CN110669462A - Label adhesive for small-caliber glass bottles and preparation method thereof - Google Patents
Label adhesive for small-caliber glass bottles and preparation method thereof Download PDFInfo
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- CN110669462A CN110669462A CN201911021158.6A CN201911021158A CN110669462A CN 110669462 A CN110669462 A CN 110669462A CN 201911021158 A CN201911021158 A CN 201911021158A CN 110669462 A CN110669462 A CN 110669462A
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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
- 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
- C09J157/00—Adhesives based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09J157/02—Copolymers of mineral oil hydrocarbons
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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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- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to the technical field of adhesives, in particular to a label adhesive for small-caliber glass bottles and a preparation method thereof. The preparation raw materials of the label adhesive comprise, by weight, 50-60 parts of styrene-based block copolymer, 60-90 parts of tackifying resin, 40-50 parts of softener and 1-2 parts of antioxidant, wherein the styrene-based block copolymer is selected from one or more of SEBS, SBS, SIS, SBR and SEPS. The invention provides a label adhesive for small-diameter glass bottles, which has high initial adhesion and sustained adhesion performance to glass bottles while ensuring good die cutting performance when the label adhesive prepared by the action of a styrene segmented copolymer, tackifying resin and a softening agent is used for labels.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a label adhesive for small-caliber glass bottles and a preparation method thereof.
Background
The label glue is also called trademark glue and refers to an adhesive used for sticking labels. With different label applications, labels prepared from different base materials and labels with different shapes and sizes are available, and the requirements on label glue are different according to different objects to be pasted. In the market, the plastic bottle or the glass bottle with a small caliber has a small caliber, the bending rate is large after the small label is attached, and the plastic bottle or the glass bottle needs to be gradually restored to a flat state under the stress action of the label paper, so that the requirements on the permanent adhesion and the initial adhesion of the hot-melt pressure-sensitive adhesive are particularly high, and in addition, the requirement on the die cutting of the label is also high due to the small size of the label. The prior label adhesive can not simultaneously meet the good performances of die cutting, permanent adhesion and initial adhesion.
Disclosure of Invention
In order to solve the problems, the invention provides a label adhesive for a small-diameter glass bottle, which is prepared from 50-60 parts by weight of styrene block copolymer, 60-90 parts by weight of tackifying resin, 40-50 parts by weight of softener and 1-2 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 embodiment of the present invention, the styrenic block copolymer is SIS.
As a preferable technical scheme of the invention, the SIS comprises SI, and the SI accounts for 40-60 wt% of the SIS.
As a preferable technical scheme of the invention, the S/I of the SIS is 10/90-20/80.
In a preferred embodiment of the present invention, the viscosity of the SIS is 600 to 1000MPa · s.
In a preferred embodiment of the present invention, the tackifying resin is one or more selected from rosin-based resins, terpene resins, hydrocarbon resins, and phenol resins.
In a preferred embodiment of the present invention, the tackifying resin is a hydrocarbon resin, and the hydrocarbon resin is one or more selected from the group consisting of C5 petroleum resin, C9 petroleum resin, hydrogenated petroleum resin, and dicyclopentadiene resin.
As a preferable technical scheme of the invention, the hydrocarbon resin also comprises 10-25 wt% of titanium dioxide modified hydrocarbon resin.
As a preferred embodiment of the present invention, the method for preparing the titanium dioxide modified hydrocarbon resin comprises the steps of:
(1) adding titanium dioxide into a solvent, adjusting the pH to 5-6, heating to 60-80 ℃, dropwise adding a silane coupling agent for reacting for 4-5 hours, washing, and drying to obtain modified titanium dioxide;
(2) and adding the tackifying resin into the solvent, stirring, adding the modified titanium dioxide, performing ultrasonic treatment for 30-60 min, grinding, and drying to obtain the titanium dioxide modified hydrocarbon resin.
The invention provides a preparation method of the label adhesive for the small-caliber glass bottles, which comprises the following steps: and blending and extruding the preparation raw materials of the label adhesive at 150-160 ℃ to obtain the label adhesive.
Compared with the prior art, the invention has the following beneficial effects: the invention provides a label adhesive for small-diameter glass bottles, which has high initial adhesion and sustained adhesion performance to glass bottles while ensuring good die cutting performance when the label adhesive prepared by the action of a styrene segmented copolymer, tackifying resin and a softening agent is used for labels.
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 label adhesive for a small-diameter glass bottle, which comprises the following raw materials, by weight, 50-60 parts of styrene-based block copolymer, 60-90 parts of tackifying resin, 40-50 parts of softener and 1-2 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 label adhesive of the present invention is prepared from 55 parts by weight of styrene block copolymer, 70 parts by weight of tackifying resin, 45 parts by weight of softener and 1 part by weight of 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 copolymer of the present invention is SIS.
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.
More preferably, the SIS comprises SI, and the SI accounts for 40-60 wt% of the SIS.
Further preferably, the SI of the present invention comprises 50 wt% of the SIS.
The SI is a polystyrene-polyisoprene diblock copolymer, has good fluidity and adhesiveness, and can be added into the SIS to adjust the physical properties of the SIS, such as viscosity and the like.
More preferably, the SIS has S/I of 10/90-20/80.
In a preferred embodiment, the SIS of the present invention has an S/I of 16/84.
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 600 to 1000 mPas.
In a further preferred embodiment, the SIS of the invention has a viscosity of 900MPa · 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 ℃.
The applicant finds that the die cutting performance of the label adhesive for labels can be improved by using the SIS as a styrene block copolymer and limiting the properties such as the viscosity and the like of the SIS through the combined action of the SIS and tackifying resin and a softening agent, and the reason is probably that the label adhesive contains a proper amount of SI blocks through limiting the content of the SI blocks in the SIS, the SI blocks are of a two-block structure and cannot form a cross-linking network of an SIS system, so that the good die cutting performance is facilitated, and the SI blocks have high chain segment activity and are beneficial to improving the initial viscosity, but the holding viscosity can be greatly reduced due to the network defect of the SI blocks.
In a further preferred embodiment, the SIS of the present invention is available under the designation SIS-1126, available from Yueyang Barring Huaxing petrochemical Co.
The SI of the SIS-1126 accounts for 50 wt% of the SIS, the S/I is 16/84, and the viscosity is 900MPa · S.
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 is selected from one or more of rosin resin, terpene resin, hydrocarbon resin, acrylic resin, phenolic resin and polyformaldehyde resin.
As examples of the rosin resin, there are, but not limited to, rosin glycerin ester, and there may be mentioned, rosin glycerin ester 138, rosin resin 145, rosin resin 146; maleic anhydride rosin resin; wood rosin; hydrogenated rosin; and (3) polymerizing the rosin.
Examples of terpene resins include, but are not limited to, α -terpene polymers, β -terpene polymers, diterpene polymers.
As examples of the hydrocarbon resin, there are, but not limited to, C5 petroleum resin, and there may be mentioned, C5 petroleum resin a 1100; c9 petroleum resin; hydrogenated petroleum resin, for example, hydrogenated petroleum resin 1102, hydrogenated petroleum resin 1204, hydrogenated petroleum resin 1304, hydrogenated petroleum resin 1401, hydrogenated petroleum resin 5300, hydrogenated petroleum resin 5400, hydrogenated petroleum resin LH-0#, hydrogenated petroleum resin LH-1 #; a dicyclopentadiene resin.
As examples of the phenolic resin, there are included, but not limited to, alkyl phenol resins.
More preferably, the tackifying resin of the present invention is a hydrocarbon resin selected from one or more of C5 petroleum resin, C9 petroleum resin, hydrogenated petroleum resin, dicyclopentadiene.
Further preferably, the hydrocarbon resin of the present invention is a hydrogenated C5 petroleum resin.
Still more preferably, the softening point of the hydrogenated C5 petroleum resin is 95-105 ℃.
In a preferred embodiment, the hydrogenated petroleum resin of the present invention has a softening point of 100 ℃.
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.
Preferably, the hydrocarbon resin further comprises 10-25 wt% of titanium dioxide modified hydrocarbon resin.
More preferably, the hydrocarbon resin of the present invention comprises 20 wt% of the titanium dioxide-modified hydrocarbon resin.
Further preferably, the method for preparing the titanium dioxide modified hydrocarbon resin of the present invention comprises the steps of:
(1) adding titanium dioxide into a solvent, adjusting the pH to 5-6, heating to 60-80 ℃, dropwise adding a silane coupling agent for reacting for 4-5 hours, washing, and drying to obtain modified titanium dioxide;
(2) adding hydrocarbon resin into a solvent, stirring, adding modified titanium dioxide, performing ultrasonic treatment for 30-60 min, grinding, and drying to obtain the titanium dioxide modified hydrocarbon resin.
Still more preferably, the weight ratio of the titanium dioxide and the silane coupling agent in the step (1) of the present invention is 1: (0.05-0.2).
Still more preferably, the weight ratio of the titanium dioxide and the silane coupling agent in the step (1) of the present invention is 1: 0.1.
still more preferably, the weight ratio of the hydrocarbon resin and the modified titanium dioxide in the step (2) of the present invention is 1: (0.1-0.2).
Still more preferably, the weight ratio of the hydrocarbon resin and the modified titanium dioxide of the present invention is 1: 0.15.
more preferably, the particle size of the titanium dioxide is 0.2-0.4 μm.
More preferably, 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.
Still more preferably, the titanium dioxide of the present invention is available under the trade designation R-818 from Jinan Quanhui chemical Co.
The particle size of the titanium dioxide R-818 is 0.2-0.26 mu m.
Still more preferably, the silane coupling agent of the present invention 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.
Examples of aminosilane coupling agents include, but are not limited to, 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), bis- [3- (triethoxysilyl) -propyl ] -amine (CAS No.: 13497-18-2).
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 silane coupling agent of the present invention comprises an alkyl silane coupling agent and an acyloxy silane coupling agent, and the weight ratio of the alkyl silane coupling agent to the acyloxy silane coupling agent is 1: (2-3).
Still more preferably, the weight ratio of the alkyl silane coupling agent and the acyloxy silane coupling agent according to the present invention is 1: 3.
still more preferably, the alkylsilane coupling agent of the present invention is a C10-C20 alkylsilane coupling agent.
In a preferred embodiment, the solvent in step (1) is selected from one or more of ethanol, tetrahydrofuran, isopropanol and water.
In a more preferred embodiment, the solvent of step (1) is ethanol.
In a further preferred embodiment, in the pH adjustment in the step (1), the pH is adjusted to 5 to 6 by adding acetic acid and sodium carbonate.
In a still further preferred embodiment, the solvent of step (2) is selected from one or more of benzene, toluene, xylene.
In a still further preferred embodiment, the solvent of step (2) is toluene.
In a further preferred embodiment, in the grinding in the step (2), the grinding is carried out for 3-5 hours.
The applicant has found that the label stock prepared by adding titanium dioxide modified hydrocarbon resin can ensure high die cutting performance and has good permanent adhesion and initial adhesion performance, which is probably because the compatibility with the hydrocarbon resin, especially hydrogenated petroleum resin is increased while agglomeration is prevented by modifying titanium dioxide with silane coupling agent so that the surface of titanium dioxide is connected with organic group, and the long alkyl chain can be intertwined with the hydrocarbon resin by using the combined action of alkyl silane coupling agent and acyloxy silane coupling agent to further promote the compatibility of titanium dioxide and hydrocarbon resin to obtain the titanium dioxide modified hydrocarbon resin, when the titanium dioxide modified hydrocarbon resin is added, the titanium dioxide can be uniformly dispersed in the label stock along with the hydrocarbon resin, and because of the existence of the long alkyl chain on the surface of titanium dioxide and high polarity acyloxy group, the adhesive is favorable for contacting and infiltrating with the glass surface, the residual hydroxyl in the titanium dioxide can also interact with the hydroxyl on the glass surface, the initial adhesion and the peeling strength are further increased, in addition, the existence of high-polarity titanium-oxygen bonds in the titanium dioxide modified hydrocarbon resin is also favorable for increasing the permanent adhesion of the label adhesive, and the titanium dioxide can also be used as a physical crosslinking site, so that the reduction of cohesive strength caused by excessive SI is compensated, and the permanent adhesion is further increased.
Applicants have found that when too much titanium dioxide is added to modify the hydrocarbon resin, tack holding and die cutting performance can be affected, probably because the density of physical cross-links formed by the titanium dioxide is greater, thereby affecting die cutting performance, and when more tackifying resin is added, the amount of titanium dioxide is greater, which can cause agglomeration, thereby affecting tack holding. In addition, the applicant found that when the titanium dioxide modified by the silane coupling agent is added separately, the initial tack and the permanent tack of the prepared label adhesive are poor, which is probably caused by that the dispersion of the titanium dioxide is affected by the styrene and isoprene segments with large polarity difference in the SIS, so that the titanium dioxide is partially agglomerated.
In a more preferred embodiment, the hydrogenated C5 petroleum resin of the present invention has the designation E1304, available from Exxon Mobil.
The softening point of the hydrogenated C5 petroleum resin E1304 was 100 ℃.
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 molecular weight of the naphthenic oil is 300-400.
Molecular weight is the sum of the relative atomic masses of the atoms in a molecular weight as measured by astm d2502-2004 viscometry.
Still more preferably, the naphthenic oil of the present invention is available under the trademark KN4006# from special oils ltd.
The KN4006# naphthenic oil has a molecular weight of 350.
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 of the present invention comprises 5(6) -carboxydiacetoxyfluorescein succinimidyl ester and superoxide dismutase.
The invention does not specifically limit the weight ratio of the 5(6) -carboxyl diacetate fluorescein succinimide ester and the superoxide dismutase, and does not influence the performance of the label adhesive.
Further preferably, the antioxidant of the present invention has a trade mark of Huann-801, wherein the Huann-801 comprises 5(6) -carboxyl diacetate fluorescein succinimide ester and superoxide dismutase.
The structural adhesive of the present invention may further comprise various additives such as ultraviolet absorbers, for example, 2- (2H-benzotriazol-2-yl) -4, 6-bis (1-methyl-1-phenylethyl) phenol, 2- [4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazin-2-yl ] -5- (octyloxy) phenol, 2- (2' -hydroxy-5 ' -methyl) -benzotriazole, 2- (2' -hydroxy-3, 5-bis [1, 1-dimethylphenyl ]) -benzotriazole, 2(2' -hydroxy-5 ' -tert-octylphenyl) benzotriazole, 2' - (2' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5 -chlorobenzotriazole; 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- α, -butyl-malonate; fillers, which may be mentioned are zinc oxide, titanium dioxide, lithopone.
The second aspect of the invention provides the preparation method of the label adhesive for the small-caliber glass bottle, which comprises the steps of blending and extruding the preparation raw materials of the label adhesive at 150-160 ℃ 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-1126, the SI accounts for 50wt percent of the SIS, the S/I is 16/84, and the viscosity is 900 MPa.s.
A2: styrenic block copolymer
The styrene block copolymer is SIS with the mark of SIS-1124, the SI accounts for 25 wt% of the SIS, the S/I is 14/86, and the viscosity is 1200 MPa.s.
B1: tackifying resins
The tackifying resin is hydrogenated C5 petroleum resin with the trade name of E1304 which is purchased from Exxon Mobil.
B2: tackifying resins
The tackifying resin was a C5 petroleum resin, brand a1100, available from puyang corporation, luck chemical ltd.
B3: tackifying resins
The tackifying resin is titanium dioxide modified hydrocarbon resin, and the preparation method of the titanium dioxide modified hydrocarbon resin comprises the following steps:
(1) adding titanium dioxide into ethanol, adjusting the pH value to 5, heating to 70 ℃, dropwise adding a silane coupling agent, and reacting for 5 hours, wherein the weight ratio of the titanium dioxide to the silane coupling agent is 1: 0.1, washing and drying to obtain modified titanium dioxide;
(2) adding hydrocarbon resin into toluene, stirring, adding modified titanium dioxide, and performing ultrasonic treatment for 50min, wherein the weight ratio of the hydrocarbon resin to the modified titanium dioxide is 1: 0.15, grinding for 4 hours, and drying to obtain the titanium dioxide modified hydrocarbon resin.
The titanium dioxide is R-818, is purchased from Jinan spring chemical Limited and has the particle size of 0.2-0.26 mu m.
The silane coupling agent comprises gamma-methacryloxypropyltriethoxysilane and hexadecyltrimethoxysilane in a weight ratio of 3: 1.
the hydrocarbon resin is hydrogenated C5 petroleum resin, available from Exxon Mobil, under the designation E1304.
B4: tackifying resins
The tackifying resin is titanium dioxide modified hydrocarbon resin, and the preparation method of the titanium dioxide modified hydrocarbon resin comprises the following steps:
(1) adding titanium dioxide into ethanol, adjusting the pH value to 5, heating to 70 ℃, dropwise adding a silane coupling agent, and reacting for 5 hours, wherein the weight ratio of the titanium dioxide to the silane coupling agent is 1: 0.1, washing and drying to obtain modified titanium dioxide;
(2) adding hydrocarbon resin into toluene, stirring, adding modified titanium dioxide, and performing ultrasonic treatment for 50min, wherein the weight ratio of the hydrocarbon resin to the modified titanium dioxide is 1: 0.15, grinding for 4 hours, and drying to obtain the titanium dioxide modified hydrocarbon resin.
The titanium dioxide is R-818, is purchased from Jinan spring chemical Limited and has the particle size of 0.2-0.26 mu m.
The silane coupling agent is hexadecyl trimethoxy silane.
The hydrocarbon resin is hydrogenated C5 petroleum resin, available from Exxon Mobil, under the designation E1304.
B5: tackifying resins
The tackifying resin is titanium dioxide modified hydrocarbon resin, and the preparation method of the titanium dioxide modified hydrocarbon resin comprises the following steps:
(1) adding titanium dioxide into ethanol, adjusting the pH value to 5, heating to 70 ℃, dropwise adding a silane coupling agent, and reacting for 5 hours, wherein the weight ratio of the titanium dioxide to the silane coupling agent is 1: 0.1, washing and drying to obtain modified titanium dioxide;
(2) adding hydrocarbon resin into toluene, stirring, adding modified titanium dioxide, and performing ultrasonic treatment for 50min, wherein the weight ratio of the hydrocarbon resin to the modified titanium dioxide is 1: 0.15, grinding for 4 hours, and drying to obtain the titanium dioxide modified hydrocarbon resin.
The titanium dioxide is R-818, is purchased from Jinan spring chemical Limited and has the particle size of 0.2-0.26 mu m.
The silane coupling agent is gamma-methacryloxypropyltriethoxysilane.
The hydrocarbon resin is hydrogenated C5 petroleum resin, available from Exxon Mobil, under the designation E1304.
B6: tackifying resins
The tackifying resin is titanium dioxide modified hydrocarbon resin, and the preparation method of the titanium dioxide modified hydrocarbon resin comprises the following steps:
(1) adding titanium dioxide into ethanol, adjusting the pH value to 5, heating to 70 ℃, dropwise adding a silane coupling agent, and reacting for 5 hours, wherein the weight ratio of the titanium dioxide to the silane coupling agent is 1: 0.1, washing and drying to obtain modified titanium dioxide;
(2) adding hydrocarbon resin into toluene, stirring, adding modified titanium dioxide, and performing ultrasonic treatment for 50min, wherein the weight ratio of the hydrocarbon resin to the modified titanium dioxide is 1: 0.15, grinding for 4 hours, and drying to obtain the titanium dioxide modified hydrocarbon resin.
The titanium dioxide is R-818, is purchased from Jinan spring chemical Limited and has the particle size of 0.2-0.26 mu m.
The silane coupling agent comprises gamma-methacryloxypropyltriethoxysilane and octyltriethoxysilane in a weight ratio of 3: 1.
the hydrocarbon resin is hydrogenated C5 petroleum resin, available from Exxon Mobil, under the designation E1304.
C: softening agent
The softener is naphthenic oil, and the grade of the naphthenic oil is KN4006# which is purchased from Suzhou Seapahan special oil products Co.
D: antioxidant agent
The antioxidant is named as Huan-801, and the Huan-801 comprises 5(6) -carboxyl diacetate fluorescein succinimide ester and superoxide dismutase.
TABLE 1
| Examples | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 |
| A1 | 55 | 50 | 60 | 55 | 55 | 55 | 55 | 55 | 55 | 55 | |
| A2 | 55 | ||||||||||
| B1 | 70 | 54 | 67.5 | 56 | 56 | 56 | 56 | 56 | 40 | 70 | |
| B2 | 56 | ||||||||||
| B3 | 6 | 22.5 | 14 | 14 | 14 | 30 | 14 | ||||
| B4 | 14 | ||||||||||
| B5 | 14 | ||||||||||
| B6 | 14 | ||||||||||
| C | 45 | 40 | 50 | 45 | 45 | 45 | 45 | 45 | 45 | 45 | 45 |
| D | 1 | 1 | 2 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
Examples 1 to 11 provide a label adhesive for a small-diameter glass bottle, and a formula of the structural adhesive for producing a paper diaper in a low-temperature environment is shown in table 1, and the formula is used in parts by weight.
Embodiments 1 to 11 provide a method for preparing a label adhesive for a small-diameter glass bottle, including the steps of: and blending and extruding the preparation raw materials of the label adhesive at 150 ℃ to obtain the label adhesive.
Evaluation of Performance
1. Initial viscosity: the maximum steel ball which can be stuck by the label adhesive for the small-caliber glass bottle provided in the embodiment 1-11 is tested according to the method A inclined plane rolling ball method of GB/T4852-2002, and the initial viscosity is measured by the type of the steel ball, and the result is shown in Table 2.
2. Viscosity retention: the label stock for small bore glass bottles provided in examples 1-11 was tested for tack according to GB/T4851-2014 and the results are shown in Table 2.
3. Die cutting performance: the label glue for the small-caliber glass bottles provided by the embodiment 1-11 is used for coating labels through a coating machine, then the label glue is matched with die cutting through a 320-type circular high-speed precision die cutting machine, when the conditions of waste paper discharge disconnection and label flying are observed, the die cutting performance is measured according to the die cutting length per minute, and the result is shown in table 2.
Table 2 characterization test of properties
| Examples | Initial viscosity (Steel ball) | Tackiness (h) | Cross cutting Property (m/min) |
| 1 | 18 | 62 | 120 |
| 2 | 20 | 85 | 139 |
| 3 | 21 | 89 | 137 |
| 4 | 21 | 90 | 140 |
| 5 | 16 | 81 | 92 |
| 6 | 17 | 80 | 104 |
| 7 | 18 | 76 | 122 |
| 8 | 18 | 74 | 127 |
| 9 | 19 | 79 | 131 |
| 10 | 13 | 68 | 86 |
| 11 | 17 | 78 | 107 |
The test results in table 2 show that the label adhesive for the small-caliber glass bottle provided by the invention has good initial adhesion and sustained adhesion while ensuring high die cutting performance, wherein the die cutting performance can reach 120m/min, the maximum bondable steel ball number can be more than 20, and the sustained adhesion can be more than 80 h.
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 (10)
1. The label adhesive for the small-caliber glass bottle is characterized by comprising 50-60 parts by weight of styrene block copolymer, 60-90 parts by weight of tackifying resin, 40-50 parts by weight of softening agent and 1-2 parts by weight of antioxidant, wherein the styrene block copolymer is selected from one or more of SEBS, SBS, SIS, SBR and SEPS.
2. The label stock for small bore glass bottles of claim 1 wherein said styrenic block copolymer is SIS.
3. The label stock for small bore glass bottles of claim 2, wherein said SIS comprises SI, said SI comprising 40 to 60 wt% of SIS.
4. The label adhesive for small-caliber glass bottles of claim 3, wherein the SIS has an S/I of 10/90-20/80.
5. The label adhesive for small-caliber glass bottles of claim 4, wherein the SIS has a viscosity of 600 to 1000 MPa-s.
6. The label stock for small-diameter glass bottles of any one of claims 1 to 5, wherein the tackifying resin is selected from one or more of rosin-based resins, terpene resins, hydrocarbon resins and phenolic resins.
7. The label stock for small-bore glass bottles of claim 6, wherein said tackifying resin is a hydrocarbon resin selected from one or more of C5 petroleum resin, C9 petroleum resin, hydrogenated petroleum resin, dicyclopentadiene resin.
8. The label adhesive for small-bore glass bottles of claim 7, wherein said hydrocarbon resin further comprises 10 to 25 wt% of a titanium dioxide modified hydrocarbon resin.
9. The label adhesive for small-caliber glass bottles of claim 8, wherein the preparation method of the titanium dioxide modified hydrocarbon resin comprises the following steps:
(1) adding titanium dioxide into a solvent, adjusting the pH to 5-6, heating to 60-80 ℃, dropwise adding a silane coupling agent for reacting for 4-5 hours, washing, and drying to obtain modified titanium dioxide;
(2) and adding the tackifying resin into the solvent, stirring, adding the modified titanium dioxide, performing ultrasonic treatment for 30-60 min, grinding, and drying to obtain the titanium dioxide modified hydrocarbon resin.
10. The preparation method of the label adhesive for the small-caliber glass bottle as claimed in any one of claims 1 to 9, characterized by comprising the following steps: and blending and extruding the preparation raw materials of the label adhesive at 150-160 ℃ to obtain the label adhesive.
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| CN201911021158.6A CN110669462B (en) | 2019-10-25 | 2019-10-25 | Label adhesive for small-caliber glass bottles and preparation method thereof |
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| CN201911021158.6A CN110669462B (en) | 2019-10-25 | 2019-10-25 | Label adhesive for small-caliber glass bottles and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113278393A (en) * | 2021-04-02 | 2021-08-20 | 江门保实捷化工有限公司 | Heat-resistant PP hot melt adhesive and preparation method and application thereof |
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