(II) Hot melt adhesive coating stage
S5: and melting the hot melt adhesive block at 170-180 ℃, wherein the melt viscosity is 10000-20000 mPa.s, and coating the hot melt adhesive block on glassine paper or a PET release film to obtain the environment-friendly hot melt adhesive tape containing the release carrier.
In the preferred embodiment, the thickness of the environmentally friendly hot melt adhesive tape is 40-300 um.
Example 4
The environment-friendly hot melt adhesive comprises the following raw materials in percentage by mass: 45% of polystyrene block copolymer, 34% of tackifying resin, 12% of plasticizer, 8.5% of heat conducting particles and 0.5% of antioxidant 1010; the polystyrene block copolymer is a mixture of a styrene-isoprene-styrene copolymer and a styrene-butadiene-styrene copolymer, and the mass ratio of the styrene-isoprene-styrene copolymer to the styrene-butadiene-styrene copolymer is 5: 1.
In this embodiment, the styrene-isoprene-styrene copolymer is preferably styrene of DEXCO POLYMER15% by mass of a styrene-isoprene diblock component4113A and styrene content of 30% by mass, styrene-isoprene diblock component<1% of4211A。
In this embodiment, the styrene-butadiene-styrene copolymer is D1116 having a styrene mass content of 23%, a styrene-butadiene diblock component having a mass content of 16%, D1192 having a styrene mass content of 30%, and a styrene-butadiene diblock component having a mass content of 10%, which are manufactured by KRATON corporation.
In the embodiment, the tackifying resin is preferably a terpene resin with a softening point of 80-120 ℃, and the terpene resin is prepared by ARIZNA CHEMICAL companyTP105。
Preferably, the plasticizer in this embodiment is an aliphatic mineral oil or a mineral oil having an aromatic ring content of < 5% that is compatible with both the diene block of the polystyrene block copolymer and the tackifying resin; the plasticizer is of Shell company6204。
The heat conducting particles are titanium carbide of KAIER NANO company, and the heat conducting particles are NANO-scale heat conducting particles with heat conductivity coefficient more than 200W/(m.K) and average particle size of 40-60 nm.
The environment-friendly hot melt adhesive tape of this embodiment has used the environment-friendly hot melt adhesive like aforementioned ratio, and environment-friendly hot melt adhesive tape sets up between the first part of light transmissivity transparent panel and the second part of light tight frame body, absorbs the energy of the laser that shines first part and is heated and softened viscidity, realizes effectively bonding to first part and second part, and its preparation method includes following step:
first, preparation stage of hot melt adhesive
S1: putting 12% by mass of plasticizer, 34% by mass of tackifying resin and 0.5% by mass of antioxidant 1010 into a reaction kettle, introducing nitrogen into the reaction kettle, heating to 120-140 ℃ while stirring, adding 8.5% by mass of titanium carbide after the solids are completely melted and uniformly mixed, and stirring for 10-30 min;
s2: then adding a polystyrene block copolymer with the mass ratio of 45%, heating to 170-180 ℃, and stirring for 1-2 hours;
s3: stopping heating, stopping introducing nitrogen, vacuumizing the reaction kettle under the condition of continuously stirring, and keeping the vacuum pressure at-0.08 MPa for 30 min;
s4: evacuating, introducing 0.1MPa compressed air into the reaction kettle, discharging, cooling the hot melt adhesive into a glue block, and packaging to obtain the environment-friendly hot melt adhesive;
(II) Hot melt adhesive coating stage
S5: and melting the hot melt adhesive block at 170-180 ℃, wherein the melt viscosity is 10000-20000 mPa.s, and coating the hot melt adhesive block on glassine paper or a PET release film to obtain the environment-friendly hot melt adhesive tape containing the release carrier.
In the preferred embodiment, the thickness of the environmentally friendly hot melt adhesive tape is 40-300 um.
Example 5
The environment-friendly hot melt adhesive comprises the following raw materials in percentage by mass: 50% of a polystyrene block copolymer, 30% of a tackifying resin, 12% of a plasticizer, 7% of thermally conductive particles and 1% of an antioxidant 1010; the polystyrene block copolymer is a mixture of a styrene-isoprene-styrene copolymer and a styrene-butadiene-styrene copolymer, and the mass ratio of the styrene-isoprene-styrene copolymer to the styrene-butadiene-styrene copolymer is 7: 1.
In this embodiment, the styrene-isoprene-styrene copolymer is prepared by DEXCO POLYMER with a styrene mass content of 15% and a styrene-isoprene diblock component with a mass content of 18%4113A and styrene content of 30% by mass, styrene-isoprene diblock component<1% of4211A。
In this embodiment, the styrene-butadiene-styrene copolymer is D4153 having a styrene content of 35% by mass and a styrene-butadiene diblock component content of 11% by mass, both of which are available from KRATON.
In the embodiment, the tackifying resin is preferably a terpene resin with a softening point of 80-120 ℃, and the terpene resin is YS (Ys of YASUHARA CHEMICAL Co.)T115。
Preferably, the plasticizer in this embodiment is an aliphatic mineral oil or a mineral oil having an aromatic ring content of < 5% that is compatible with both the diene block of the polystyrene block copolymer and the tackifying resin; the plasticizer is of Shell company451。
The heat conducting particles are boron carbide of KAIER NANO company, and the heat conducting particles are NANO-scale heat conducting particles with heat conductivity coefficient more than 200W/(m.K) and average particle size of 40-60 nm.
The environment-friendly hot melt adhesive tape of this embodiment has used the environment-friendly hot melt adhesive like aforementioned ratio, and environment-friendly hot melt adhesive tape sets up between the first part of light transmissivity transparent panel and the second part of light tight frame body, absorbs the energy of the laser that shines first part and is heated and softened viscidity, realizes effectively bonding to first part and second part, and its preparation method includes following step:
first, preparation stage of hot melt adhesive
S1: putting 12% by mass of plasticizer, 30% by mass of tackifying resin and 0.5% by mass of antioxidant 1010 into a reaction kettle, introducing nitrogen into the reaction kettle, heating to 120-140 ℃ while stirring, adding 7.5% by mass of boron carbide after the solids are completely melted and uniformly mixed, and stirring for 10-30 min;
s2: then adding 50 mass percent of polystyrene block copolymer, heating to 170-180 ℃, and stirring for 1-2 hours;
s3: stopping heating, stopping introducing nitrogen, vacuumizing the reaction kettle under the condition of continuously stirring, and keeping the vacuum pressure at-0.08 MPa for 30 min;
s4: evacuating, introducing 0.1MPa compressed air into the reaction kettle, discharging, cooling the hot melt adhesive into a glue block, and packaging to obtain the environment-friendly hot melt adhesive;
(II) Hot melt adhesive coating stage
S5: and melting the hot melt adhesive block at 170-180 ℃, wherein the melt viscosity is 10000-20000 mPa.s, and coating the hot melt adhesive block on glassine paper or a PET release film to obtain the environment-friendly hot melt adhesive tape containing the release carrier.
In the preferred embodiment, the thickness of the environmentally friendly hot melt adhesive tape is 40-300 um.
Example 6
The environment-friendly hot melt adhesive comprises the following raw materials in percentage by mass: 55% of a polystyrene block copolymer, 26% of a tackifying resin, 15% of a plasticizer, 3% of thermally conductive particles and 1% of an antioxidant 1010; the polystyrene block copolymer is a mixture of a styrene-isoprene-styrene copolymer and a styrene-butadiene-styrene copolymer, and the mass ratio of the styrene-isoprene-styrene copolymer to the styrene-butadiene-styrene copolymer is 10: 1.
In this embodiment, the styrene-isoprene-styrene copolymer is prepared by mixing 30% of styrene by mass and 30% of styrene-isoprene diblock component by mass<1% of4211A。
In this embodiment, the styrene-butadiene-styrene copolymer is preferably D1192 having a styrene mass content of 30%, a styrene-butadiene diblock component having a mass content of 10%, D1153 having a styrene mass content of 29%, and a styrene-butadiene diblock component having a mass content of 5%, manufactured by KRATON.
In the embodiment, the tackifying resin is preferably a terpene resin with a softening point of 80-120 ℃, and the terpene resin is prepared by ARIZNA CHEMICAL companyTP115。
Preferably, the plasticizer in this embodiment is an aliphatic mineral oil or a mineral oil having an aromatic ring content of < 5% that is compatible with both the diene block of the polystyrene block copolymer and the tackifying resin; the plasticizer is of Shell company956。
The heat conducting particles are boron carbide of KAIER NANO company, and the heat conducting particles are NANO-scale heat conducting particles with heat conductivity coefficient more than 200W/(m.K) and average particle size of 40-60 nm.
The environment-friendly hot melt adhesive tape of this embodiment has used the environment-friendly hot melt adhesive like aforementioned ratio, and environment-friendly hot melt adhesive tape sets up between the first part of light transmissivity transparent panel and the second part of light tight frame body, absorbs the energy of the laser that shines first part and is heated and softened viscidity, realizes effectively bonding to first part and second part, and its preparation method includes following step:
first, preparation stage of hot melt adhesive
S1: putting 15% by mass of plasticizer, 26% by mass of tackifying resin and 1% by mass of antioxidant 1010 into a reaction kettle, introducing nitrogen into the reaction kettle, heating to 120-140 ℃ while stirring, adding 3% by mass of boron carbide after the solids are completely melted and uniformly mixed, and stirring for 10-30 min;
s2: then adding 55 mass percent of polystyrene block copolymer, heating to 170-180 ℃, and stirring for 1-2 hours;
s3: stopping heating, stopping introducing nitrogen, vacuumizing the reaction kettle under the condition of continuously stirring, and keeping the vacuum pressure at-0.08 MPa for 30 min;
s4: evacuating, introducing 0.1MPa compressed air into the reaction kettle, discharging, cooling the hot melt adhesive into a glue block, and packaging to obtain the environment-friendly hot melt adhesive;
(II) Hot melt adhesive coating stage
S5: and melting the hot melt adhesive block at 170-180 ℃, wherein the melt viscosity is 10000-20000 mPa.s, and coating the hot melt adhesive block on glassine paper or a PET release film to obtain the environment-friendly hot melt adhesive tape containing the release carrier.
In the preferred embodiment, the thickness of the environmentally friendly hot melt adhesive tape is 40-300 um.
In order to test the performance of the hot melt adhesive tapes in examples 1 to 6, a common pressure sensitive adhesive tape laminated by a manual roller and a hot melt adhesive film tape laminated by hot pressing were introduced as a comparison, the thickness of each of the 8 types of tapes was 100um, the lamination pressures of the three lamination methods were all 0.2MPa, and the objects to be laminated were glass plates and aluminum plates. After the lamination is finished, the three adhesive films are subjected to the drawing force and shearing force tests, and the test results are as follows:
as can be seen from the table, the drawing force and the shear strength of the environment-friendly hot melt adhesive tape of the invention are obviously higher than those of the pressure-sensitive adhesive tape and the hot-press-fit hot melt adhesive tape, which shows that the environment-friendly hot melt adhesive tape of the invention has excellent bonding reliability.
In the previous description, numerous specific details were set forth in order to provide a thorough understanding of the present invention. The foregoing description is only a preferred embodiment of the invention, which can be embodied in many different forms than described herein, and therefore the invention is not limited to the specific embodiments disclosed above. And that those skilled in the art may, using the methods and techniques disclosed above, make numerous possible variations and modifications to the disclosed embodiments, or modify equivalents thereof, without departing from the scope of the claimed embodiments. Any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the scope of the technical solution of the present invention.
Claims (10)
1. The utility model provides an environment-friendly hot melt adhesive which characterized in that: comprises the following raw materials in percentage by mass: 30-55% of polystyrene block copolymer, 26-55% of tackifying resin, 5-15% of plasticizer, 3-10% of heat conducting particles and 0.5-1.0% of antioxidant 1010; the polystyrene block copolymer is a mixture of a styrene-isoprene-styrene copolymer and a styrene-butadiene-styrene copolymer, and when the content of the styrene-isoprene-styrene copolymer is 100 parts by weight, the content of the styrene-butadiene-styrene copolymer is 10-40 parts by weight; the tackifying resin is one of rosin resin, terpene resin and petroleum resin; the plasticizer is aliphatic mineral oil or mineral oil with aromatic ring content less than 5 percent which is compatible with the diene block of the polystyrene block copolymer and the tackifying resin; the heat conducting particles are nano-scale heat conducting particles with heat conductivity coefficient more than 200W/(m.K) and average particle size of 40-60 nm.
2. The environment-friendly hot melt adhesive according to claim 1, wherein: the styrene-isoprene-styrene copolymer contains 10-40% by mass of styrene and 0-40% by mass of a styrene-isoprene diblock component.
4. The environment-friendly hot melt adhesive according to claim 1, wherein: the styrene-butadiene-styrene copolymer contains 10-35% by mass of styrene and 0-20% by mass of a styrene-butadiene diblock component.
5. The environment-friendly hot melt adhesive according to claim 1, wherein: the styrene-butadiene-styrene copolymer is one or more of D-1102JS, DX-405JOP, D1116, D1192, D1153 and D4153 of KRATON company.
6. The environment-friendly hot melt adhesive according to claim 1, wherein: the tackifying resin is preferably a terpene resin, the softening point of the terpene resin is 80-120 ℃, and the terpene resin is YS (Ys of YASUHARA CHEMICAL Co.)T80、YST100、YST115, or ARIZNA CHEMICALTP95、TP105、One of the TPs 115.
8. The environment-friendly hot melt adhesive according to claim 1, wherein: the heat conducting particles are one of silicon carbide, titanium carbide or boron carbide of KAIER NANO company.
9. The utility model provides an environment-friendly hot melt adhesive tape which characterized in that: the environment-friendly hot melt adhesive according to any one of claims 1 to 8 is used, wherein the environment-friendly hot melt adhesive tape is arranged between the first part of the light-transmitting transparent panel and the second part of the light-proof frame body, absorbs the energy of laser irradiated on the first part, is heated and softened, and has viscosity, so that the first part and the second part are effectively bonded.
10. The method for preparing the environment-friendly hot melt adhesive tape as claimed in claim 9, wherein the method comprises the following steps: the method comprises the following steps:
first, preparation stage of hot melt adhesive
S1: weighing a plasticizer, tackifying resin and an antioxidant 1010 according to a formula, putting into a reaction kettle, introducing nitrogen into the reaction kettle, heating to 120-140 ℃ while stirring, adding heat conducting particles weighed according to the formula after all solids are melted and uniformly mixed, and stirring for 10-30 min;
s2: then adding the weighed polystyrene block copolymer, heating to 170-180 ℃, and stirring for 1-2 hours;
s3: stopping heating, stopping introducing nitrogen, vacuumizing the reaction kettle under the condition of continuously stirring, and keeping the vacuum pressure at-0.08 MPa for 30 min;
s4: evacuating, introducing 0.1MPa compressed air into the reaction kettle, discharging, cooling the hot melt adhesive into a glue block, and packaging to obtain the environment-friendly hot melt adhesive;
(II) Hot melt adhesive coating stage
S5: and melting the hot melt adhesive block at 170-180 ℃, wherein the melt viscosity is 10000-20000 mPa.s, and coating the hot melt adhesive block on glassine paper or a PET release film to obtain the environment-friendly hot melt adhesive tape containing the release carrier.
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