CN110643311B - Special high-temperature-aging-resistant adhesive for magic tape and preparation method thereof - Google Patents
Special high-temperature-aging-resistant adhesive for magic 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
- 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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- 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
- C09J11/08—Macromolecular additives
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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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- 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
- 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
- C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
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Abstract
The invention discloses a special high-temperature aging resistant glue for a magic tape, which comprises the following raw materials in parts by mass: 40-50 parts of composite elastomer, 20-30 parts of tackifying resin, 6-10 parts of tackifying resin, 10-12 parts of softener, 2-4 parts of antioxidant, 1-3 parts of ultraviolet absorbent and 1-2 parts of pigment. Experimental test results show that the special adhesive for the magic tape, prepared by the invention, has excellent initial adhesion, good permanent adhesion, high peel strength and good cohesive strength. In addition, the special adhesive for the magic tape prepared by the invention also has excellent high-temperature aging resistance, can keep excellent initial adhesion and good permanent adhesion even if being in a high-temperature condition for a long time, and can be applied to various technical fields and regions with higher requirements on the high-temperature aging resistance; the adhesive can also meet the bonding requirements of different stuck base materials, has strong wetting property of the base materials, and has strong industrial application value and development prospect.
Description
Technical Field
The invention relates to the field of pressure-sensitive adhesives, in particular to a special adhesive for a magic tape with high temperature aging resistance and a preparation method thereof.
Background
The magic tape is also called as a magic tape or a squeaky button and is generally divided into a female surface magic tape and a sub surface magic tape, wherein one surface of the female surface magic tape is fine and soft round hair, one surface of the sub surface magic tape is hard barbed hair with hooks, and the round hair and the barbed hair on the surfaces of the female surface magic tape and the sub surface magic tape can achieve the effect similar to bonding due to anchoring when in use. The product is widely applied to various fields of clothes, vehicle-mounted instruments, medical instruments and the like due to the characteristic. After the special adhesive for the magic tape is coated on the back surface of the magic tape, the adhesive can be randomly stuck on various base materials. With the continuous expansion of the application field of the magic tape, various industries also put new requirements on the pressure-sensitive adhesive used when the magic tape is stuck on the base material.
The back adhesive type magic tape in the market at present is under a high-temperature condition or a high-temperature environment for a long time, the environmental temperature (90-110 ℃) is close to or exceeds the softening point of a styrene physical cross-linking phase in a formula, the colloid can be gradually softened, and a gap is formed between the colloid and a bonded base material, so that the problems of reduced bonding strength or complete non-sticking and the like are caused. These problems not only affect the actual use experience of the user, but may even cause safety accidents. Particularly, for tropical regions with high temperature such as south Asia and Africa, the popularization and the use of the adhesive-backed magic tape product in the regions are seriously influenced by insufficient high-temperature aging resistance; or the technical field with higher requirement on high-temperature aging resistance, such as decoration and accessories for automobiles in summer in some areas, is difficult to meet the comprehensive performance requirement of the magic tape. Therefore, there is a need to develop a special adhesive for hook and loop fasteners, which has excellent initial adhesion and high temperature resistance, good holding adhesion, high peel strength and good cohesive strength.
Disclosure of Invention
In order to solve the technical problems, the invention provides a special glue for a magic tape with high temperature aging resistance, which comprises the following raw materials in parts by mass: 40-50 parts of composite elastomer, 20-30 parts of tackifying resin, 6-10 parts of tackifying resin, 10-12 parts of softener, 2-4 parts of antioxidant, 1-3 parts of ultraviolet absorbent and 1-2 parts of pigment.
As a preferred technical solution, the composite elastomer is a mixture of a thermoplastic elastomer a and a thermoplastic elastomer B; the thermoplastic elastomer A is an SIS thermoplastic elastomer with diblock content of 47-53 wt%; the thermoplastic elastomer B is an SIS thermoplastic elastomer with diblock content of 16-20 wt%.
As a preferable technical solution, the mass ratio of the thermoplastic elastomer a to the thermoplastic elastomer B in the composite elastomer is 1: (1-2).
As a preferable technical scheme, the tackifying resin is selected from one or more of rosin resin, terpene resin and petroleum resin.
In a preferred embodiment, the tackifying resin is a polyolefin resin.
As a preferable technical scheme, the polyolefin resin is selected from one or more of polyethylene resin, polypropylene resin, polyacrylic resin and polybutylene resin.
As a preferable embodiment, the polyolefin resin is a modified polyolefin resin.
As a preferable technical scheme, the mass ratio of the composite elastomer, the tackifying resin and the tackifying resin is 1: (0.5-0.6): (0.1-0.3).
As a preferable technical scheme, the softening agent is selected from one or more of naphthenic oil, white oil, dioctyl phthalate DOP, dibutyl phthalate DBP, tributyl phosphate TBP, triphenyl phosphate TPP, alkyl phenyl sulfonate, alkyl methyl phenyl sulfonate and B type petroleum ester.
The second aspect of the invention provides a preparation method of special glue for a magic tape, which comprises the following steps:
the method comprises the following steps: adding the composite elastomer, the reinforcing resin, the softener, the antioxidant, the ultraviolet absorbent and the pigment into a stirrer, and stirring for 30-50 min at the temperature of 145-155 ℃ to obtain a mixture;
step two: and (3) adding tackifying resin into the mixture obtained in the step one, stirring for 1-2 h at the temperature of 170-180 ℃, and filtering and removing bubbles to obtain the special adhesive for the magic tape.
Has the advantages that: the invention mainly uses the composite elastomer, tackifying resin and a small amount of environmental protection auxiliary agent to prepare the special adhesive for the magic tape with excellent performance. Experimental test results show that the special adhesive for the magic tape, prepared by the invention, has excellent initial adhesion, good permanent adhesion, high peel strength and good cohesive strength. In addition, the composite elastomer with higher molecular weight, the tackifying resin with high softening point and the reduced using amount of the tackifier and the mineral oil are adopted, so that the special adhesive for the magic tape prepared by the method also has excellent high-temperature aging resistance, can keep excellent initial viscosity and good permanent viscosity even under a high-temperature condition for a long time, and can be applied to various technical fields and regions with higher requirements on the high-temperature aging resistance; the adhesive can also meet the bonding requirements of different stuck base materials, has strong wetting property of the base materials, and has strong industrial application value and development prospect.
Detailed Description
The technical features of the technical solutions provided by the present invention are further clearly and completely described below with reference to the specific embodiments, and the scope of protection is not limited thereto.
The words "preferred", "more preferred", and the like, in the present invention refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
In order to solve the technical problems, the invention provides a special glue for a magic tape with high temperature aging resistance, which comprises the following raw materials in parts by mass: 40-50 parts of composite elastomer, 20-30 parts of tackifying resin, 6-10 parts of tackifying resin, 10-12 parts of softener, 2-4 parts of antioxidant, 1-3 parts of ultraviolet absorbent and 1-2 parts of pigment.
In a preferred embodiment, the glue specially used for the magic tape comprises the following raw materials in parts by mass: 45 parts of composite elastomer, 25 parts of tackifying resin, 8 parts of tackifying resin, 11 parts of softener, 3 parts of antioxidant, 2 parts of ultraviolet absorbent and 1.5 parts of pigment.
< Complex elastomer >
The composite elastomer is a high polymer material which is formed by optimally combining two or more material components with different chemical and physical properties, has obvious deformation under weak stress and can be quickly recovered to be close to the original state and size after the stress is relaxed.
In a preferred embodiment, the composite elastomer is a mixture of thermoplastic elastomer a and thermoplastic elastomer B.
(thermoplastic elastomer)
Thermoplastic elastomers, known by the english name Thermoplastic Elastomer (TPE), are also known as elastomers or synthetic rubbers. It has the double characteristics of rubber and plastics, and has the toughness and elasticity of rubber at room temp. and can be formed by means of flow plasticization at high temp.
In a preferred embodiment, the thermoplastic elastomer is an SIS thermoplastic elastomer.
The SIS thermoplastic elastomer comprises SIS-8291, SIS-8161, SIS-8152, SIS-8151, SIS-1300, SIS-1250, SIS-1120, SIS-1100, SIS-1209, SIS-1126, SIS-1106, SIS-1105 and the like.
SIS thermoplastic ElastomersBody
SIS thermoplastic elastomers, styrene-isoprene-styrene, are a triblock copolymer consisting of two polymer blocks linked by covalent bonds. The SIS thermoplastic elastomer has excellent corrugated sealing performance and high-temperature retention, the unique microscopic phase-splitting structure determines that the SIS thermoplastic elastomer has unique superiority when being used as an adhesive, and the prepared pressure-sensitive adhesive and hot melt adhesive are widely applied to the fields of medical treatment, electrical insulation, packaging, protection and masking, marking, bonding and fixing and the like.
In a preferred embodiment, the thermoplastic elastomer A is an SIS thermoplastic elastomer having a diblock content of 47 to 53 wt%.
In a more preferred embodiment, the thermoplastic elastomer A is an SIS thermoplastic elastomer having a diblock content of 47 to 51 wt%.
In a further preferred embodiment, the thermoplastic elastomer a is an SIS thermoplastic elastomer with a diblock content of 50 wt.%.
In a preferred embodiment, the thermoplastic elastomer B is an SIS thermoplastic elastomer having a diblock content of 16 to 20 wt%.
In a more preferred embodiment, the thermoplastic elastomer B is an SIS thermoplastic elastomer having a diblock content of 16 to 18 wt%.
In a further preferred embodiment, the thermoplastic elastomer B is an SIS thermoplastic elastomer with a diblock content of 18 wt.%.
The method of measuring the diblock content described herein may be measured using methods well known to those skilled in the art, such as liquid chromatography.
In a preferred embodiment, the mass ratio of the thermoplastic elastomer a to the thermoplastic elastomer B in the composite elastomer is 1: (1-2).
In a more preferred embodiment, the mass ratio of thermoplastic elastomer a and thermoplastic elastomer B in the composite elastomer is 1: 1.5.
the thermoplastic elastomer A is SIS-8152, is purchased from Ningbo gold Haihesheng photochemical company Limited, and has the model of JH8152, the diblock content of 47-51 wt percent, and the average value of 50wt percent.
The thermoplastic elastomer B is SIS-8161, is purchased from Ningbo gold Haiheshen photochemical Co., Ltd, and has the model of JH8161, the diblock content of 16-18 wt percent, and the average value of 18wt percent.
< tackifying resin >
Tackifying resins are small molecule compounds that increase the tack, especially surface tack, of rubber materials.
In a preferred embodiment, the tackifying resin is selected from one or more of rosin resin, terpene resin, petroleum resin.
(rosin resin)
Rosin resin is a tricyclic diterpenoid compound, has a high softening point through high polymerization (dimerization), high viscosity, and better oxidation resistance, and is completely resistant to crystallization in a liquid state or in a solution. It has many uses including paint, drying agent, synthetic resin, automobile ink, floor tile, rubber composition, soldering flux, soldering paste, and various adhesives and protective paint. The rosin resin comprises: rosin resin 138, rosin resin 145, rosin resin 146, and the like.
Examples of rosin resins include, but are not limited to, rosin esters, wood rosins, hydrogenated rosins, glycerol rosinate.
(terpene resin)
Terpene resins, also known as polyterpene or pinene resins. It is mainly a series of linear polymers from liquid to solid which are obtained by using alpha-pinene or beta-pinene of turpentine through cationic polymerization under the action of a Friedel-crafts catalyst.
Examples of terpene resins include, but are not limited to, alpha-pinene polymers, beta-pinene polymers, diterpene polymers.
(Petroleum resin)
Petroleum resin, the English name of which is hydrocarbonresin, is a low molecular weight thermoplastic resin produced by pretreating, polymerizing and distilling C5 and C9 fractions which are byproducts of petroleum cracking. It is insoluble in water, soluble in organic solvent, low in acid value, high in adhesion, water resistant, chemical resistant and other features. The petroleum resin comprises petroleum resin A1100, petroleum resin LH-0#, petroleum resin LH-1#, petroleum resin 1102, petroleum resin 1204, petroleum resin 1304, petroleum resin 1401, petroleum resin 5300 and petroleum resin 5400.
Examples of the petroleum resin include, but are not limited to, C5 aliphatic petroleum resin, C5 hydrogenated petroleum resin, C9 aromatic petroleum resin, C5 and C9 copolymerized petroleum resin, dicyclopentadiene petroleum resin.
In a more preferred embodiment, the tackifying resin is a petroleum resin.
In a further preferred embodiment, the petroleum resin is a C5 aliphatic petroleum resin.
The C5 aliphatic petroleum resin, also called C5 petroleum resin, is a low molecular polymer, is the petroleum resin which has the most extensive application in the world at present, has good compatibility with elastomer, and the prepared hot melt pressure sensitive adhesive has good mechanical property.
The C5 aliphatic petroleum resin is purchased from Shanghai Kaiyn chemical Co., Ltd, and has the model of E1304.
The inventors found in the course of development that when the mass ratio of the thermoplastic elastomer a to the thermoplastic elastomer B used is 1: (1-2), when the thermoplastic elastomer A is an SIS thermoplastic elastomer with the diblock content of 47-53 wt%, and the thermoplastic elastomer B is an SIS thermoplastic elastomer with the diblock content of 16-20 wt%, the two elastomers in the obtained colloid have good compatibility with tackifying resin, the cohesiveness of the colloid and the back of the magic tape is improved, and meanwhile, the cohesive strength of the colloid and the initial adhesiveness of the colloid and a base material are also obviously improved. The inventor believes that when the content of the diblock in the system is too high, on one hand, the hard segment in the mixture is relatively reduced, the physical crosslinking points are reduced, a stable network structure cannot be formed, and the cohesive strength is low; on the other hand, the soft segment in the mixture is relatively increased, so that the winding of the elastomer and the tackifying resin molecular chain is facilitated, the compatibility of the elastomer and the tackifying resin is promoted, the adhesive property of the colloid and the back surface of the magic tape is further improved, and the initial adhesion of the prepared colloid and the base material is ensured. When the mass ratio of the thermoplastic elastomer a to the thermoplastic elastomer B is 1: (1-2), when the thermoplastic elastomer A is an SIS thermoplastic elastomer with the diblock content of 47-53 wt%, and the thermoplastic elastomer B is an SIS thermoplastic elastomer with the diblock content of 16-20 wt%, the diblock content in the system is moderate, and the compatibility of the system, the cohesive strength of colloid and the initial viscosity all reach excellent levels.
The back surface of the magic tape refers to the surface of the female surface magic tape without round hair and the surface of the sub surface magic tape without stabbing hair.
< tackifying resin >
The reinforcing resin is a polymer which can improve the comprehensive performance of the rubber material and expand the application value of the rubber material.
In a preferred embodiment, the tackifying resin is a polyolefin resin.
In a more preferred embodiment, the polyolefin resin is selected from one or more of polyethylene resin, polypropylene resin, polyacrylic resin, and polybutylene resin.
In a further preferred embodiment, the polyolefin resin is a modified polyolefin resin.
In a still further preferred embodiment, the modified polyolefin resin is a maleic anhydride modified polyolefin resin.
Maleic anhydride, cis-butenedioic anhydride, CAS number: 108-31-6, maleic anhydride for short, is anhydride of maleic acid, which is a colorless or white solid with sour taste at room temperature.
In a preferred embodiment, the method for preparing the maleic anhydride-modified polyolefin resin comprises the steps of:
sequentially adding 3-5 parts by mass of maleic anhydride, 0.5-1 part by mass of initiator, 20-30 parts by mass of polyolefin resin and 10-20 mL of solvent A into a device provided with a reflux condenser pipe in a nitrogen atmosphere, heating to 40-60 ℃, and stirring for 40-50 min to obtain a mixture;
quickly heating the obtained mixture to 70-80 ℃, reacting at a constant temperature for 3-5 h, pouring into 80-120 mL of solvent B, and continuously stirring to obtain floccules;
and step three, filtering, washing and drying the floccule obtained in the step two to obtain the maleic anhydride modified polyolefin resin.
In a more preferred embodiment, the method for preparing the maleic anhydride-modified polyolefin resin comprises the steps of:
sequentially adding 4 parts by mass of maleic anhydride, 0.7 part by mass of initiator, 25 parts by mass of polyolefin resin and 15mL of solvent A into a device provided with a reflux condenser pipe in a nitrogen atmosphere, heating to 50 ℃, and stirring for 45min to obtain a mixture;
step two, quickly heating the obtained mixture to 75 ℃, reacting at a constant temperature for 4 hours, pouring into 100mL of solvent B, and continuously stirring to obtain floccules;
and step three, filtering, washing and drying the floccule obtained in the step two to obtain the maleic anhydride modified polyolefin resin.
The maleic anhydride was purchased from Shanghai Aladdin Biotech, Inc.
In a preferred embodiment, the polyolefin resin is a polypropylene resin.
The polypropylene resin was purchased from sierra splendor plasticator, su under model 3204.
In a preferred embodiment, the initiator is selected from one or more combinations of dicumyl peroxide (DCP), dibenzoyl peroxide (BPO), Azobisisoheptonitrile (ABVN), Azobisisobutyronitrile (AIBN).
In a more preferred embodiment, the initiator is dicumyl peroxide (DCP) (CAS number: 80-43-3).
The dicumyl peroxide is purchased from Shanghai Allantin Biotechnology Ltd.
In a preferred embodiment, the solvent a is selected from one or more combinations of ortho-xylene, para-xylene, meta-xylene.
In a more preferred embodiment, the solvent a is ortho-xylene.
The o-xylene was purchased from Shanghai Aladdin Biotechnology Ltd.
In a preferred embodiment, the solvent B is selected from one or more of acetone, ethanol, diethyl ether and methanol.
In a more preferred embodiment, the solvent B is acetone.
In a preferred embodiment, the mass ratio of the composite elastomer, the tackifying resin and the tackifying resin is 1: (0.5-0.6): (0.1-0.3).
In a more preferred embodiment, the mass ratio of the composite elastomer, the tackifying resin and the tackifying resin is 1: 0.56: 0.18.
the inventors have improved the compatibility of the resulting colloid, cohesive strength of the colloid and initial tack, but the cohesive strength of the colloid remains poor, by adding the thermoplastic elastomer a and the thermoplastic elastomer B in the stated ratios by mass and diblock content. The inventors have surprisingly found that when maleic anhydride modified polyolefin resin is added, in particular the mass ratio of the composite elastomer, tackifying resin and tackifying resin is 1: (0.5-0.6): (0.1-0.3), the viscosity retention and peel strength of the obtained colloid are remarkably increased, and the initial viscosity and cohesive strength are further improved. The inventor conjectures that after a certain amount of modified polyolefin resin is introduced, the specific effective groups on the modified polyolefin resin can generate hydrogen bond crosslinking between molecules, the peel strength of colloid is increased, and the cohesive strength and creep resistance, namely the viscosity, are also obviously improved; meanwhile, the special effective groups on the modified polyolefin resin can also increase the wettability of the colloid and the polar base material, and further improve the initial viscosity of the colloid. However, when the amount of the modified polyolefin resin is gradually increased, the density of the crosslinked network in the system is too high, the rigidity of the molecular chain is enhanced, the wettability of the colloid and the base material is reduced, and the initial viscosity and the peel strength of the colloid are not increased or decreased. Meanwhile, when the amount of tackifying resin in the system is fixed, partial chains in the system are mutually wound and crosslinked, so that the peeling strength of the colloid is improved; however, when the amount of the tackifier resin in the system is too large, the degree of molecular crosslinking in the colloid becomes too large, the steric internal resistance becomes large, and the peel strength is drastically reduced. Therefore, in practical application, the quality of the composite elastomer, the tackifying resin and the tackifying resin also needs to be controlled within a proper proportion range.
< softening agent >
Softeners, which are an aid for improving the processability and the application properties of rubber. The softener comprises white oil-100 #, white oil-500N, naphthenic oil-4006 and the like.
In a preferred embodiment, the softening agent is selected from one or more of naphthenic oil, white oil, dioctyl phthalate (DOP), dibutyl phthalate (DBP), tributyl phosphate (TBP), triphenyl phosphate (TPP), phenyl alkyl sulfonate, methyl phenyl alkyl sulfonate, and b-type petroleum ester.
In a more preferred embodiment, the softening agent is naphthenic oil.
Naphthenic oil, known by the english name naphthinic oil, has a saturated cyclic carbon chain structure, and has low pour point, high density, high viscosity, and no toxic or side effects.
The naphthenic oil is purchased from special oil products of Suzhou Seapahan, and the model is naphthenic oil-4006.
< antioxidant >
Antioxidants are a class of chemicals which, when present in only small amounts in a polymer system, retard or inhibit the progress of the polymer oxidation process, thereby preventing aging of the polymer and extending its useful life.
In a preferred embodiment, the antioxidant is selected from one or more of the group consisting of antioxidant 1010, antioxidant 1076, antioxidant 168, and antioxidant 264.
In a more preferred embodiment, the antioxidant is antioxidant 1010.
Antioxidant 1010, i.e., pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], CAS number: 6683-19-8, is a white crystalline powder with stable chemical properties.
The antioxidant 1010 is purchased from Yuansheng chemical Co., Ltd, Yuansheng-1010.
< ultraviolet absorber >
The ultraviolet absorbent is a light stabilizer which is widely applied at present, can absorb the ultraviolet part in sunlight and a fluorescent light source, and does not change.
The ultraviolet absorber used in the present invention is not particularly limited, and any one or more ultraviolet absorbers known to those skilled in the art may be used, and may be commercially available, including risperidone-326 (UV-326), risperidone-329, and the like. For example, UV-326, an ultraviolet absorber is commercially available from Tianjin Rianlong New materials Ltd under the type Rianlong-326.
The UV-326 has a CAS number of 3896-11-5 and is a benzotriazole light stabilizer.
< pigments >
The pigment used in the present invention is not particularly limited, and those skilled in the art can use any one or more pigments known to those skilled in the art according to the actual needs, and the pigments are commercially available, including Shanghai-Li De powder, Zinc oxide, Black paste HW901, titanium white powder-R518, etc. For example, lithopone is commercially available from Shanghai Hujiang industries, Inc. under the type lithopone-B311.
The lithopone is a mixture of zinc sulfide and barium sulfate, and is white crystalline powder.
The second aspect of the invention provides a preparation method of special glue for a magic tape, which comprises the following steps:
the method comprises the following steps: adding the composite elastomer, the reinforcing resin, the softener, the antioxidant, the ultraviolet absorbent and the pigment into a stirrer, and stirring for 30-50 min at the temperature of 145-155 ℃ to obtain a mixture;
step two: and (3) adding tackifying resin into the mixture obtained in the step one, stirring for 1-2 h at the temperature of 170-180 ℃, and filtering and removing bubbles to obtain the special adhesive for the magic tape.
In a preferred embodiment, the preparation method of the special glue for the magic tape comprises the following steps:
the method comprises the following steps: adding the composite elastomer, the tackifying resin, the softener, the antioxidant, the ultraviolet absorbent and the pigment into a stirrer, and stirring at the temperature of 150 ℃ for 40min to obtain a mixture;
step two: and (3) adding tackifying resin into the mixture obtained in the step one, stirring for 1.5h at the temperature of 175 ℃, and filtering and discharging bubbles to obtain the special adhesive for the magic tape.
The present invention will now be described in detail by way of examples, and the starting materials used are commercially available unless otherwise specified.
Examples
Example 1
The embodiment 1 of the invention provides a special adhesive for a magic tape, which comprises the following raw materials in parts by mass: 45 parts of composite elastomer, 25 parts of tackifying resin, 8 parts of tackifying resin, 11 parts of softener, 3 parts of antioxidant, 2 parts of ultraviolet absorbent and 1.5 parts of pigment.
The composite elastomer is a mixture of a thermoplastic elastomer A and a thermoplastic elastomer B; the thermoplastic elastomer A is an SIS thermoplastic elastomer with a diblock content of 50 wt%; the thermoplastic elastomer B is an SIS thermoplastic elastomer with a diblock content of 18 wt%; the mass ratio of the thermoplastic elastomer A to the thermoplastic elastomer B in the composite elastomer is 1: 1.5.
the tackifying resin is petroleum resin; the petroleum resin is C5 aliphatic petroleum resin.
The reinforcing resin is polyolefin resin; the polyolefin resin is a modified polyolefin resin; the modified polyolefin resin is maleic anhydride modified polyolefin resin.
The preparation method of the maleic anhydride modified polyolefin resin comprises the following steps:
sequentially adding 4 parts by mass of maleic anhydride, 0.7 part by mass of initiator, 25 parts by mass of polyolefin resin and 15mL of solvent A into a device provided with a reflux condenser pipe in a nitrogen atmosphere, heating to 50 ℃, and stirring for 45min to obtain a mixture;
step two, quickly heating the obtained mixture to 75 ℃, reacting at a constant temperature for 4 hours, pouring into 100mL of solvent B, and continuously stirring to obtain floccules;
and step three, filtering, washing and drying the floccule obtained in the step two to obtain the maleic anhydride modified polyolefin resin.
The polyolefin resin is polypropylene resin; the initiator is dicumyl peroxide (DCP); the solvent A is o-xylene; the solvent B is acetone.
The softener is naphthenic oil; the antioxidant is 1010; the ultraviolet absorbent is UV-326; the pigment is lithopone-B311.
The preparation method of the special glue for the magic tape comprises the following steps:
the method comprises the following steps: adding the composite elastomer, the tackifying resin, the softener, the antioxidant, the ultraviolet absorbent and the pigment into a stirrer, and stirring at the temperature of 150 ℃ for 40min to obtain a mixture;
step two: and (3) adding tackifying resin into the mixture obtained in the step one, stirring for 1.5h at the temperature of 175 ℃, and filtering and discharging bubbles to obtain the special adhesive for the magic tape.
Example 2
The embodiment 2 of the invention provides a special adhesive for a magic tape, which comprises the following raw materials in parts by mass: 40 parts of composite elastomer, 20 parts of tackifying resin, 6 parts of tackifying resin, 10 parts of softener, 2 parts of antioxidant, 1 part of ultraviolet absorbent and 1 part of pigment.
The composite elastomer is a mixture of a thermoplastic elastomer A and a thermoplastic elastomer B; the thermoplastic elastomer A is an SIS thermoplastic elastomer with a diblock content of 50 wt%; the thermoplastic elastomer B is an SIS thermoplastic elastomer with a diblock content of 18 wt%; the mass ratio of the thermoplastic elastomer A to the thermoplastic elastomer B in the composite elastomer is 1: 1.5.
the tackifying resin is petroleum resin; the petroleum resin is C5 aliphatic petroleum resin.
The reinforcing resin is polyolefin resin; the polyolefin resin is a modified polyolefin resin; the modified polyolefin resin is maleic anhydride modified polyolefin resin.
The preparation method of the maleic anhydride-modified polyolefin resin was the same as in example 1.
The polyolefin resin is polypropylene resin; the initiator is dicumyl peroxide (DCP); the solvent A is o-xylene; the solvent B is acetone.
The softener is naphthenic oil; the antioxidant is 1010; the ultraviolet absorbent is UV-326; the pigment is lithopone-B311.
The preparation method of the special adhesive for the magic tape is the same as that of the embodiment 1.
Example 3
The embodiment 3 of the invention provides a special adhesive for a magic tape, which comprises the following raw materials in parts by mass: 50 parts of composite elastomer, 30 parts of tackifying resin, 10 parts of tackifying resin, 12 parts of softener, 4 parts of antioxidant, 3 parts of ultraviolet absorbent and 2 parts of pigment.
The composite elastomer is a mixture of a thermoplastic elastomer A and a thermoplastic elastomer B; the thermoplastic elastomer A is an SIS thermoplastic elastomer with a diblock content of 50 wt%; the thermoplastic elastomer B is an SIS thermoplastic elastomer with a diblock content of 18 wt%; the mass ratio of the thermoplastic elastomer A to the thermoplastic elastomer B in the composite elastomer is 1: 1.5.
the tackifying resin is petroleum resin; the petroleum resin is C5 aliphatic petroleum resin.
The reinforcing resin is polyolefin resin; the polyolefin resin is a modified polyolefin resin; the modified polyolefin resin is maleic anhydride modified polyolefin resin.
The preparation method of the maleic anhydride-modified polyolefin resin was the same as in example 1.
The polyolefin resin is polypropylene resin; the initiator is dicumyl peroxide (DCP); the solvent A is o-xylene; the solvent B is acetone.
The softener is naphthenic oil; the antioxidant is 1010; the ultraviolet absorbent is UV-326; the pigment is lithopone-B311.
The preparation method of the special adhesive for the magic tape is the same as that of the embodiment 1.
Example 4
Embodiment 4 of the present invention provides a special glue for a hook and loop fastener, which has a specific implementation manner similar to that of embodiment 1, except that the mass ratio of the thermoplastic elastomer a to the thermoplastic elastomer B in the composite elastomer is from 1: 1.5 replacement by 1: 0.5.
example 5
Embodiment 5 of the present invention provides a special glue for a hook and loop fastener, which has a specific implementation manner similar to that of embodiment 1, except that the mass ratio of the thermoplastic elastomer a to the thermoplastic elastomer B in the composite elastomer is from 1: 1.5 replacement by 1: 2.5.
example 6
Example 6 of the present invention provides a special adhesive for a magic tape, which is implemented in a similar manner to example 1, except that the diblock content of the thermoplastic elastomer a is changed from 50 wt% to 55 wt%, which is purchased from lignum Cinnamomi Camphorae head hong base plasticizing business, model 4116N.
Example 7
Embodiment 7 of the present invention provides a special adhesive for a magic tape, which is implemented in a similar manner to embodiment 1, except that the diblock content of the thermoplastic elastomer B is replaced by 20wt% from 18 wt%, which is purchased from Ningbo Haihchen photochemical company Limited and has a model number of JH-8153.
Example 8
Embodiment 8 of the present invention provides a special adhesive for a hook and loop fastener, which is implemented in a similar manner to embodiment 1, except that the tackifying resin is replaced by 32 parts by mass from 25 parts.
Example 9
Embodiment 9 of the present invention provides a special adhesive for a magic tape, which is implemented in a similar manner to embodiment 1, except that the mass part of the tackifying resin is replaced by 15 parts from 8 parts.
Example 10
Embodiment 10 of the present invention provides a special adhesive for a magic tape, which is implemented in a similar manner to embodiment 1, except that the mass part of the tackifying resin is replaced by 0 part from 8 parts.
Example 11
Embodiment 11 of the present invention provides a special adhesive for a hook and loop fastener, which is implemented in a similar manner to embodiment 1, except that the tackifying resin is a polypropylene resin.
Evaluation of Performance
The glue special for the magic tape obtained in the embodiment 1-11 is melted at 175 ℃ to prepare a glue sample for standby.
1. Initial tack test: the special adhesive for the magic tape obtained in the embodiment 1-11 is prepared according to GB/T4852 & 2002 & lt & gt method for testing initial adhesion of pressure-sensitive adhesive tape (ball-rolling method) & gt, and the adhesive sample is prepared according to 20-30 g/m2The gluing amount of the adhesive tape is uniformly coated on the back surface of a magic tape with the thickness of 25mm multiplied by 250 mm. Wherein, the test method adopts a method A: the angle of the inclined plane is 30 degrees by the inclined plane rolling ball method. The magic tape is fixed on the inclined plane with the side coated with the glue sample facing upwards, and the rolling ball device is horizontally fixed on the test board. And rolling the test steel ball from small to large sequentially from the rolling-assisting section at the position of 10cm of the inclined plane, and recording the maximum ball number which can be stuck by the glue sample, namely the initial sticking force. After 5 tests on each sample, the results are averaged as shown in Table 1.
2. Tack-holding test: the special adhesive for the magic tape obtained in the embodiment 1-11 is prepared according to GB/T4851-2The gluing amount of the adhesive tape is uniformly coated on the back surface of a magic tape with the thickness of 25mm multiplied by 100 mm. Dividing a steel plate for testing into a test plate and a loading plate, pasting the surface of the magic tape coated with the glue sample on the test plate in parallel with the longitudinal direction of the plate, sticking the magic tape on the test plate, pressing the magic tape back and forth for three times at the speed of 300mm/min by using a press roller, and then placing the magic tape for 20 min. Will be provided withThe test plate was vertically fixed to the test stand, and a 1kg weight was attached to one end of the load plate to record the time at which the sample completely separated. After 5 tests on each sample, the results are averaged as shown in Table 1.
3.180 ° peel strength test: according to GB/T2792-1998 test method for 180-degree peel strength of pressure-sensitive adhesive tape, the special adhesive for magic tapes obtained in examples 1-11 is used for preparing an adhesive sample with the weight of 20-30 g/m2The gluing amount of the adhesive tape is uniformly coated on the back surface of a magic tape with the thickness of 25mm multiplied by 250 mm. And (3) sticking one surface of the magic tape coated with the glue sample to the cleaned test board, pressing the surface of the magic tape back and forth three times at the speed of 300mm/min by using a press roller, and standing for 20min after no air bubbles exist at the bonding position of the test sample and the test board. The test piece was peeled from the test plate at 180 ℃ by a peeling machine at a speed of 300mm/min, and the 180 ℃ peel strength was calculated by recording a curve by an instrument. After 5 tests on each sample, the results are averaged as shown in Table 1.
Table 1 results of performance testing
The combination of the above experimental results shows that: the invention mainly uses the composite elastomer, tackifying resin and a small amount of environmental protection auxiliary agent to prepare the special adhesive for the magic tape with excellent performance. Experimental test results show that the maximum ball number of the special adhesive for the magic tape, which is prepared by the invention, can be adhered to be 16 through an initial adhesion test, and the special adhesive has excellent initial adhesion; through a permanent viscosity test, a weight of 1kg can be suspended for 75 hours, and the permanent viscosity is good; the 180 DEG peel strength test shows that the 180 DEG peel strength can reach 0.75kN/m and the adhesive has good cohesive strength. In addition, the composite elastomer with higher molecular weight, the tackifying resin with high softening point and the reduced using amount of the tackifier and the mineral oil are adopted, so that the special adhesive for the magic tape prepared by the method also has excellent high-temperature aging resistance, can keep excellent initial viscosity and good permanent viscosity even under a high-temperature condition for a long time, and can be applied to various technical fields and regions with higher requirements on the high-temperature aging resistance; the adhesive can also meet the bonding requirements of different stuck base materials, has strong wetting property of the base materials, and has strong industrial application value and development prospect.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. The invention is not limited to the embodiments described above, but rather, many modifications and variations may be made by one skilled in the art without departing from the scope of the invention.
Claims (4)
1. The special glue for the magic tape with high temperature aging resistance is characterized by comprising the following raw materials in parts by mass: 40-50 parts of composite elastomer, 20-30 parts of tackifying resin, 6-10 parts of tackifying resin, 10-12 parts of softener, 2-4 parts of antioxidant, 1-3 parts of ultraviolet absorbent and 1-2 parts of pigment;
the composite elastomer is a mixture of a thermoplastic elastomer A and a thermoplastic elastomer B; the thermoplastic elastomer A is an SIS thermoplastic elastomer with diblock content of 47-53 wt%; the thermoplastic elastomer B is an SIS thermoplastic elastomer with diblock content of 16-20 wt%;
the mass ratio of the thermoplastic elastomer A to the thermoplastic elastomer B in the composite elastomer is 1: (1-2);
the thickening resin is maleic anhydride modified polyolefin resin.
2. The special adhesive for magic tapes as claimed in claim 1, wherein said tackifying resin is selected from rosin resin, terpene resin, petroleum resin, or their combination.
3. The special glue for magic tapes according to claim 1, wherein the softening agent is selected from one or more of naphthenic oil, white oil, dioctyl phthalate, dibutyl phthalate, tributyl phosphate, triphenyl phosphate, phenyl alkyl sulfonate and methyl phenyl alkyl sulfonate.
4. A method for preparing the special glue for the magic tape according to any one of claims 1 to 3, which is characterized by comprising the following steps:
the method comprises the following steps: adding the composite elastomer, the reinforcing resin, the softener, the antioxidant, the ultraviolet absorbent and the pigment into a stirrer, and stirring for 30-50 min at the temperature of 145-155 ℃ to obtain a mixture;
step two: and (3) adding tackifying resin into the mixture obtained in the step one, stirring for 1-2 h at the temperature of 170-180 ℃, and filtering and removing bubbles to obtain the special adhesive for the magic tape.
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| CN112210314B (en) * | 2020-09-22 | 2022-08-30 | 广东新时代新材料科技有限公司 | Heat preservation blanket adhesive tape |
| CN112409879B (en) * | 2020-10-27 | 2022-07-15 | 广东顺联动漫科技有限公司 | Coating material, preparation method and application thereof |
| CN114292622A (en) * | 2021-12-14 | 2022-04-08 | 佛山市南海骏驰新材料有限公司 | Hot-melt pressure-sensitive adhesive for house interior decoration wall sticker and preparation method thereof |
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