CN110746913B - Special hot-melt pressure-sensitive adhesive for foot paste bottom support and preparation method thereof - Google Patents
Special hot-melt pressure-sensitive adhesive for foot paste bottom support and preparation method thereof Download PDFInfo
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- CN110746913B CN110746913B CN201911018323.2A CN201911018323A CN110746913B CN 110746913 B CN110746913 B CN 110746913B CN 201911018323 A CN201911018323 A CN 201911018323A CN 110746913 B CN110746913 B CN 110746913B
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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
- C09J11/02—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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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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
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- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to the technical field of hot-melt pressure-sensitive adhesives, in particular to a special hot-melt pressure-sensitive adhesive for a foot patch bottom support and a preparation method thereof. The hot-melt pressure-sensitive adhesive is prepared from the raw materials of, by weight, 60-80 parts of a styrene-based block copolymer, 40-60 parts of tackifying resin, 15-30 parts of a softening agent and 1-3 parts of an antioxidant, wherein the styrene-based block copolymer is selected from one or more of SEBS, SBS, SIS, SBR and SEPS. The invention provides a special hot-melt pressure-sensitive adhesive for a sole pad of a foot patch, which can increase the waterproof performance of the hot-melt pressure-sensitive adhesive and further increase the holding viscosity by the combined action of the preparation raw materials of the hot-melt pressure-sensitive adhesive, thereby meeting the requirements of the hot-melt pressure-sensitive adhesive for the sole pad of the foot patch.
Description
Technical Field
The invention relates to the technical field of hot-melt pressure-sensitive adhesives, in particular to a special hot-melt pressure-sensitive adhesive for a foot patch bottom support and a preparation method thereof.
Background
The foot patch is a health care product for physical therapy, the foot therapy has a long history in China, and the foot patch is a traditional Chinese medicine health care product for foot therapy through subcutaneous administration on the sole of a foot. The foot patch is applied to the sole of a foot, the relevant reflecting area of the sole of the foot is stimulated, the blood circulation is promoted, sufficient power is provided for the transport protein of subcutaneous tissues, the medicine is absorbed through the skin under the action of the transport protein, and harmful substances are also removed through the skin under the action of the transport protein along with the blood circulation entering the body; harmful free radicals in the body can be combined with ions in the foot patch and are discharged out of the body in a diffusion mode; the combination of the two forms can effectively remove the toxin of the human body from the body and promote the health of the human body. The existing foot patch comprises a medicine bag and a bottom support, wherein the medicine is placed on the sole of a foot, and then the bottom support is used for sticking the medicine bag and is adhered to a sole plate. However, the sweat resistance and water resistance and the lasting viscosity of foot pastes on the market are insufficient, the time for attaching the bottom support to the sole with much sweat or the sole with beriberi is usually limited, the bottom support can be automatically separated from the sole after a period of time, and the medicine property of the medicine package can not be completely released.
Disclosure of Invention
In order to solve the problems, the first aspect of the invention provides a special hot-melt pressure-sensitive adhesive for a foot patch base, which comprises 60-80 parts by weight of styrene block copolymer, 40-60 parts by weight of tackifying resin, 15-30 parts by weight of softener and 1-3 parts by weight of antioxidant, wherein the styrene block copolymer is selected from one or more of SEBS, SBS, SIS, SBR and SEPS.
As a preferred technical solution of the present invention, the styrene block copolymer comprises SIS and SBS, and the weight ratio of SIS to SBS is 1: (0.2-0.3).
As a preferable technical scheme of the invention, the S/I of the SIS is 10/90-18/82.
In a preferred embodiment of the present invention, the SIS has a viscosity of 1000 to 1500MPa · s.
As a preferable technical scheme of the invention, the S/B of the SBS is 20/80-30/70, and the viscosity of the SBS is 4000-5000 MPa.
As a preferable technical scheme, the preparation raw materials of the hot-melt pressure-sensitive adhesive also comprise 0.5-2 parts of an anti-ultraviolet agent, and the anti-ultraviolet agent is selected from one or more of titanium dioxide, zinc oxide, iron oxide and silicon dioxide.
As a preferred technical scheme of the invention, the uvioresistant agent comprises titanium dioxide and zinc oxide, and the weight ratio of the titanium dioxide to the zinc oxide is 1: (1-3).
As a preferred technical scheme of the invention, the titanium dioxide is modified titanium dioxide, the modifier of the titanium dioxide is a silane coupling agent, and the silane coupling agent is selected from one or more of aminosilane coupling agent, epoxy silane coupling agent, acyloxy silane coupling agent, vinyl silane coupling agent, alkyl silane coupling agent and phenyl silane coupling agent.
As a preferred technical scheme of the invention, the weight ratio of the titanium dioxide to the silane coupling agent is 1: (0.05-0.2).
The invention provides a preparation method of the special hot-melt pressure-sensitive adhesive for the foot patch bottom support, which comprises the following steps:
blending the preparation raw materials of the hot-melt pressure-sensitive adhesive at 155-170 ℃, and extruding to obtain the hot-melt pressure-sensitive adhesive.
Compared with the prior art, the invention has the following beneficial effects: the invention provides a special hot-melt pressure-sensitive adhesive for a sole pad of a foot patch, which can increase the waterproof performance of the hot-melt pressure-sensitive adhesive and further increase the holding viscosity by the combined action of the preparation raw materials of the hot-melt pressure-sensitive adhesive, thereby meeting the requirements of the hot-melt pressure-sensitive adhesive for the sole pad of the foot patch.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.
The invention provides a special hot-melt pressure-sensitive adhesive for a foot patch bottom support, which comprises the following raw materials, by weight, 60-80 parts of styrene-based block copolymer, 40-60 parts of tackifying resin, 15-30 parts of softener and 1-3 parts of antioxidant, wherein the styrene-based block copolymer is selected from one or more of SEBS, SBS, SIS, SBR and SEPS.
In a preferred embodiment, the raw materials for preparing the hot melt pressure sensitive adhesive comprise, by weight, 70 parts of a styrene-based block copolymer, 50 parts of a tackifying resin, 20 parts of a softener and 1 part of an antioxidant.
Styrenic block copolymer
The styrene block copolymer is selected from one or more of SEBS, SBS, SIS, SBR and SEPS.
Examples of SIS include, but are not limited to, SIS-1105, SIS-1106, SIS-1209, SIS-1100, SIS-1120, SIS-1124, SIS-1126, SIS-1128.
Examples of SBS include, but are not limited to, SBS-791, SBS-792, SBS-796, SBS-188.
Preferably, the styrenic block copolymers of the present invention comprise SIS.
More preferably, the styrenic block copolymer comprises SIS and SBS in a weight ratio of 1: (0.2-0.3).
SIS is a triblock copolymer consisting of styrene and isoprene. The soft rubber chain segments of polyisoprene isolated from each other are arranged in the middle, the hard plastic chain segments of the polyphenylene are arranged on two sides, the rubber has the performance of vulcanized rubber at room temperature, can be plastic at high temperature, has the advantages of good elasticity and bonding strength, low temperature resistance, good solubility resistance, low solution viscosity, fast curing and the like, is usually used for adhesives such as hot melt adhesives, pressure sensitive adhesives and the like, and can be used for interlayer bonding and the like of paper diapers, medical treatment, electrical insulation, packaging, protection and masking, marks, bonding and fixation, composite bags and the like.
SBS is polystyrene-polybutadiene-polystyrene ternary block copolymer, wherein the polystyrene chain segment and Polybutadiene (PB) chain segment are obviously in two-phase structure, are not compatible with each other and are in phase separation state. SBS has excellent tensile strength, elasticity and electrical property, small permanent deformation, good flexibility and rebound resilience and large surface friction. The ozone, oxygen and ultraviolet irradiation resistance is similar to that of styrene butadiene rubber. Because the main chain contains unsaturated double bonds, the aging resistance of SBS is poor, and under the oxidation condition of high temperature air, the butadiene block will be cross-linked, thus increasing the hardness and viscosity. SBS is soluble in cyclohexane, toluene, benzene, methyl ethyl ketone, ethyl acetate, dichloroethane, insoluble in water, ethanol, solvent gasoline, etc.
Further preferably, the weight ratio of SIS to SBS according to the present invention is 1: 0.2.
more preferably, the SIS has S/I of 10/90-18/82.
In a preferred embodiment, the SIS of the present invention has an S/I of 14/86.
S/I is the weight ratio of S (styrene) to I (isoprene) in SIS, wherein the S/I test method described in the present invention is a method well known to those skilled in the art, such as liquid chromatography.
In a more preferred embodiment, the SIS of the present invention has a viscosity of 1000 to 1500 MPa.s.
In a further preferred embodiment, the SIS of the present invention has a viscosity of 1250MPa · s.
Viscosity refers to the resistance that a fluid exhibits to flow. The viscosity according to the invention is determined by viscometer measurements and is the viscosity in a 25 wt.% toluene solution at 25 ℃.
In a further preferred embodiment, the SIS of the present invention is available under the designation SIS-1124 from Yueyang Barring Huaxing petrochemical Co.
The SIS-1124 has an S/I of 14/86 and a viscosity of 1250MPa · S.
In a further preferred embodiment, the SBS of the invention has an S/B of 20/80-30/70 and a viscosity of 4000-5000 MPa.
In a further preferred embodiment, said SBS of the present invention has an S/B of 23/77 and said SBS has a viscosity of 4800 MPa.
S/B is the weight ratio of S (styrene) to B (butadiene) in SBS, wherein the S/B test method described herein is a method well known to those skilled in the art, such as liquid chromatography.
In a further preferred embodiment, the SBS of the present invention is available under the brand name SBS-796 available from Yueyang Barring Huaxing petrochemical Co.
The S/B of the SBS-796 is 23/77, and the viscosity of the SBS is 4800 MPa.
Tackifying resins
The tackifying resin is generally a low molecular polymer formed by a monomer containing an aliphatic cyclic structure, or an organic acid ester containing an aliphatic cyclic structure, or a monomer polymer capable of forming an aliphatic cyclic structure during polymerization; the general name of the amorphous thermoplastic polymer with the molecular weight of hundreds to thousands and the softening point of 60-150 ℃. Tackifying resins have a clear index (softening point) control, which depends primarily on the size of the relative molecular mass and the steric structure of the resin. SBS and SIS have no adhesiveness, and need to be matched with proper tackifying resin to improve wettability, cohesion, peel strength and shear strength, increase initial adhesion and permanent adhesion strength, reduce melt viscosity of hot melt adhesive, improve wettability of bonded materials and improve operating performance.
Preferably, the tackifying resin of the present invention is selected from one or more of rosin resin, terpene resin, hydrocarbon resin and phenolic resin.
Examples of rosin resins include, but are not limited to, glycerol rosins, maleic anhydride rosin resins, wood rosins, hydrogenated rosins, polymerized rosins.
Examples of terpene resins include, but are not limited to, α -terpene polymers, β -terpene polymers, diterpene polymers.
Examples of the hydrocarbon resin include, but are not limited to, C5 petroleum resin, C9 petroleum resin, hydrogenated petroleum resin, dicyclopentadiene.
Examples of the so-called phenol resin include, but are not limited to, alkylphenol resins.
More preferably, the tackifying resins of the present invention are selected from hydrocarbon resins.
Further preferably, the hydrocarbon resin of the present invention is one or more selected from the group consisting of C5 petroleum resin, C9 petroleum resin, hydrogenated petroleum resin, dicyclopentadiene.
Still more preferably, the hydrocarbon resin of the present invention is a hydrogenated petroleum resin.
In a preferred embodiment, the hydrogenated petroleum resin of the present invention is selected from one or more of hydrogenated C5 resin, hydrogenated C9 resin, hydrogenated C5/C9 copolymer resin.
In a more preferred embodiment, the hydrogenated petroleum resin of the present invention is a hydrogenated C5/C9 copolymer resin.
In a further preferred embodiment, the hydrogenated C5/C9 copolymer resin of the present invention has a softening point of 100 to 120 ℃.
In a still further preferred embodiment, the hydrogenated C5/C9 copolymer resin of the present invention has a softening point of 103 ℃.
The softening point is the temperature at which the material softens. Mainly the temperature at which the amorphous polymer starts to soften. It is not only related to the structure of the polymer, but also to the size of its molecular weight. The softening point of the present invention is measured according to ASTM E28.
In a still further preferred embodiment, the hydrogenated C5/C9 copolymer resin of the present invention has the designation E5600, available from Exxon Mobil.
The E5600 hydrogenated C5/C9 copolymer resin had a softening point of 103 ℃.
Softening agent
The softening agent is a substance which can reduce the glass transition temperature or melting temperature of a high molecular compound, improve the brittleness of an adhesive layer, improve the fluidity of a molten substance and enable the adhesive layer to have flexibility; the main functions of the adhesive are weakening intermolecular force of polymers in the adhesive, increasing mobility of polymer molecular chains and reducing crystallinity of the polymer molecular chains, so that the hardness, modulus and brittleness of a glue film formed by the adhesive are reduced, the elongation, flexibility and flexibility are improved, and the physical and mechanical properties of the adhesive are improved.
Preferably, the softener of the invention is selected from one or more of naphthenic oil, white oil, vacuum pump oil, engine oil, dimethyl phthalate, dioctyl phthalate and chlorinated paraffin.
More preferably, the softening agent of the present invention is naphthenic oil.
Further preferably, the naphthenic oil has a molecular weight of 400-500.
Molecular weight is the sum of the relative atomic masses of the atoms in a molecular weight, as measured by viscosity measurement according to ASTM D2502-2004.
Still more preferably, the naphthenic oil of the present invention is available under the trademark KN4010 from Suzhou Seapahan specialty oils, Inc.
The KN4006 naphthenic oil has a molecular weight of 405.
Antioxidant agent
The antioxidant is a substance capable of delaying the chemical combination and oxidation of high polymers, thereby prolonging the service life of products. The unsaturated rubber phase of thermoplastic elastomers such as SBS and SIS is subject to thermal oxidative aging in air under the action of air, ozone and ultraviolet rays, and the aging is more serious especially when hot melt adhesives are prepared and melt coated at high temperature. Secondly, the tackifying resin is stirred at high temperature, and the stability is poor, so that an antioxidant needs to be added.
Preferably, the antioxidant of the present invention is selected from the group consisting of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) -propionate, 2, 6-di-tert-butyl-4-cresol, tris (2, 4-di-tert-butylphenyl) phosphite, p' -diisopropylphenyldiphenylamine, thioethylenebis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], pentaerythritol beta-dodecylthiopropionate, 4- [ (4, 6-dioctylthio-1, 3, 5-triazin-2-yl) amino ] -2, 6-di-tert-butylphenol, and mixtures thereof, One or more of bis (3, 5-di-tert-butyl) pentaerythritol diphosphite, 5(6) -carboxydiacetoxyfluorescein succinimidyl ester (CAS number: 150347-59-4), and superoxide dismutase (CAS number: 9054-89-1).
More preferably, the antioxidant is beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) -propionic acid octadecyl ester.
Beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) -propionic acid octadecyl ester (CAS number: 2082-79-3) is a good anti-aging agent, has good heat resistance and water extraction resistance, and is widely used in polyolefin, polyamide, polyester, polyvinyl chloride and petroleum products.
In a preferred embodiment, the raw materials for preparing the hot melt pressure sensitive adhesive further comprise 0.5-2 parts of an anti-ultraviolet agent, wherein the anti-ultraviolet agent is one or more selected from titanium dioxide, zinc oxide, iron oxide and silicon dioxide.
In a preferred embodiment, the raw materials for preparing the hot melt pressure sensitive adhesive further comprise 1.8 parts of an ultraviolet resistant agent.
Anti-ultraviolet agent
The anti-ultraviolet agent is a substance capable of absorbing or absorbing ultraviolet light, and is generally added in order to prevent the unsaturated part of thermoplastic elastomers such as SIS and SBS from being modified by ultraviolet light.
Preferably, the uvioresistant agent comprises titanium dioxide and zinc oxide, and the weight ratio of the titanium dioxide to the zinc oxide is 1: (1-3).
More preferably, the weight ratio of the titanium dioxide to the zinc oxide is 1: 2.
titanium dioxide, namely titanium dioxide, is a white solid or powdery amphoteric oxide, has high refractivity and high photoactivity, and can efficiently block ultraviolet rays.
Zinc oxide is an oxide of zinc, is insoluble in water, and can shield ultraviolet rays by absorbing and scattering the ultraviolet rays.
Further preferably, the titanium dioxide is modified titanium dioxide, the modifier of the titanium dioxide is a silane coupling agent, and the silane coupling agent is one or more selected from aminosilane coupling agent, epoxy silane coupling agent, acyloxy silane coupling agent, vinyl silane coupling agent, alkyl silane coupling agent and phenyl silane coupling agent.
As examples of the aminosilane coupling agent, there are included, but not limited to, primary amine silane coupling agents, gamma-aminopropyltrimethoxysilane (CAS No.: 13822-56-5), N- (. beta. -aminoethyl) -gamma-aminopropylmethyldimethoxysilane (CAS No.: 3069-29-2), N-N-butyl-3-aminopropyltrimethoxysilane (CAS No.: 31024-56-3), N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane (CAS No.: 70240-34-5); secondary amine silane coupling agents include bis- [3- (triethoxysilyl) -propyl ] -amine (CAS number: 13497-18-2) and bis- [3- (trimethoxysilyl) -propyl ] -amine (CAS number: 82985-35-1).
Examples of the epoxy silane coupling agent include, but are not limited to, gamma-glycidoxypropyltrimethoxysilane (CAS number: 2530-83-8), 3-glycidoxypropyltriethoxysilane (CAS number: 2602-34-8), gamma-glycidoxypropylmethyldimethoxysilane (CAS number: 65799-47-5), 3-glycidoxypropylmethyldiethoxysilane (CAS number: 2897-60-1), 2- (3, 4-epoxycyclohexylalkyl) ethyltrimethoxysilane (CAS number: 3388-04-3).
Examples of the acyloxysilane coupling agent include, but are not limited to, gamma-methacryloxypropyltriethoxysilane (CAS No.: 21142-29-0), 3-methacryloxypropyltriisopropoxysilane (CAS No.: 80750-05-6), 3-acryloxypropyltrimethoxysilane (CAS No.: 4369-14-6), gamma-methacryloxypropylmethyldimethoxysilane (CAS No.: 14513-34-9), gamma-methacryloxypropyltrimethoxysilane (CAS No.: 2530-85-0).
As examples of the vinylsilane coupling agent, there are included, but not limited to, vinyltris (2-methoxyethoxy) silane (CAS number: 1067-53-4), vinyltriethoxysilane (CAS number: 78-08-0).
Examples of the alkylsilane coupling agent include, but are not limited to, 1, 2-bis (triethoxysilyl) ethane (CAS number: 16068-37-4), octyltriethoxysilane (CAS number: 2943-75-1), dodecyltrimethoxysilane (CAS number: 3069-21-4), dodecyltriethoxysilane (CAS number: 18536-91-9), hexadecyltrimethoxysilane (CAS number: 16415-12-6), octadecyltrimethoxysilane (CAS number: 3069-42-9).
Examples of the phenylsilane coupling agent include, but are not limited to, diphenyldimethoxysilane (CAS No.: 6843-66-9), diphenyldiethoxysilane (CAS No.: 2553-19-7), phenyltrimethoxysilane (CAS No.: 2996-92-1), phenyltriethoxysilane (CAS No.: 780-69-8).
Still more preferably, the weight ratio of the titanium dioxide powder and the silane coupling agent is 1: (0.05-0.2).
In a preferred embodiment, the weight ratio of the titanium dioxide powder and the silane coupling agent is 1: 0.1.
in a more preferred embodiment, the silane coupling agent of the present invention comprises an aminosilane coupling agent and a phenylsilane coupling agent, and the weight ratio of the aminosilane coupling agent to the phenylsilane coupling agent is (2-3): (2-3).
In a further preferred embodiment, the weight ratio of aminosilane coupling agent to phenylsilane coupling agent according to the invention is 3: 2.
in a still further preferred embodiment, the aminosilane coupling agents of the present invention are selected from primary amine silane coupling agents and/or secondary amine silane coupling agents.
In a still further preferred embodiment, the aminosilane coupling agent of the present invention is a primary amine silane coupling agent.
Preferably, the particle size of the titanium dioxide is 0.2-0.4 μm.
In a further preferred embodiment, the particle size of the titanium dioxide is 0.2-0.3 μm.
The particle size is divided into a single particle size representing the size of a single particle and an average particle size representing a particle group composed of particles of different sizes. Since the shape of an actual particle is usually non-spherical and it is difficult to directly express its size by diameter, in the field of particle size testing, the particle size of a non-spherical particle is usually characterized by an equivalent particle size (generally referred to as particle size). The equivalent particle size refers to the equivalent particle size (or particle size distribution) of a particle to be measured when the physical property or behavior of the particle is most similar to that of a homogeneous sphere (or combination) of a certain diameter. The particle size in the present invention is an average particle size, which is an equivalent diameter of the largest particle when the cumulative distribution in a particle size distribution curve is 50%. Methods for testing average particle size are well known to those skilled in the art.
More preferably, the titanium dioxide of the invention has the mark R-818 and is purchased from Jinan spring Convergence chemical Co.
The particle size of the titanium dioxide R-818 is 0.2-0.26 mu m.
Further preferably, the preparation method of the modified titanium dioxide comprises the following steps:
adding titanium dioxide into a solvent, adjusting the pH value to 5-6, heating to 60-80 ℃, dropwise adding a silane coupling agent for reacting for 4-5 h, washing, and drying to obtain the modified titanium dioxide.
Still more preferably, in the preparation method of the modified titanium dioxide, the solvent is selected from one or more of ethanol, tetrahydrofuran, isopropanol and water.
In a preferred embodiment, in the preparation method of the modified titanium dioxide, the solvent is ethanol.
In a more preferable embodiment, in the preparation method of the modified titanium dioxide, the pH is adjusted to 5-6 by adding acetic acid and sodium carbonate.
Preferably, the particle size of the zinc oxide is 30-100 nm.
More preferably, the particle size of the zinc oxide of the present invention is 100 nm.
Further preferably, the zinc oxide of the invention is purchased from Beijing Dekko island gold science and technology Co., Ltd, and has a particle size of 100 nm.
The applicant finds that the water resistance and the viscosity of the hot melt pressure sensitive adhesive can be increased by adding the anti-ultraviolet agent, particularly the modified titanium dioxide and the zinc oxide as the anti-ultraviolet agent, which is probably because the compatibility with tackifying resin, thermoplastic elastomer and the like can be increased by using the modified titanium dioxide, particularly the titanium dioxide modified by the amino coupling agent and the phenyl coupling agent, so as to promote the dispersion uniformity of the anti-ultraviolet agent such as the titanium dioxide and the zinc oxide in the hot melt adhesive, and because the large phenyl group and the polar group such as amino are added on the surface of the titanium dioxide, the agglomeration of the titanium dioxide and the zinc oxide can be prevented from influencing the caking property, and a system with different particle sizes can be formed by controlling the particle sizes of the zinc oxide and the titanium dioxide, wherein the titanium dioxide with large particle size tends to move to the surface of the hot melt pressure sensitive adhesive due to factors such as gravity, and the zinc oxide with small particle, wherein the large conjugate structure such as polar group such as amino on titanium white powder surface and phenyl, the absorption to human skin can be increased, thereby increasing the viscosity, when meeting the effect of water, the residual hydroxyl on the titanium white powder surface in the part that the pressure sensitive adhesive outside and water contact acts on with amino and water, hinder the infiltration of water, and the large hydrophobic phenyl on silica surface can further prevent water to get into inside the pressure sensitive adhesive, in addition, the pressure sensitive adhesive outside is because the effect on water and titanium white powder surface, cause near space increase of titanium white powder, the zinc oxide removal of small particle size is filled near the space this moment, because zinc oxide titanium white powder is hydrophobic, can not cause the increase of space with water effect, thereby make water can't get into inside the pressure sensitive adhesive, destroy the viscosity that holds of pressure sensitive adhesive.
The applicant finds that the weight ratio of the modified titanium dioxide and the zinc oxide is in a proper range, and when the amount of the modified titanium dioxide is too much, part of the titanium dioxide is easy to agglomerate due to the strong titanium-oxygen bond of the modified titanium dioxide and the action of the residual hydroxyl on the surface, so that the cohesiveness of the hot melt adhesive is influenced. In addition, the applicant found that when an imine silane coupling agent and a phenyl silane coupling agent are used together, a good waterproof effect is obtained, which is probably because the primary amine group has too high affinity for water, which easily causes damage to the structure of the hot melt adhesive.
The structural adhesives of the invention may also comprise various additives, such as light stabilizers, for example, poly [1- (2' -hydroxy) -2,2,6, 6-tetramethyl-4-hydroxypiperidine succinate ], bis 2,2,6, 6-tetramethylpiperidinol sebacate, poly- { [6- [ (1,1,3,3, -tetramethylbutyl) -amino ]1,3,5, -triazine-2, 4-diyl ] [ (2,2,6, 6-tetramethylpiperidyl) -imino ] -1, 6-hexanediyl- [ (2,2,6, 6-tetramethylpiperidyl) -imino ] } and/or bis (1,2,2,6, 6-pentamethylpiperidinol) - α - (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl-alpha, -butyl-malonate; examples of the filler include lithopone.
The second aspect of the invention provides a preparation method of the special hot-melt pressure-sensitive adhesive for the bottom support of the foot paste, which is characterized in that the preparation raw materials of the label adhesive are blended and extruded at 155-170 ℃ to obtain the label adhesive.
Examples
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
A1: styrenic block copolymer
The styrene block copolymer is SIS with the mark of SIS-1124 and is purchased from Yueyang Ba Ling Huaxing petrochemical company Limited; the SIS-1124 has an S/I of 14/86 and a viscosity of 1250MPa · S.
A2: styrenic block copolymer
The styrene block copolymer is SIS with the mark of SIS-1128 and is purchased from Yueyang Ba Ling Huaxing petrochemical company Limited; the SIS-1128 has the S/I of 15/85 and the viscosity of 600MPa S.
A3: styrenic block copolymer
The styrene block copolymer is SBS with the brand of SBS-796 and is purchased from Yueyang Ba Ling Huaxing petrochemical company Limited; the S/B of the SBS-796 is 23/77, and the viscosity of the SBS is 4800 MPa.
A4: styrenic block copolymer
The styrene block copolymer is SBS with the brand number of SBS-792, and is purchased from Yueyang Ba Ling Huaxing petrochemical company Limited; the SBS-792 has an S/B of 38/62 and the SBS has a viscosity of 1050 MPa.
B1: tackifying resins
The tackifying resin is hydrogenated C5/C9 copolymer resin with the trade name of E5600 and is purchased from Exxon Mobil; the E5600 hydrogenated C5/C9 copolymer resin had a softening point of 103 ℃.
B2: tackifying resins
The tackifying resin is hydrogenated C5 petroleum resin with the trade name of E5300 and is purchased from Exxon Mobil; the softening point of the E5300 hydrogenated C5 petroleum resin is 103 ℃.
C: softening agent
The softener is naphthenic oil with the trade name of KN4010 and is purchased from Suzhou Seapahan special oil products Co., Ltd; the KN4006 naphthenic oil has a molecular weight of 405.
D: antioxidant agent
The antioxidant is beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) -octadecyl propionate.
E1: anti-ultraviolet agent
The uvioresistant agent is titanium dioxide with the brand number of R-818 and is purchased from Jinan spring chemical company Limited; the particle size of the titanium dioxide R-818 is 0.2-0.26 mu m.
E2: anti-ultraviolet agent
The uvioresistant agent is modified titanium dioxide, and the preparation method of the modified titanium dioxide comprises the following steps:
adding titanium dioxide into ethanol, adjusting the pH value to 5 by adding acetic acid and sodium carbonate, heating to 70 ℃, dropwise adding a silane coupling agent for reacting for 5 hours, washing, and drying to obtain modified titanium dioxide; the weight ratio of the titanium dioxide to the silane coupling agent is 1: 0.1; the silane coupling agent is bis- [3- (triethoxy silicon) -propyl ] -amine and phenyl triethoxysilane, and the weight ratio is 3: 2.
the titanium dioxide is R-818 and purchased from Jinan spring Convergence chemical Co.Ltd; the particle size of the titanium dioxide R-818 is 0.2-0.26 mu m.
E3: anti-ultraviolet agent
The uvioresistant agent is modified titanium dioxide, and the preparation method of the modified titanium dioxide comprises the following steps:
adding titanium dioxide into ethanol, adjusting the pH value to 5 by adding acetic acid and sodium carbonate, heating to 70 ℃, dropwise adding a silane coupling agent for reacting for 5 hours, washing, and drying to obtain modified titanium dioxide; the weight ratio of the titanium dioxide to the silane coupling agent is 1: 0.1. the silane coupling agent is gamma-aminopropyl trimethoxy silane and phenyl triethoxy silane 3: 2.
the titanium dioxide is R-818 and purchased from Jinan spring Convergence chemical Co.Ltd; the particle size of the titanium dioxide R-818 is 0.2-0.26 mu m.
E4: anti-ultraviolet agent
The uvioresistant agent is modified titanium dioxide, and the preparation method of the modified titanium dioxide comprises the following steps:
adding titanium dioxide into ethanol, adjusting the pH value to 5 by adding acetic acid and sodium carbonate, heating to 70 ℃, dropwise adding a silane coupling agent for reacting for 5 hours, washing, and drying to obtain modified titanium dioxide; the weight ratio of the titanium dioxide to the silane coupling agent is 1: 0.1; the silane coupling agent is bis- [3- (triethoxy silicon) -propyl ] -amine.
The titanium dioxide is R-818 and purchased from Jinan spring Convergence chemical Co.Ltd; the particle size of the titanium dioxide R-818 is 0.2-0.26 mu m.
E5: anti-ultraviolet agent
The uvioresistant agent is modified titanium dioxide, and the preparation method of the modified titanium dioxide comprises the following steps:
adding titanium dioxide into ethanol, adjusting the pH value to 5 by adding acetic acid and sodium carbonate, heating to 70 ℃, dropwise adding a silane coupling agent for reacting for 5 hours, washing, and drying to obtain modified titanium dioxide; the weight ratio of the titanium dioxide to the silane coupling agent is 1: 0.1; the silane coupling agent is phenyl triethoxysilane.
The titanium dioxide is R-818 and purchased from Jinan spring Convergence chemical Co.Ltd; the particle size of the titanium dioxide R-818 is 0.2-0.26 mu m.
E6: anti-ultraviolet agent
The uvioresistant agent is zinc oxide, is purchased from Beijing Deke island gold science and technology Limited and has the grain diameter of 100 nm.
E7: anti-ultraviolet agent
The uvioresistant agent is zinc oxide, is purchased from Beijing Deke island gold science and technology Limited and has the grain diameter of 200 nm.
TABLE 1
Attached table 1
| Examples | 8 | 9 | 10 | 11 | 12 | 13 | 14 |
| A1 | 58 | 58 | 58 | 58 | 58 | 58 | 58 |
| A2 | |||||||
| A3 | 12 | 12 | 12 | 12 | 12 | 12 | 12 |
| A4 | |||||||
| B1 | 50 | 50 | 50 | 50 | 50 | 50 | 50 |
| B2 | |||||||
| C | 20 | 20 | 20 | 20 | 20 | 20 | 20 |
| D | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
| E1 | 0.6 | ||||||
| E2 | 0.6 | 1.8 | |||||
| E3 | 0.6 | ||||||
| E4 | 0.6 | ||||||
| E5 | 0.6 | ||||||
| E6 | 1.2 | 1.2 | 1.2 | 1.2 | 1.8 | ||
| E7 | 1.2 |
Embodiments 1 to 14 provide a special hot-melt pressure-sensitive adhesive for a foot patch base, wherein a formula of the special hot-melt pressure-sensitive adhesive for the foot patch base is shown in table 1, and the formula is used in parts by weight.
Embodiments 1 to 14 provide a preparation method of a special hot-melt pressure-sensitive adhesive for a foot patch bottom support, including the following steps: and blending and extruding the preparation raw materials of the hot-melt pressure-sensitive adhesive at 160 ℃ to obtain the hot-melt pressure-sensitive adhesive.
Evaluation of Performance
1. Viscosity retention: the special hot-melt pressure-sensitive adhesive for the foot patch bottom support provided by the embodiments 1-14 is subjected to a permanent adhesion test according to GB/T4851-.
2. Water resistance: the peel strength p of the special hot-melt pressure-sensitive adhesive for the foot patch bottom support provided by the embodiments 1-14 is tested according to JC/T863-1And peel strength p after 24h soaking in water at 25 ℃2And according to p2/p1The peeling strength retention rate is obtained by multiplying 100%, so that the waterproof performance of the hot melt pressure sensitive adhesive is measured, and the result is shown in table 2.
Table 2 characterization test of properties
| Examples | Viscosity per hour | Water resistance/% |
| 1 | 65 | 65％ |
| 2 | 78 | 89％ |
| 3 | 81 | 90％ |
| 4 | 80 | 92％ |
| 5 | 71 | 74％ |
| 6 | 73 | 77％ |
| 7 | 76 | 80％ |
| 8 | 73 | 71％ |
| 9 | 78 | 76％ |
| 10 | 74 | 81％ |
| 11 | 75 | 79％ |
| 12 | 78 | 78％ |
| 13 | 76 | 75％ |
| 14 | 69 | 71％ |
The test results in table 2 show that the special hot-melt pressure-sensitive adhesive for the foot paste bottom support provided by the invention has high waterproof performance and high adhesion maintaining performance, and can be used as the hot-melt pressure-sensitive adhesive for the foot paste bottom support.
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. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (7)
1. The special hot-melt pressure-sensitive adhesive for the bottom support of the foot paste is characterized in that the preparation raw materials of the hot-melt pressure-sensitive adhesive comprise, by weight, 60-80 parts of styrene-based block copolymer, 40-60 parts of tackifying resin, 15-30 parts of softener and 1-3 parts of antioxidant, wherein the styrene-based block copolymer is selected from one or more of SEBS, SBS, SIS, SBR and SEPS;
the raw materials for preparing the hot-melt pressure-sensitive adhesive also comprise 0.5-2 parts of an anti-ultraviolet agent; the uvioresistant agent comprises titanium dioxide and zinc oxide, and the weight ratio of the titanium dioxide to the zinc oxide is 1: (1-3);
the titanium dioxide is modified titanium dioxide, the modifying agent of the titanium dioxide is a silane coupling agent, the silane coupling agent comprises an aminosilane coupling agent and a phenylsilane coupling agent, and the weight ratio of the aminosilane coupling agent to the phenylsilane coupling agent is (2-3): (2-3);
the particle size of the titanium dioxide is 0.2-0.4 mu m;
the particle size of the zinc oxide is 30-100 nm.
2. The special hot-melt pressure-sensitive adhesive for the footwears according to claim 1, wherein the styrene block copolymer comprises SIS and SBS, and the weight ratio of SIS to SBS is 1: (0.2-0.3).
3. The special hot-melt pressure-sensitive adhesive for the foot patch bottom support according to claim 2, wherein the S/I of the SIS is 10/90-18/82.
4. The special hot-melt pressure-sensitive adhesive for the foot patch base support according to claim 3, wherein the viscosity of the SIS is 1000-1500 MPa-s.
5. The special hot-melt pressure-sensitive adhesive for the foot patch bottom support according to claim 2, wherein the S/B of SBS is 20/80-30/70, and the viscosity of SBS is 4000-5000 MPa.
6. The special hot-melt pressure-sensitive adhesive for the foot patch bottom support according to claim 1, wherein the weight ratio of the titanium dioxide to the silane coupling agent is 1: (0.05-0.2).
7. The preparation method of the special hot-melt pressure-sensitive adhesive for the foot patch bottom support according to any one of claims 1 to 6, characterized by comprising the following steps:
blending the preparation raw materials of the hot-melt pressure-sensitive adhesive at 155-170 ℃, and extruding to obtain the hot-melt pressure-sensitive adhesive.
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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 |
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| FR2993897B1 (en) * | 2012-07-30 | 2015-08-21 | Bostik Sa | SELF-ADHESIVE SELF-ADHESIVE FOR REFERMABLE PACKAGING WITH IMPROVED ORGANOLEPTIC PROPERTIES |
| CN106047287B (en) * | 2016-05-30 | 2018-04-10 | 广东荣嘉新材料科技有限公司 | Disposable sanitary articles Low Temperature Hot-Melt Pressure Sensitive and preparation method thereof |
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