CN106327994A - Antimicrobial sealing label capable of being torn and stuck for plurality of times and preparation method and application of antimicrobial sealing label - Google Patents
Antimicrobial sealing label capable of being torn and stuck for plurality of times and preparation method and application of antimicrobial sealing label Download PDFInfo
- Publication number
- CN106327994A CN106327994A CN201610692919.0A CN201610692919A CN106327994A CN 106327994 A CN106327994 A CN 106327994A CN 201610692919 A CN201610692919 A CN 201610692919A CN 106327994 A CN106327994 A CN 106327994A
- Authority
- CN
- China
- Prior art keywords
- antimicrobial
- sensitive adhesive
- patch
- pressure sensitive
- repeatedly
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
- G09F3/02—Forms or constructions
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
- C08K5/31—Guanidine; Derivatives thereof
-
- 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
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
- G09F3/02—Forms or constructions
- G09F2003/023—Adhesive
- G09F2003/0241—Repositionable or pressure sensitive adhesive
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Theoretical Computer Science (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesive Tapes (AREA)
- Medicinal Preparation (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses an antimicrobial sealing label capable of being torn and stuck for a plurality of times and a preparation method and application of the antimicrobial sealing label. The antimicrobial sealing label capable of being torn and stuck for the plurality of times comprises a thin film base material which has oxygen permeability lower than 5.0mL/(m<2> 24h 0.1MPa) and moisture permeability lower than 5g/(m<2> 24h) and contains a PVDC (Polyvinyl Dichloride) coating material, an antimicrobial pressure-sensitive adhesive composition with viscous force greater than 44mN/m and adhesive force greater than 2N/inch, and a release type substrate which has release force smaller than 25g/inch and contains a silicone oil coating. After an antimicrobial sealing label material is cut into a label, the label is used for sealing a product package and has an antibiotic inhibition effect; the sanitation and safety can be effectively ensured, the number of times of tearing and sticking the sealing label and the sealing effect are improved, and a phenomenon that the sealing label is torn from and stuck on an stuck object and an adhesive is remained is avoided.
Description
Technical field
The invention belongs to label and field of material technology thereof, be specifically related to a kind of antimicrobial that can repeatedly tear patch and seal mark
Sign material, label and its preparation method and application.
Background technology
Cutting out the pressure-sensitive adhesive label of body as information, be seen everywhere in daily life, its basic function is to carry to be pasted
Commodity and the information of maker thereof, intersperse and beautify by patch commodity.Along with the development of material science, commodity and packaged form thereof
The most varied, the higher function cutting out body label as information requires the most various.Therefore, the exploitation of functionality tabs
With application variation the most therewith, occur in that many functionalization labels, such as high temperature resistant labels, stand freezing label, printable mark
Label, organic solvent-resistant wiping label, line production process label, inducing QI reticulate pattern label etc..
In order to meet the needs of different purposes, industry further developed such as multiple Wet paper towel packing bag seal labers, baby children
The wet tissue that degreases used in the packaging bag seal laber of youngster's hygienic article, the packaging bag seal laber of sanltary towel, kitchen
One classes such as packaging bag seal laber repeated multiple times can tear the seal laber of patch；This kind of label is to post one in the packaging bag of commodity
Open the pressure sensitive adhesive Sealing piece that repeated multiple times can tear patch of " sealing ".Evaluate this pressure sensitive adhesive Sealing piece the most qualified main
Standard is to see to leave cull after the most repeatedly tearing patch in commodity packaging；Therefore the seal laber of patch can repeatedly be torn
It is a kind of typical binding agent functional label, there is the performance characteristic that can repeatedly tear patch.The repeated multiple times seal laber tearing patch should
When the sealing of pack content wet paper towel etc., due to by patch product content there are a certain amount of moisture (such as:
Water, alcohol or other liquid mediums) label cohesive force function can be offset, thus the bond strength of adhesive, therefore, viscose glue can be reduced
The viscosity of agent is an important indicator of the seal laber that can repeatedly tear patch；The existing seal laber that can repeatedly tear patch is used
Adhesive along with tear patch number of times be incremented by and be gradually lowered and even lose cement properties, cause sealing function to lack.
For being applied in the seal laber that can repeatedly tear patch of typical wet product, " sealing " is by film substrate pair
Being carried out airtight by the moisture (such as: water, alcohol or other liquid mediums) of the content of patch product and intercept, film substrate has low
Oxygen permeability and low-moisture permeability are to investigate the airtight important indicator with barrier property of seal laber；Chinese patent application
The film substrate of seal laber disclosed in CN201280076406.7 is to use polyolefin, polyethylene terephthalate, polychlorostyrene
A kind of single layer structure in ethylene or two or more multiple structures；Currently used this kind of film substrate oxygen permeability
Too big with poisture-penetrability, cause label barrier property low, sealing effectiveness is poor.
For personal hygiene article, such as wet paper towel, infant Dribble towel, sanltary towel, nursing facial film, and currently exist
Technology, product, market tourism the most leaved for development, health, nursing, health product, the health of its product, sterilizing also meet some certainly
Rule standard and pressure standard are inevitable, and as being applied to the seal laber that can repeatedly tear patch of health, sterilising prods, many
Secondary unpacking, airtight, then break seal, the most airtight during, low except the viscosity of binding agent described above and film substrate
Beyond oxygen permeability and low-moisture permeability, antimicrobial function, bacteriostasis and the safe and sanitary of seal laber is also important index
One of.
To sum up, the existing seal laber that can repeatedly tear patch is primarily present problems with: 1) commonly used film substrate
Oxygen permeability and poisture-penetrability are too big, cause label barrier property low, and sealing effectiveness is poor；2) label having does not has the defence of antibiotic and sterilizing
Barrier, causes label repeatedly to open and is prone to by microbial attack, and safe and sanitary is the most up to standard；3) existing label through repeatedly tear open,
After stickup, the bonding force reduction of adhesive is even lost, and causes and seals unsuccessfully；4) not enough because of the coated face surface tension of face material, when
When seal laber is pasted on stratiform bag and/or the container of high surface tension, easily causes and repeatedly tear the adhesive transfer of patch also
Residue on affixed object.
Summary of the invention
In order to overcome the deficiencies in the prior art, it is an object of the invention to provide a kind of antimicrobial that can repeatedly tear patch close
Envelope label material, improves tearable patch number of times and the sealing effectiveness of seal laber while ensureing safe and sanitary, it is to avoid seal mark
Label are attached to adhesive residue on affixed object because repeatedly tearing.
For solving the problems referred to above, the technical solution adopted in the present invention is as follows:
A kind of antimicrobial seal laber material that can repeatedly tear patch, comprising:
Oxygen permeability is less than 5.0mL/ (m224h 0.1MPa), poisture-penetrability is less than 5g/ (m224h) containing PVDC be coated with
The film substrate of thing；
Glutinous base power more than 44mN/m, cohesive force more than the antimicrobial pressure sensitive adhesive compositions of 2N/ inch；
Off-type force is less than the release substrate of the silicate-containing oil coating of 25g/ inch.
As further scheme, film substrate of the present invention be TPO, polyethylene terephthalate,
Polrvinyl chloride etc., comprise the thin film or two or more of a kind of material in polypropylene, polyethylene, polyester, synthesis PP, synthesis BCA
Material is blended coextruded film.
As further scheme, antimicrobial pressure sensitive adhesive compositions of the present invention is by Acrylate pressure sensitive
Adhesive and the compositions of hibitane composition, wherein the concentration of hibitane is 1wt%-5wt%.
As further scheme, Acrylic Pressure Sensitive Adhesive of the present invention is polymerized by following component by weight
Form:
Acrylic acid 30-40 part, butyl acrylate 20-30 part, acrylic acid methyl ester. 50-70 part, Isooctyl acrylate monomer 10-20
Part, Colophonium 2-10 part, glycerol 5-10 part, ethyl acetate 180-270 part, initiator 3-5 part, isocyanate curing agent 0.7-1.5
Part.
As further scheme, the antimicrobial seal laber of patch that can repeatedly tear of the present invention is through 50-150 time
Repeatedly tear and be attached on affixed object not adhesive residue.
As further scheme, the thickness of PVDC coating material of the present invention is 0.8-3.0 μm.
Another object of the present invention is to provide the preparation side of a kind of antimicrobial seal laber material that can repeatedly tear patch
Method, by the method obtain a kind of tearable patch often with the antimicrobial seal laber material that can repeatedly tear patch of good sealing effect
Material；Scheme is as follows:
The preparation method of a kind of antimicrobial seal laber material that can repeatedly tear patch, this preparation method includes following step
Rapid:
1) preparation film substrate containing PVDC coating material: film substrate is positioned over unreeling of double coating head web coatable machine
On station, the first web coatable device is coated with silane coupling agent and forms priming coat, by the second reticulate pattern on priming coat after drying
Apparatus for coating line coating PVDC coating material baking and curing；Then on double coating head web coatable machines line cooling, rolling from
Line, is positioned over ripening 40-50h in the environment of 40-60 DEG C, obtains the film substrate containing PVDC coating material；
2) antimicrobial pressure sensitive adhesive compositions is prepared: be mixed anti-by Acrylic Pressure Sensitive Adhesive and hibitane
Microorganism pressure sensitive adhesive compositions；
3) the antimicrobial seal laber material of patch can be repeatedly torn in preparation: by coating machine by antimicrobial pressure-sensitive adhesive
Coat on release substrate, baking and curing formed antimicrobial formation of pressure-sensitive adhesive layer, then by step 1) obtain containing PVDC
The film substrate of coating material is combined to antimicrobial formation of pressure-sensitive adhesive layer, by the composite pressure of coating machine and release substrate
Antimicrobial formation of pressure-sensitive adhesive layer is transferred to the film substrate layer containing PVDC coating material by off-type force, cold by coating machine line
Radiator cooler cools down, and rolling, off-line are positioned over 45-55 DEG C of environment ripening 120-150h, and the antimicrobial obtaining repeatedly tearing patch is close
Envelope label material.
As further scheme, the step 2 described in above-mentioned preparation method) in Acrylic Pressure Sensitive Adhesive pressed by following
Weight meter component is polymerized:
Acrylic acid 30-40 part, butyl acrylate 20-30 part, acrylic acid methyl ester. 50-70 part, Isooctyl acrylate monomer 10-20
Part, Colophonium 2-10 part, glycerol 5-10 part, ethyl acetate 180-270 part, initiator 3-5 part, isocyanate curing agent 0.7-1.5
Part；
The concrete preparation method of antimicrobial pressure sensitive adhesive compositions is as follows；
A: 1-3 part initiator is dissolved in 30-50 part ethyl acetate solution, is then sequentially added into the propylene of formula ratio
Acid, butyl acrylate, acrylic acid methyl ester., Isooctyl acrylate monomer, glycerol, obtain mixed liquor after being thoroughly mixed uniformly；
B: 30-50 part ethyl acetate is added in reactor and is warming up to 76-80 DEG C, slowly drip 1/2 after backflow is stable
The above-mentioned mixed liquor of volume, 80-82 DEG C of stirring reaction 1.5-2 hour；
C: remaining initiator is dissolved in the ethyl acetate solution forming initiator in remaining ethyl acetate, and this is drawn
The mixed liquor sending out the ethyl acetate solution of agent and above-mentioned remaining 1/2 volume synchronizes to be added drop-wise to step 2 slowly) reaction system
In, continue to drip the rosin milk of 2-10 part after dripping in reaction system, keep 80-82 DEG C of continuation reaction 0.5-1.5 little
Time, obtain Acrylic Pressure Sensitive Adhesive；
D: after Acrylic Pressure Sensitive Adhesive is cooled to room temperature, drips 3-5 part chlorhexidine gluconate, i.e. obtains anti-micro-
Biological pressure sensitive adhesive compositions.
E: before coating antimicrobial pressure sensitive adhesive compositions, isocyanate curing agent 0.7-1.5 part is added to combination
In thing, homogenizer stirs 15-25 minute, stands 10-20 minute.
As further scheme, the thickness of priming coat of the present invention is 0.2-0.5 μm；Described PVDC coating material
Thickness be 0.8-3.0 μm, the thickness of antimicrobial formation of pressure-sensitive adhesive layer is 12-30 μm.
Third object of the present invention be to provide a kind of tearable patch often with good sealing effect can repeatedly tear the anti-of patch
Microorganism-tight label, can avoid being attached to adhesive residue on affixed object because repeatedly tearing simultaneously.
A kind of antimicrobial seal laber that can repeatedly tear patch, it is by the anti-micro-life that can repeatedly tear patch of the present invention
Thing seal laber material is formed after printing, cross cutting.
Fourth object of the present invention is that the described antimicrobial seal laber that can repeatedly tear patch is at layer structure bag
Application in pack or packing container.Can repeatedly tear the antimicrobial seal laber of patch for packaging bag or packing container opening
Seal.
5th purpose of the present invention is to provide the packaging of a kind of antimicrobial seal laber comprising and can repeatedly tearing patch
Container, scheme is as follows:
A kind of packaging bag or packing container, it includes packaging bag body or packing container body, described packaging bag body or
Packing container body is provided with the opening picking and placeing content, and described opening part is with the anti-micro-life that can repeatedly tear patch of the present invention
Thing seal laber seals.
Compared to existing technology, the beneficial effects of the present invention is:
The film substrate of the antimicrobial seal laber material that can repeatedly tear patch the most of the present invention is coated with by PVDC
Thing is coated with, and reaches oxygen permeability and the low film substrate of poisture-penetrability, and can be effectively improved seal laber containing PVDC coating material
Intercept moisture and the performance of oxygen and sealing effectiveness；
Containing antimicrobial pressure-sensitive adhesive in the antimicrobial seal laber material that can repeatedly tear patch the most of the present invention
Agent compositions can be effectively improved tearable patch number of times, sets up defensive barrier, it is ensured that microorganism is difficult to invasion, has antibiotic and sterilizing and makees
With, it is ensured that the safety and sanitation of packing material, adhesive residue on packing container or packaging bag can be prevented effectively from simultaneously.
Below in conjunction with detailed description of the invention, the present invention is described in further detail.
Accompanying drawing explanation
Fig. 1 be 10 groups of antimicrobial pressure sensitive adhesive seal laber antimicrobial of the present invention testing respectively of Quine's method and
Bacteriostasis result.
Detailed description of the invention
" adherend " or " affixed object " appeared in the present invention refer to of the present invention with of the present invention can be many
The bonding of the secondary antimicrobial seal laber tearing patch or the object of laminating, such as, can be stratiform packaging bag or packing container.
Term used in the present invention " antimicrobial ", " antibacterial " and " mildew-resistant ", description is to antibacterial, yeast, fungus
Or algae kills and the suppression that grows it and prevent it to grow；Term " antimicrobial pressure sensitive adhesive compositions " refers to
Acrylic Pressure Sensitive Adhesive is mixed with described dosage broad-spectrum antimicrobial agent, described described dosage broad-spectrum antimicrobial agent
The compositions formed with Acrylic Pressure Sensitive Adhesive existed with the use cycle of seal laber, and to seal laber and pasted
Thing plays antimicrobial, antibacterial, mildew-proof function.
The antimicrobial seal laber material that can repeatedly tear patch of the present invention, comprising:
Oxygen permeability is less than 5.0mL/ (m224h 0.1MPa), poisture-penetrability is less than 5g/ (m224h) containing PVDC be coated with
The film substrate of thing；
Glutinous base power more than 44mN/m, cohesive force more than the antimicrobial pressure sensitive adhesive compositions of 2N/ inch；
Off-type force is less than the release substrate of the silicate-containing oil coating of 25g/ inch.
PVDC resin is as composite or monomer material and coextruded film, and PVDC is strong due to its intermolecular cohesive force, knot
Crystalline substance degree is high, and the chlorine atom in PVDC molecule has hydrophobicity, will not form hydrogen bond, oxygen molecule and hydrone and be difficult in PVDC molecule
Mobile, thus make it have excellent oxygen barrier and hinder moist, and its oxygen barrier is not affected by ambient humidity；Namely
Saying, under the conditions of any temperature and humidity, have brilliance concurrently intercepts steam, oxygen, abnormal smells from the patient and the ability of fragrance.Of the present invention
PVDC be the abbreviation of macromolecular compound polyvinylidene chloride, due to polyvinylidene chloride homopolymer poor heat stability, molding
Poor processability, it is impossible to be applied to the plastics processing method machine-shaping of routine, so, in the present invention by by PVDC being
PVDC latex is coated on TPO, polyethylene terephthalate etc. and comprises poly-by the coating process of vinylidene chloride routine
Propylene, polyethylene, polyester, polrvinyl chloride, PP synthesis, BCA synthesize and formation are blended on any one thin film of coextruded film
The PVDC thin layer of highly crystalline.In the research of the present invention, find that PVDC is coated on film substrate, gathering with biaxial tension
As a example by Polypropylene film, after coating, its oxygen transmission rate reduces by 1000 times, and permeability rate reduces by 3 times；Coating can be the most single with single or multiple lift
Layer is applied to 2 μm and can obtain good barrier.The present invention use the film substrate containing PVDC coating material have good
Gas barrier property and resistance are moist, and wherein gas barrier property refers to delay the generation of the content oxidation deterioration phenomenon of packaging, it is possible to avoid
Scattering and disappearing and the intrusion of the outside abnormal flavour of obstruct of the content of packaging, particularly fragrance and alcohol；Hinder moist referring to and prevent packaging
Content, the highest moisture content, high alcohol-content, liquor aromas etc. occur dehydration to become dry, prevent quantitative goods generation from naturally damaging
Consumption (weightless).Additionally, be dry products for pack content, such as sanltary towel, baby paper diaper etc., PVDC moisture barrier property
Outside moisture is enough stoped to invade, and, the gas barrier properties of PVDC of the present invention does not changes because of the change of ambient humidity, i.e.
Make in hot and humid environment, the most do not cause the rotten of content and variable.
As further scheme, film substrate of the present invention be TPO, polyethylene terephthalate,
Polrvinyl chloride etc., comprise the thin film or two or more of a kind of material in polypropylene, polyethylene, polyester, synthesis PP, synthesis BCA
Material is blended coextruded film.
In the present invention, owing to using oxygen permeability less than 5.0mL/ (m224h 0.1MPa), poisture-penetrability is less than 5g/
(m2The film substrate containing PVDC coating material 24h), even if being chronically exposed to outdoor, directly exposing to sunlight, also will not
Label is occurred to fade or catabiosis, safety and environmental protection, and by FDA (FDA Food and Drug Administration) certification, for food, medicine
Product, the packaging of nursing health products escort safely.
" glutinous base power (keying) " specifically refer to adhesive and base material or adhesive and silane coupling agent and silane coupling agent and base material it
Between cohesive force.Glutinous base power of the present invention, refer to by described antimicrobial pressure-sensitive adhesive and base material or adhesive with
Bonding strength between silane coupling agent and silane coupling agent and base material.Base material or be coated on the surface free energy of silane coupling agent above base material
Size and the cohesive strength of described antimicrobial pressure-sensitive adhesive, be the essential condition determining glutinous base power size.In existing skill
In art, oneself being formed as pressure-sensitive adhesive label, its glutinous base power size cannot characterize with test.Present invention research finds, pressure
The glutinous base power of quick glue goods needs surface tension mN/m (dyne) with base material (and/or silane coupling agent) to characterize.Of the present invention
Glutinous base power more than 44mN/m, be the described antimicrobial seal laber that can repeatedly tear patch to be pasted on surface tension be more than
In the bread board of 44mN/m, i.e. 46mN/m or 48mN/m or 50mN/m, it is then passed through 66 DEG C, the high temperature of relative humidity 80%
The degradation of high humidity 48-96h, and with the speed of 5-50/s and the angle of about 120 °, label is peeled off from bread board,
Test with this and confirm that the adhesive that can repeatedly tear the antimicrobial seal laber of patch does not residues on affixed object, and passing through
Hot and humid and 48-96h test carrys out this seal laber of anticipation and is pasted on described packaging bag and 1 year of packing container and 2 years
Period in whether adhesive residue (" pressure-sensitive adhesive applied on the same day in the present invention referring in detail to the present inventor on affixed object
Goods cull rank test method ").As can be seen here, glutinous base power of the present invention can be repeatedly for described more than 44mN/m
Tear the antimicrobial seal laber of patch and be pasted on the unlatching, airtight that described packaging bag and packing container are through 1-150 time, be then turned on,
The most airtight sealing applications is useful.
Cohesive force of the present invention, more than the antimicrobial pressure sensitive adhesive seal laber of 2N/ inch, is particularly applied to bag
During content-filled sealing for wet paper towel etc., owing to be there are a certain amount of moisture (such as: water, alcohol by the content of patch product
Or other liquid mediums) label cohesive force function can be offset, thus the bonding strength of adhesive can be reduced；Meanwhile, described sealing
Labeling requirement repeatedly tear label and after pasting through long period (if Product transport is on the way or product treats pin in storehouse, including half a year
Or 1 year, the most longer period) and therefore cohesive force can not reduce or become repeatedly to tear described in big grade and paste seal laber
Characteristic, and it is different from some pressure-sensitive adhesive label of prior art, its cohesive force is the bigger the better, or after label stickup over time
Passage cohesive force is along with becoming big.The patch seal laber such as cohesive force that repeatedly tears of the present invention declines, and the sealing function of label will funeral
Lose；As cohesive force becomes big, or become big through long period after pasting because of label, by the unlatching of label, airtight, be then turned on, the closeest
Closing and cause difficulty, particularly with the packaging bag of layer structure, label cohesive force becomes will tear packaging bag greatly, make sealing failure.This
The seal laber that can repeatedly tear patch described in invention, its described cohesive force is more than 2N/ inch, or 2.5-10N/ inch, is
Realized by the regulation of Acrylic Pressure Sensitive Adhesive disclosed in this invention and component amount thereof, and be more than with described glutinous base power
44mN/m and formula middle-molecular-weihydroxyethyl is little realizes described cohesive force more than 2N/ inch, and the 2.5-10N/ inch according to design
The cohesive force of relative constancy, and do not reduce because repeatedly tearing patch or prolonged period and become big.
As further scheme, antimicrobial pressure sensitive adhesive compositions of the present invention is by Acrylate pressure sensitive
Adhesive and the compositions of hibitane composition, wherein the concentration of hibitane is 1wt%-5wt%.
Hibitane of the present invention has another name called chlorhexidine, and chemical name is 1, double (n-to the chlorobenzene biguanide) hexane of 6-, has another name called
Chlorhexidine.So-called guanidine can regard that the oxygen atom in urea molecular structure (-NH-C0-NH-) is taken by imino group (=NH) as
Generation and the compound that generates, remove the group after a hydrogen atom guanidine radicals in guanidine molecule, guanidine radicals is feature official's energy of hibitane
Group.Due to the existence of imido group, hibitane, originally as alkaline matter, owing to it is difficult to ionize, thus is insoluble in water.But can
With mineral acid, such as acetic acid, hydrochloric acid, or organic acid, such as gluconic acid, form chlorhexidine salt, stable existence soluble in water.Wash
Acid reaction that must be safe from different, draws different salt, as with acetic acid reaction, obtain chlorhexidine acetate (Chlorhexidine
Acetate, CHA)；With hydrochloric acid reaction, obtain chlorhexidine hydrochloride (Chlorhexidine hydrochloride, CHH)；With Portugal
Grape saccharic acid reacts, and obtains chlorhexidine gluconate (Chlorhexidine Gluconate, CHG).Becoming the acetic acid after salt to wash must
Thailand, chlorhexidine hydrochloride, chlorhexidine gluconate are neutral substance.Wherein the water solubility with chlorhexidine gluconate is maximum
(20%), it is secondly chlorhexidine acetate (1.8%), chlorhexidine hydrochloride (0.06%), it is preferred that hibitane of the present invention
For chlorhexidine gluconate.
As further scheme, Acrylic Pressure Sensitive Adhesive of the present invention is polymerized by following component by weight
Form:
Acrylic acid 30-40 part, butyl acrylate 20-30 part, acrylic acid methyl ester. 50-70 part, Isooctyl acrylate monomer 10-20
Part, Colophonium 2-10 part, glycerol 5-10 part, ethyl acetate 180-270 part, initiator 3-5 part, isocyanate curing agent 0.7-1.5
Part.
The present invention finds in research process, and the cohesive force of adhesive and viscous-elastic behaviour are close with the molecular size range of monomer
Relevant, the molecular weight of monomer is little, and cohesive force is low, and viscous-elastic behaviour is high, such as: acrylic acid (molecular weight 72.06), acrylic acid methyl ester.
(molecular weight 86.09), glycerol (molecular weight 92.09), butyl acrylate (molecular weight 128.17), Isooctyl acrylate monomer (molecular weight
184.28), Colophonium (molecular weight 302.46)；The seal laber that can repeatedly tear patch of the present invention, its described cohesive force is big
In 2N/ inch, 2.5-10N/ inch, it is that the regulation of the component amount of rosin resin by the tackifying resin of high molecular realizes
, the seal laber that can repeatedly tear patch described in the addition of the rosin resin of the tackifying resin of high molecular, effectively realization binds
Power, especially, by the seal laber that can repeatedly tear patch described in the regulation effectively realization of the component amount to thickening rosin resin
Cohesive force from the range of accommodation of 2.0-10N/ inch；Cohesive force is not reduced significantly because repeatedly tearing patch (50-150 time).But
It is that, it should be noted that the addition of tackifying resin needs to control within the specific limits, otherwise seal laber pastes prolonged period
After, the unlatching for seal laber will cause difficulty；Chlorhexidine gluconate (CHG, molecular weight due to antimicrobial property
111.549) molecular weight is little, and in component, content is high, and antimicrobial, antibacterial, mildew-resistant characteristic significantly improve, its described seal laber
Significantly extend with affixed object surface antimicrobial, effective period antibacterial, mildew-resistant；But the feature that its CHG molecular weight is little, works as mixing
In the component of acrylate adhesive, make the visco-elastic body deliquescing of viscous-elastic behaviour, make the creep resistance of pressure sensitive adhesive decline.Therefore,
The each acrylate monomer molecule in component and CHG can be made in the present invention by adjusting the consumption of the component of isocyanates
Molecule is full cross-linked, it is achieved the hardness of visco-elastic body improves, so that the creep resistance of pressure sensitive adhesive significantly improves, meets anti-micro-life
Thing can repeatedly tear the functional characteristic of the seal laber of patch, and realize having antimicrobial and can repeatedly tear seal laber gluing of patch
The viscous-elastic behaviour of agent, meets and repeatedly tears little dB (Decibel) decibels that patch process is soft.
By the intermediate performance that the organic synthesis thing of isocyanates is important, strengthen Acrylic Pressure Sensitive Adhesive to thin film
The throwing anchor-hold of base material, makes Acrylic Pressure Sensitive Adhesive stick base power and is more than 44mN/m, thus realize containing acrylate pressure-sensitive adhesive
Stick and hibitane form the described glutinous base power of the antimicrobial pressure-sensitive adhesive that compositions is formed and are more than 44mN/m, make this
The bright described antimicrobial seal laber that can repeatedly tear patch is attached on affixed object not remain gluing through 1-150 time repeatedly tear
Agent.
As further scheme, the thickness of PVDC coating material of the present invention is 0.8-3.0 μm.
Another object of the present invention is to provide the preparation side of a kind of antimicrobial seal laber material that can repeatedly tear patch
Method, by the method obtain a kind of tearable patch often with the antimicrobial seal laber material that can repeatedly tear patch of good sealing effect
Material；Scheme is as follows:
The preparation method of a kind of antimicrobial seal laber material that can repeatedly tear patch, this preparation method includes following step
Rapid:
1) preparation film substrate containing PVDC coating material: film substrate is positioned over unreeling of double coating head web coatable machine
On station, the first web coatable device is coated with silane coupling agent and forms priming coat, by the second reticulate pattern on priming coat after drying
Apparatus for coating line coating PVDC coating material baking and curing；Then on double coating head web coatable machines line cooling, rolling from
Line, is positioned over ripening 40-50h in the environment of 40-60 DEG C, obtains the film substrate containing PVDC coating material；
2) antimicrobial pressure sensitive adhesive compositions is prepared: be mixed anti-by Acrylic Pressure Sensitive Adhesive and hibitane
Microorganism pressure sensitive adhesive compositions；
3) the antimicrobial seal laber material of patch can be repeatedly torn in preparation: by coating machine by antimicrobial pressure-sensitive adhesive
Coat on release substrate, baking and curing formed antimicrobial formation of pressure-sensitive adhesive layer, then by step 1) obtain containing PVDC
The film substrate of coating material is combined to antimicrobial formation of pressure-sensitive adhesive layer, by the composite pressure of coating machine and release substrate
Antimicrobial formation of pressure-sensitive adhesive layer is transferred to the film substrate layer containing PVDC coating material by off-type force, cold by coating machine line
Radiator cooler cools down, and rolling, off-line are positioned over 45-55 DEG C of environment ripening 120-150h, and the antimicrobial obtaining repeatedly tearing patch is close
Envelope label material.
In the preparation method of the antimicrobial seal laber material that can repeatedly tear patch of the present invention, described thin film
Base material before the coating, must carry out surface process, to reach the best apparent condition, it is ensured that obtain continuous, free of pinholes
PVDC coating and PVDC coating are with having good binding strength between film substrate.Film substrate surface processes conventional method
Having sided corona treatment and primer coating two big classes, sided corona treatment can make the surface of film substrate that chemical reaction, polarization base occur
Group, increases the surface tension of film substrate, contributes to the PVDC latex infiltration on film substrate surface, improve Painting effect；?
During sided corona treatment, also can make to produce on the surface of film substrate certain roughening effect, thus improve between coating and film substrate
Bond strength.But, for low-surface-energy and nonpolar film substrate, sided corona treatment effect can passage in time and go out
Lose, especially, PVDC latex is polar molecule, its surface tension between 40-44mN/m, in conjunction with biphase surface tension should phase
To balance.So, polyurethane silane coupling agent of the present invention be then by specific coating formed silane coupling agent, make film substrate and
PVDC is coated with the combination of interlayer, changes the combination into the combination of silane coupling agent and film substrate and silane coupling agent with PVDC coating, thus protects
Demonstrate,prove the permanent firmness of PVDC coating, and not because of hot and humid environment, the dipping of the highest alcohol environment and coating shedding.
The silane coupling agent of the present invention can be selected from vinyl group resin, polyurethanes copolymer, polyolefin copolymers, propylene
Any one of acid copolymer or its mixture.The selection of silane coupling agent and use proper, can make PVDC Painting effect bright
Aobvious lifting.Preferably, silane coupling agent of the present invention is selected from polyurethanes silane coupling agent.Further in scheme, of the present invention
The thickness of priming coat be 0.2-0.5 μm.
Owing to PVDC coating layer thickness and drying condition have its substantial connection, the coating of disposable coating is the thickest, easily causes
Surface drying and form coating be full of cracks, destroy barrier property, and PVDC coating thickness and barrier property become direct ratio, coating layer thickness is more
Thickness, barrier property is the highest.So, extraordinary barrier property to be obtained, the work that double spread, two-sided secondary are coated with can be used
Skill.The coating thickness of PVDC coating material of the present invention is 0.8-3.0 micron, can pass through an one side or the most two-sided painting
Cloth technique.
As further scheme, the thickness of described antimicrobial formation of pressure-sensitive adhesive layer is 12-30 μm.
As further scheme, the step 2 described in above-mentioned preparation method) in Acrylic Pressure Sensitive Adhesive pressed by following
Weight meter component is polymerized:
Acrylic acid 30-40 part, butyl acrylate 20-30 part, acrylic acid methyl ester. 50-70 part, Isooctyl acrylate monomer 10-20
Part, Colophonium 2-10 part, glycerol 5-10 part, ethyl acetate 180-270 part, initiator 3-5 part, isocyanate curing agent 0.7-1.5
Part；
The concrete preparation method of antimicrobial pressure sensitive adhesive compositions is as follows；
A: 1-3 part initiator is dissolved in 30-50 part ethyl acetate solution, is then sequentially added into the propylene of formula ratio
Acid, butyl acrylate, acrylic acid methyl ester., Isooctyl acrylate monomer, glycerol, obtain mixed liquor after being thoroughly mixed uniformly；
B: 30-50 part ethyl acetate is added in reactor and is warming up to 76-80 DEG C, slowly drip 1/2 after backflow is stable
The above-mentioned mixed liquor of volume, 80-82 DEG C of stirring reaction 1.5-2 hour；
C: remaining initiator is dissolved in the ethyl acetate solution forming initiator in remaining ethyl acetate, and this is drawn
The mixed liquor sending out the ethyl acetate solution of agent and above-mentioned remaining 1/2 volume synchronizes to be added drop-wise to step 2 slowly) reaction system
In, continue to drip the rosin milk of 5-10 part after dripping in reaction system, keep 80-82 DEG C of continuation reaction 0.5-1.5 little
Time, obtain Acrylic Pressure Sensitive Adhesive；
D: after Acrylic Pressure Sensitive Adhesive is cooled to room temperature, drips 3-5 part chlorhexidine gluconate, i.e. obtains anti-micro-
Biological pressure sensitive adhesive compositions.
E: before coating antimicrobial pressure sensitive adhesive compositions, isocyanate curing agent 0.7-1.5 part is added to combination
In thing, homogenizer stirs 15-25 minute, stands 10-20 minute.
Third object of the present invention be to provide a kind of tearable patch often with good sealing effect can repeatedly tear the anti-of patch
Microorganism-tight label, can avoid being attached to adhesive residue on affixed object because repeatedly tearing simultaneously.
A kind of antimicrobial seal laber that can repeatedly tear patch, it is by the anti-micro-life that can repeatedly tear patch of the present invention
Thing seal laber material is formed after printing, cross cutting.
Fourth object of the present invention is that the described antimicrobial seal laber that can repeatedly tear patch is at layer structure bag
Application in pack or packing container.Can repeatedly tear the antimicrobial seal laber of patch for packaging bag or packing container opening
Seal.
5th purpose of the present invention is to provide the packaging of a kind of antimicrobial seal laber comprising and can repeatedly tearing patch
Container, scheme is as follows:
A kind of packaging bag or packing container, it includes packaging bag body or packing container body, described packaging bag body or
Packing container body is provided with the opening picking and placeing content, and described opening part is with the anti-micro-life that can repeatedly tear patch of the present invention
Thing seal laber seals.
The following is specific embodiment of the present invention, equipment, raw material and the reagent used in the following embodiments
To be obtained by commercial channel.
Embodiment 1
A kind of antimicrobial seal laber material that can repeatedly tear patch is prepared by the following method and forms:
1) preparation film substrate containing PVDC coating material: film substrate is positioned over unreeling of double coating head web coatable machine
On station, the first web coatable device is coated with polyurethane silane coupling agent and forms priming coat, by the on priming coat after drying
Two web coatable device line coating PVDC coating material baking and curing；Then line cooling on double coating head web coatable machines,
Rolling off-line, is positioned over ripening 50h in the environment of 40 DEG C, obtains the film substrate containing PVDC coating material；
2) antimicrobial pressure sensitive adhesive compositions is prepared: be mixed anti-by Acrylic Pressure Sensitive Adhesive and hibitane
Microorganism pressure sensitive adhesive compositions；
Acrylic Pressure Sensitive Adhesive is polymerized by following component by weight:
30 parts of acrylic acid, butyl acrylate 20 parts, acrylic acid methyl ester. 50 parts, Isooctyl acrylate monomer 10 parts, Colophonium 3 parts, sweet
Oil 5 parts, ethyl acetate 180 parts, initiator 3 parts, isocyanate curing agent 0.7 part；
The concrete preparation method of antimicrobial pressure sensitive adhesive compositions is as follows；
A: 1 part of initiator is dissolved in 30 parts of ethyl acetate solutions, is then sequentially added into the acrylic acid of formula ratio, propylene
Acid butyl ester, acrylic acid methyl ester., Isooctyl acrylate monomer, glycerol, obtain mixed liquor after being thoroughly mixed uniformly；
B: 30 parts of ethyl acetate are added in reactor and is warming up to 76 DEG C, slowly drip 1/2 volume after backflow is stable
Above-mentioned mixed liquor, 80 DEG C of stirring reactions 1.5 hours；
C: remaining initiator is dissolved in the ethyl acetate solution forming initiator in remaining ethyl acetate, and this is drawn
The mixed liquor sending out the ethyl acetate solution of agent and above-mentioned remaining 1/2 volume synchronizes to be added drop-wise to step 2 slowly) reaction system
In, continue to drip rosin milk after dripping in reaction system, keep 80 DEG C to continue reaction 0.5 hour, obtain acrylate
Pressure-sensitive adhesive；
D: after Acrylic Pressure Sensitive Adhesive is cooled to room temperature, drips 3 parts of chlorhexidine gluconates, i.e. obtains anti-micro-life
Thing pressure sensitive adhesive compositions.
E: before coating antimicrobial pressure sensitive adhesive compositions, isocyanate curing agent is added to compositions, at a high speed
Blender stirs 15 minutes, stands 10 minutes.
3) the antimicrobial seal laber material of patch can be repeatedly torn in preparation: by coating machine by antimicrobial pressure-sensitive adhesive
Coat on release substrate, baking and curing formed antimicrobial formation of pressure-sensitive adhesive layer, then by step 1) obtain containing PVDC
The film substrate of coating material is combined to antimicrobial formation of pressure-sensitive adhesive layer, release by the composite pressure of coating machine and substrate
Antimicrobial formation of pressure-sensitive adhesive layer is transferred to the film substrate layer containing PVDC coating material by power, by coating machine line cooling dress
Put cooling, rolling, off-line, be positioned over 45 DEG C of environment ripening 150h, obtain repeatedly tearing the antimicrobial seal laber material of patch.
Through test, by, in the antimicrobial seal laber material that can repeatedly tear patch that said method obtains, containing
The oxygen permeability of the film substrate of PVDC coating material is 4.5mL/ (m224h 0.1MPa), poisture-penetrability is less than 4.8g/ (m2·
24h)；
The glutinous base power of antimicrobial pressure sensitive adhesive compositions is 46mN/m, cohesive force is 4.8N/ inch；
The off-type force of the release substrate of silicate-containing oil coating is 12g/ inch；
The thickness of described priming coat is 0.4 μm；The thickness of described PVDC coating material is 1.5 μm, antimicrobial pressure sensitive adhesive
The thickness of adhesive layer is 18 μm.
Application Example 1
By obtained by embodiment 1 can repeatedly tear the antimicrobial seal laber material of patch through printing trade mark or pattern,
Obtain repeatedly tearing the antimicrobial seal laber of patch after cross cutting, and this label is affixed on the opening of baby paper diaper packaging bag
Place.
Embodiment 2
A kind of antimicrobial seal laber material that can repeatedly tear patch is prepared by the following method and forms:
1) preparation film substrate containing PVDC coating material: film substrate is positioned over unreeling of double coating head web coatable machine
On station, the first web coatable device is coated with polyurethane silane coupling agent and forms priming coat, by the on priming coat after drying
Two web coatable device line coating PVDC coating material baking and curing；Then line cooling on double coating head web coatable machines,
Rolling off-line, is positioned over ripening 45h in the environment of 45 DEG C, obtains the film substrate containing PVDC coating material；
2) antimicrobial pressure sensitive adhesive compositions is prepared: be mixed anti-by Acrylic Pressure Sensitive Adhesive and hibitane
Microorganism pressure sensitive adhesive compositions；
Acrylic Pressure Sensitive Adhesive is polymerized by following component by weight:
35 parts of acrylic acid, butyl acrylate 25 parts, acrylic acid methyl ester. 55 parts, Isooctyl acrylate monomer 15 parts, Colophonium 5 parts, sweet
Oil 6 parts, ethyl acetate 200 parts, initiator 4 parts, isocyanate curing agent 1 part；
The concrete preparation method of antimicrobial pressure sensitive adhesive compositions is as follows；
A: 2 parts of initiators are dissolved in 40 parts of ethyl acetate solutions, are then sequentially added into the acrylic acid of formula ratio, propylene
Acid butyl ester, acrylic acid methyl ester., Isooctyl acrylate monomer, glycerol, obtain mixed liquor after being thoroughly mixed uniformly；
B: 40 parts of ethyl acetate are added in reactor and is warming up to 76 DEG C, slowly drip 1/2 volume after backflow is stable
Above-mentioned mixed liquor, 82 DEG C of stirring reactions 1.5 hours；
C: remaining initiator is dissolved in the ethyl acetate solution forming initiator in remaining ethyl acetate, and this is drawn
The mixed liquor sending out the ethyl acetate solution of agent and above-mentioned remaining 1/2 volume synchronizes to be added drop-wise to step 2 slowly) reaction system
In, continue to drip rosin milk after dripping in reaction system, keep 82 DEG C to continue reaction 1 hour, obtain acrylate pressure
Sensitive adhesive；
D: after Acrylic Pressure Sensitive Adhesive is cooled to room temperature, drips 4 parts of chlorhexidine gluconates, i.e. obtains anti-micro-life
Thing pressure sensitive adhesive compositions.
E: before coating antimicrobial pressure sensitive adhesive compositions, isocyanate curing agent is added to compositions, at a high speed
Blender stirs 20 minutes, stands 15 minutes.
3) the antimicrobial seal laber material of patch can be repeatedly torn in preparation: by coating machine by antimicrobial pressure-sensitive adhesive
Coat on release substrate, baking and curing formed antimicrobial formation of pressure-sensitive adhesive layer, then by step 1) obtain containing PVDC
The film substrate of coating material is combined to antimicrobial formation of pressure-sensitive adhesive layer, release by the composite pressure of coating machine and substrate
Antimicrobial formation of pressure-sensitive adhesive layer is transferred to the film substrate layer containing PVDC coating material by power, by coating machine line cooling dress
Put cooling, rolling, off-line, be positioned over 50 DEG C of environment ripening 130h, obtain repeatedly tearing the antimicrobial seal laber material of patch.
Through test, by, in the antimicrobial seal laber material that can repeatedly tear patch that said method obtains, containing
The oxygen permeability of the film substrate of PVDC coating material is 4.3mL/ (m224h 0.1MPa), poisture-penetrability is less than 4.9g/ (m2·
24h)；
The glutinous base power of antimicrobial pressure sensitive adhesive compositions is 46mN/m, cohesive force is 5.5N/ inch；
The off-type force of the release substrate of silicate-containing oil coating is 16g/ inch；
The thickness of described priming coat is 0.3 μm；The thickness of described PVDC coating material is 1.5 μm, antimicrobial pressure sensitive adhesive
The thickness of adhesive layer is 20 μm.
Application Example 2
By obtained by embodiment 2 can repeatedly tear the antimicrobial seal laber material of patch through printing trade mark or pattern,
Obtain repeatedly tearing the antimicrobial seal laber of patch after cross cutting, and this label is affixed on the opening part of moisture saver mask packaging bag.
Embodiment 3
A kind of antimicrobial seal laber material that can repeatedly tear patch, is prepared by the following method and forms:
1) preparation film substrate containing PVDC coating material: film substrate is positioned over unreeling of double coating head web coatable machine
On station, the first web coatable device is coated with polyurethane silane coupling agent and forms priming coat, by the on priming coat after drying
Two web coatable device line coating PVDC coating material baking and curing；Then line cooling on double coating head web coatable machines,
Rolling off-line, is positioned over ripening 48h in the environment of 55 DEG C, obtains the film substrate containing PVDC coating material；
2) antimicrobial pressure sensitive adhesive compositions is prepared: be mixed anti-by Acrylic Pressure Sensitive Adhesive and hibitane
Microorganism pressure sensitive adhesive compositions；
Acrylic Pressure Sensitive Adhesive is polymerized by following component by weight:
28 parts of acrylic acid, butyl acrylate 28 parts, acrylic acid methyl ester. 65 parts, Isooctyl acrylate monomer 18 parts, Colophonium 6 parts, sweet
Oil 8 parts, ethyl acetate 250 parts, initiator 4 parts, isocyanate curing agent 1.2 parts；
The concrete preparation method of antimicrobial pressure sensitive adhesive compositions is as follows；
A: 2 parts of initiators are dissolved in 45 parts of ethyl acetate solutions, are then sequentially added into the acrylic acid of formula ratio, propylene
Acid butyl ester, acrylic acid methyl ester., Isooctyl acrylate monomer, glycerol, obtain mixed liquor after being thoroughly mixed uniformly；
B: 50 parts of ethyl acetate are added in reactor and is warming up to 78 DEG C, slowly drip 1/2 volume after backflow is stable
Above-mentioned mixed liquor, 80 DEG C of stirring reactions 2 hours；
C: remaining initiator is dissolved in the ethyl acetate solution forming initiator in remaining ethyl acetate, and this is drawn
The mixed liquor sending out the ethyl acetate solution of agent and above-mentioned remaining 1/2 volume synchronizes to be added drop-wise to step 2 slowly) reaction system
In, continue to drip rosin milk after dripping in reaction system, keep 80 DEG C to continue reaction 1.2 hours, obtain acrylate
Pressure-sensitive adhesive；
D: after Acrylic Pressure Sensitive Adhesive is cooled to room temperature, drips 2 parts of chlorhexidine gluconates, i.e. obtains anti-micro-life
Thing pressure sensitive adhesive compositions.
E: before coating antimicrobial pressure sensitive adhesive compositions, isocyanate curing agent is added to compositions, at a high speed
Blender stirs 25 minutes, stands 20 minutes.
3) the antimicrobial seal laber material of patch can be repeatedly torn in preparation: by coating machine by antimicrobial pressure-sensitive adhesive
Coat on release substrate, baking and curing formed antimicrobial formation of pressure-sensitive adhesive layer, then by step 1) obtain containing PVDC
The film substrate of coating material is combined to antimicrobial formation of pressure-sensitive adhesive layer, by the composite pressure of coating machine and release paper from
Antimicrobial formation of pressure-sensitive adhesive layer is transferred to the film substrate layer containing PVDC coating material by type power, is cooled down by coating machine line
Device cools down, and rolling, off-line are positioned over 52 DEG C of environment ripening 144h, obtain repeatedly tearing the antimicrobial seal laber material of patch
Material.
Through test, by, in the antimicrobial seal laber material that can repeatedly tear patch that said method obtains, containing
The oxygen permeability of the film substrate of PVDC coating material is 3.9mL/ (m224h 0.1MPa), poisture-penetrability be 4.1g/ (m2·24h)；
The glutinous base power of antimicrobial pressure sensitive adhesive compositions is 48mN/m, cohesive force is 5.8N/ inch；
The off-type force of the release substrate of silicate-containing oil coating is 15g/ inch；
The thickness of described priming coat is 0.4 μm；The thickness of described PVDC coating material is 2.0 μm, antimicrobial pressure sensitive adhesive
The thickness of adhesive layer is 25 μm.
Application Example 3
By obtained by embodiment 3 can repeatedly tear the antimicrobial seal laber material of patch through printing trade mark or pattern,
Obtain repeatedly tearing the antimicrobial seal laber of patch after cross cutting, and this label is affixed on sanltary towel packaging bag and dry towel
Opening part on packing container.
Embodiment 4
A kind of antimicrobial seal laber material that can repeatedly tear patch is prepared by the following method and forms:
1) preparation film substrate containing PVDC coating material: film substrate is positioned over unreeling of double coating head web coatable machine
On station, the first web coatable device is coated with polyurethane silane coupling agent and forms priming coat, by the on priming coat after drying
Two web coatable device line coating PVDC coating material baking and curing；Then line cooling on double coating head web coatable machines,
Rolling off-line, is positioned over ripening 40h in the environment of 60 DEG C, obtains the film substrate containing PVDC coating material；
2) antimicrobial pressure sensitive adhesive compositions is prepared: be mixed anti-by Acrylic Pressure Sensitive Adhesive and hibitane
Microorganism pressure sensitive adhesive compositions；
Acrylic Pressure Sensitive Adhesive is polymerized by following component by weight:
40 parts of acrylic acid, butyl acrylate 30 parts, acrylic acid methyl ester. 70 parts, Isooctyl acrylate monomer 20 parts, Colophonium 4 parts, sweet
Oil 10 parts, ethyl acetate 270 parts, initiator 5 parts, isocyanate curing agent 1.2 parts；
The concrete preparation method of antimicrobial pressure sensitive adhesive compositions is as follows:
A: 1 part of initiator is dissolved in 50 parts of ethyl acetate solutions, is then sequentially added into the acrylic acid of formula ratio, propylene
Acid butyl ester, acrylic acid methyl ester., Isooctyl acrylate monomer, glycerol, obtain mixed liquor after being thoroughly mixed uniformly；
B: 50 parts of ethyl acetate are added in reactor and is warming up to 80 DEG C, slowly drip 1/2 volume after backflow is stable
Above-mentioned mixed liquor, 82 DEG C of stirring reactions 1.5 hours；
C: remaining initiator is dissolved in the ethyl acetate solution forming initiator in remaining ethyl acetate, and this is drawn
The mixed liquor sending out the ethyl acetate solution of agent and above-mentioned remaining 1/2 volume synchronizes to be added drop-wise to step 2 slowly) reaction system
In, continue to drip rosin milk after dripping in reaction system, keep 82 DEG C to continue reaction 0.5 hour, obtain acrylate
Pressure-sensitive adhesive；
D: after Acrylic Pressure Sensitive Adhesive is cooled to room temperature, drips 3 parts of chlorhexidine gluconates, i.e. obtains anti-micro-life
Thing pressure sensitive adhesive compositions.
E: before coating antimicrobial pressure sensitive adhesive compositions, isocyanate curing agent is added to compositions, at a high speed
Blender stirs 18 minutes, stands 18 minutes.
3) the antimicrobial seal laber material of patch can be repeatedly torn in preparation: by coating machine by antimicrobial pressure-sensitive adhesive
Coat on release substrate, baking and curing formed antimicrobial formation of pressure-sensitive adhesive layer, then by step 1) obtain containing PVDC
The film substrate of coating material is combined to antimicrobial formation of pressure-sensitive adhesive layer, by pressure and the off-type force of release paper of coating machine
Antimicrobial formation of pressure-sensitive adhesive layer is transferred to the film substrate layer containing PVDC coating material, by coating machine connection cooling device
Cooling, rolling, off-line, it is positioned over 55 DEG C of environment ripening 120h, obtains repeatedly tearing the antimicrobial seal laber material of patch.
Through test, by, in the antimicrobial seal laber material that can repeatedly tear patch that said method obtains, containing
The oxygen permeability of the film substrate of PVDC coating material is 3.0mL/ (m224h 0.1MPa), poisture-penetrability be 4.1g/ (m2·24h)；
The glutinous base power of antimicrobial pressure sensitive adhesive compositions is 48mN/m, cohesive force is 6.1N/ inch；
The off-type force of the release substrate of silicate-containing oil coating is 13g/ inch；
The thickness of described priming coat is 0.5 μm；The thickness of described PVDC coating material is 3.0 μm, antimicrobial pressure sensitive adhesive
The thickness of adhesive layer is 26 μm.
Application Example 4
By obtained by embodiment 4 can repeatedly tear the antimicrobial seal laber material of patch through printing trade mark or pattern,
Obtain repeatedly tearing the antimicrobial seal laber of patch after cross cutting, and this label is affixed on the opening of high alcohol Wet paper towel packing bag
Place.
Effect and performance detection
1. the antimicrobial seal laber that can repeatedly tear patch in pair Application Example 1-4 carries out effect and performance test,
Project and the result of test see table 1.
Table 1
2. the test of antimicrobial pressure sensitive adhesive seal laber antimicrobial and effect thereof
Test philosophy: experiment bacterium solution is directly dripped on the gluing surface of label, makes antibacterial fully on the gluing surface of label
Contact exposes certain time, is then covered by culture medium, makes remaining thalli growth.Relatively antimicrobial sample bacterium amount declines percentage rate,
Its antibacterial ability is judged.Use magnifier counting colony-forming units.
Operate as follows: 1) prepared by bacterium solution: take the fresh broth culture of escherichia coli 24h, after shaking up, stand 20min, dilute
Being interpreted into bacterium number is 105～106The bacterium solution of cfu/mL；2) microbiological contamination: be the label of 5.0 × 5.0cm size, its gluing surface is upwards put
Enter in the sterilized petri dishes of diameter 9cm, uniformly dropping 1.5mL bacterium solution so that it is be uniformly distributed on the gluing surface of label and absorb, often
Individual sample repeats 6 pieces, is dried 1h in putting 37 DEG C of incubators；3) put down smooth for the gluing surface of dried microbiological contamination label in Nutrient agar
Plate surface, then the surface of the gluing surface with semisolid nutrient agar fat uniform fold microbiological contamination label, thickness is moderate, puts 37 DEG C of incubators
Interior cultivation 48h；4) observed result: be added on above-mentioned semisolid nutrient agar fat dyeing 1h with husky xanthochromia color drop, use magnifier
Count the clump count on the gluing surface of every label, calculate clump count meansigma methods the record of 6 pieces of samples；5) comparison: in experiment
If the pressure sensitive adhesive goods control sample of homogeneity non-antimicrobial agent performance；6) antibacterial bacteriostatic rate is calculated: above-mentioned experiment in triplicate, takes
Meansigma methods employing following manner calculating antimicrobial and bacteriostasis rate:
Antimicrobial and bacteriostasis rate=[(A-B)/A] × 100%
In formula: A is for compareing common pressure sensitive adhesive goods average colony number；B is average bacterium on the gluing surface of antimicrobial label
Fall number.
Antimicrobial experimental result and analysis thereof
The 10 groups of antimicrobial seal labers of the present invention (1-10 example) tested respectively with above-mentioned Quine's method, it resists micro-
Biological and bacteriostasis result is shown in Fig. 1；Meanwhile, the 10 groups of antimicrobial seal laber (1-10 of the present invention tested respectively
Example), its antimicrobial and bacteriostasis repeat test in three times, and its result together embodies at Fig. 1.
Quine's method is bacterium solution directly to be dripped on the label of antimicrobial compositions of the present invention, covers to cultivate
Base, the contact of reinforcement microorganism and antimicrobial label is to show its anti-bacteriostasis, and experimental result is according to anti-bacteriostasis rate size
Judge；The present invention resists the test of bacteriostasis and additionally uses dyeing liquor and dye bacterium colony, makes test effect be easier to see
Examining, method is feasible, and result is accurately and reliably.It is real that bacterium colony under husky yellow double solid agar medium of dyeing liquor covers carries out dyeing
Testing, the bacterium colony after its dyeing takes on a red color, and bacterium colony is clear, it is easy to observes, improves test accuracy and reliability.The present invention is respectively
Testing the antimicrobial seal laber sample that can repeatedly tear patch containing hibitane (1-5%) of 10 groups of different contents, it resists
Microorganism and fungistatic effect reach the Expected Results of the present invention the most in various degree.For verifying that it is repeatable, so adopting further
Repeating test with 3 times, 10 groups of antimicrobial compositions all have antibacterial bacteriostatic effect to escherichia coli etc..
Above-mentioned embodiment is only the preferred embodiment of the present invention, it is impossible to limit the scope of protection of the invention with this,
The change of any unsubstantiality that those skilled in the art is done on the basis of the present invention and replacement belong to institute of the present invention
Claimed scope.
Claims (12)
1. the antimicrobial seal laber material that can repeatedly tear patch, it is characterised in that comprising:
Oxygen permeability is less than 5.0mL/ (m224h 0.1MPa), poisture-penetrability is less than 5g/ (m224h) containing PVDC coating material
Film substrate；
Glutinous base power more than 44mN/m, cohesive force more than the antimicrobial pressure sensitive adhesive compositions of 2N/ inch；
Off-type force is less than the release substrate of the silicate-containing oil coating of 25g/ inch.
The antimicrobial seal laber material that can repeatedly tear patch the most according to claim 1, it is characterised in that described thin film
Base material is TPO, polyethylene terephthalate, polrvinyl chloride etc., comprise polypropylene, polyethylene, polyester, synthesis PP,
Thin film or the two or more material of a kind of material in synthesis BCA are blended coextruded film.
The antimicrobial seal laber material that can repeatedly tear patch the most according to claim 1, it is characterised in that described anti-micro-
The compositions that biological pressure sensitive adhesive compositions is made up of Acrylic Pressure Sensitive Adhesive and hibitane, wherein hibitane is dense
Degree is 1wt%-5wt%.
The antimicrobial seal laber material that can repeatedly tear patch the most according to claim 3, it is characterised in that described propylene
Acid esters pressure-sensitive adhesive is polymerized by following component by weight:
Acrylic acid 30-40 part, butyl acrylate 20-30 part, acrylic acid methyl ester. 50-70 part, Isooctyl acrylate monomer 10-20 part, pine
Fragrant 2-10 part, glycerol 5-10 part, ethyl acetate 180-270 part, initiator 3-5 part, isocyanate curing agent 0.7-1.5 part.
The antimicrobial seal laber material that can repeatedly tear patch the most according to claim 1, it is characterised in that this can be repeatedly
The antimicrobial seal laber tearing patch is attached on affixed object not adhesive residue through 1-150 time repeatedly tear.
The antimicrobial seal laber material that can repeatedly tear patch the most according to claim 1, it is characterised in that described PVDC
The thickness of coating material is 0.8-3.0 μm.
7. the preparation side of the antimicrobial seal laber material that can repeatedly tear patch as described in any one of claim 1-6
Method, it is characterised in that this preparation method comprises the following steps:
1) preparation film substrate containing PVDC coating material: what film substrate was positioned over double coating head web coatable machine unreels station
On, the first web coatable device is coated with silane coupling agent and forms priming coat, by the second web coatable on priming coat after drying
Device line coating PVDC coating material baking and curing；Then line cooling, rolling off-line on double coating head web coatable machines, put
It is placed in ripening 40-50h in the environment of 40-60 DEG C, obtains the film substrate containing PVDC coating material；
2) antimicrobial pressure sensitive adhesive compositions is prepared: Acrylic Pressure Sensitive Adhesive and hibitane are mixed and made into anti-micro-life
Thing pressure sensitive adhesive compositions；
3) the antimicrobial seal laber material of patch can be repeatedly torn in preparation: be coated with by antimicrobial pressure-sensitive adhesive by coating machine
On release substrate, baking and curing formed antimicrobial formation of pressure-sensitive adhesive layer, then by step 1) obtain containing PVDC be coated with
The film substrate of thing is combined to antimicrobial formation of pressure-sensitive adhesive layer, release by the composite pressure of coating machine and release substrate
Antimicrobial formation of pressure-sensitive adhesive layer is transferred to the film substrate layer containing PVDC coating material by power, by coating machine line cooling dress
Putting cooling, rolling, off-line, be positioned over 45-55 DEG C of environment ripening 120-150h, the antimicrobial obtaining repeatedly tearing patch seals mark
Sign material.
Preparation method the most according to claim 7, it is characterised in that step 2) in Acrylic Pressure Sensitive Adhesive by following
Component by weight is polymerized:
Acrylic acid 30-40 part, butyl acrylate 20-30 part, acrylic acid methyl ester. 50-70 part, Isooctyl acrylate monomer 10-20 part, pine
Fragrant 2-10 part, glycerol 5-10 part, ethyl acetate 180-270 part, initiator 3-5 part, isocyanate curing agent 0.7-1.5 part；
The concrete preparation method of antimicrobial pressure sensitive adhesive compositions is as follows:
A: 1-3 part initiator is dissolved in 30-50 part ethyl acetate solution, be then sequentially added into the acrylic acid of formula ratio, third
Olefin(e) acid butyl ester, acrylic acid methyl ester., Isooctyl acrylate monomer, glycerol, obtain mixed liquor after being thoroughly mixed uniformly；
B: 30-50 part ethyl acetate is added in reactor and is warming up to 76-80 DEG C, slowly drip 1/2 volume after backflow is stable
Above-mentioned mixed liquor, 80-82 DEG C stirring reaction 1.5-2 hour；
C: remaining initiator is dissolved in the ethyl acetate solution forming initiator in remaining ethyl acetate, and by this initiator
Ethyl acetate solution and above-mentioned remaining 1/2 volume mixed liquor synchronize be added drop-wise to step 2 slowly) reaction system in,
Continue to drip the rosin milk of 2-10 part after dripping in reaction system, keep 80-82 DEG C to continue reaction 0.5-1.5 hour,
Obtain Acrylic Pressure Sensitive Adhesive；
D: after Acrylic Pressure Sensitive Adhesive is cooled to room temperature, drips 3-5 part chlorhexidine gluconate, i.e. obtains antimicrobial
Pressure sensitive adhesive compositions.
E: before coating antimicrobial pressure sensitive adhesive compositions, isocyanate curing agent 0.7-1.5 part is added to compositions
In, homogenizer stirs 15-25 minute, stands 10-20 minute.
Preparation method the most according to claim 7, it is characterised in that the thickness of described priming coat is 0.2-0.5 μm；Described
The thickness of PVDC coating material be 0.8-3.0 μm, the thickness of antimicrobial formation of pressure-sensitive adhesive layer is 12-30 μm.
10. the antimicrobial seal laber that can repeatedly tear patch, it is characterised in that it is by any one of claim 1-6 institute
The antimicrobial seal laber material that can repeatedly tear patch stated is formed after printing, cross cutting.
The 11. antimicrobial seal labers that can repeatedly tear patch as claimed in claim 10 hold in layer structure packaging bag or packaging
Application in device.
12. 1 kinds of packaging bag/packing containers, it is characterised in that it includes packaging bag body or packing container body, described packaging
Bag or packing container body are provided with the opening picking and placeing content, can repeatedly tear patch described in described opening part claim 10
Antimicrobial seal laber seal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610692919.0A CN106327994B (en) | 2016-08-18 | 2016-08-18 | Antimicrobial seal laber of patch and its preparation method and application can repeatedly be torn |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610692919.0A CN106327994B (en) | 2016-08-18 | 2016-08-18 | Antimicrobial seal laber of patch and its preparation method and application can repeatedly be torn |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106327994A true CN106327994A (en) | 2017-01-11 |
| CN106327994B CN106327994B (en) | 2018-07-17 |
Family
ID=57744644
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610692919.0A Active CN106327994B (en) | 2016-08-18 | 2016-08-18 | Antimicrobial seal laber of patch and its preparation method and application can repeatedly be torn |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106327994B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107146891A (en) * | 2017-05-10 | 2017-09-08 | 上海亮仓能源科技有限公司 | A kind of MEA preparation methods of noble metal catalyst particles distribution gradient |
| CN107699154A (en) * | 2017-10-17 | 2018-02-16 | 广州市金万正印刷材料有限公司 | Seal laber material, food contact seal laber and preparation method and application again again for food contact |
| CN108004292A (en) * | 2017-12-12 | 2018-05-08 | 安徽医科大学 | The production method that a kind of proteus vulgaris migrates shape growth teaching plate |
| CN109355033A (en) * | 2017-10-17 | 2019-02-19 | 广州市金万正印刷材料有限公司 | Food contacts solvent-type acrylic pressure-sensitive label, adhesive tape and preparation method |
| CN111925740A (en) * | 2020-06-04 | 2020-11-13 | 深圳昌茂粘胶新材料有限公司 | Nano-silver antibacterial mildew-proof polyethylene label material and preparation method thereof |
| CN113122166A (en) * | 2021-04-19 | 2021-07-16 | 黑龙江大学 | Composite antibacterial pressure-sensitive adhesive composition and preparation method thereof |
| WO2022141462A1 (en) * | 2020-12-31 | 2022-07-07 | Upm Raflatac Oy | Sealing label with disinfecting properties |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1517422A (en) * | 2003-01-18 | 2004-08-04 | 广州宏昌胶粘带厂 | Stripping-type emulsion pressure sensitive adhesive and prossure sentitire adhesive tape |
| CN102226067A (en) * | 2011-05-16 | 2011-10-26 | 永一胶粘(中山)有限公司 | Acrylate solvent-based pressure sensitive adhersive and product thereof |
| CN102941707A (en) * | 2012-11-01 | 2013-02-27 | 广州市金万正印刷材料有限公司 | Soft laser self-adhesive label film and preparation method thereof |
| CN103709832A (en) * | 2013-12-26 | 2014-04-09 | 深圳市桑泰防伪材料有限公司 | Water-based ink, preparation method thereof and water-sense anti-counterfeiting material |
| CN105073934A (en) * | 2013-02-07 | 2015-11-18 | 艾利丹尼森公司 | Antimicrobial adhesives having improved properties |
| CN105400464A (en) * | 2015-12-24 | 2016-03-16 | 广州市金万正印刷材料有限公司 | Freeze-tolerant acrylate pressure-sensitive adhesive, preparation method thereof, and application thereof in production of freeze-tolerant acrylate pressure-sensitive labels |
-
2016
- 2016-08-18 CN CN201610692919.0A patent/CN106327994B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1517422A (en) * | 2003-01-18 | 2004-08-04 | 广州宏昌胶粘带厂 | Stripping-type emulsion pressure sensitive adhesive and prossure sentitire adhesive tape |
| CN102226067A (en) * | 2011-05-16 | 2011-10-26 | 永一胶粘(中山)有限公司 | Acrylate solvent-based pressure sensitive adhersive and product thereof |
| CN102941707A (en) * | 2012-11-01 | 2013-02-27 | 广州市金万正印刷材料有限公司 | Soft laser self-adhesive label film and preparation method thereof |
| CN105073934A (en) * | 2013-02-07 | 2015-11-18 | 艾利丹尼森公司 | Antimicrobial adhesives having improved properties |
| CN103709832A (en) * | 2013-12-26 | 2014-04-09 | 深圳市桑泰防伪材料有限公司 | Water-based ink, preparation method thereof and water-sense anti-counterfeiting material |
| CN105400464A (en) * | 2015-12-24 | 2016-03-16 | 广州市金万正印刷材料有限公司 | Freeze-tolerant acrylate pressure-sensitive adhesive, preparation method thereof, and application thereof in production of freeze-tolerant acrylate pressure-sensitive labels |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107146891A (en) * | 2017-05-10 | 2017-09-08 | 上海亮仓能源科技有限公司 | A kind of MEA preparation methods of noble metal catalyst particles distribution gradient |
| CN107146891B (en) * | 2017-05-10 | 2020-06-09 | 河南豫氢动力有限公司 | Preparation method of MEA (membrane electrode assembly) with noble metal catalyst particles distributed in gradient |
| CN107699154A (en) * | 2017-10-17 | 2018-02-16 | 广州市金万正印刷材料有限公司 | Seal laber material, food contact seal laber and preparation method and application again again for food contact |
| CN109355033A (en) * | 2017-10-17 | 2019-02-19 | 广州市金万正印刷材料有限公司 | Food contacts solvent-type acrylic pressure-sensitive label, adhesive tape and preparation method |
| WO2019076261A1 (en) * | 2017-10-17 | 2019-04-25 | Guangzhou Jinwanzheng Printing Material Co., Ltd | Food contact resealing label material, food contact resealing label, preparation method of materials and application materials |
| EP3673024A4 (en) * | 2017-10-17 | 2020-11-25 | Guangzhou Jinwanzheng Printing Material Co., Ltd | Food contact resealing label material, food contact resealing label, preparation method of materials and application materials |
| CN108004292A (en) * | 2017-12-12 | 2018-05-08 | 安徽医科大学 | The production method that a kind of proteus vulgaris migrates shape growth teaching plate |
| CN111925740A (en) * | 2020-06-04 | 2020-11-13 | 深圳昌茂粘胶新材料有限公司 | Nano-silver antibacterial mildew-proof polyethylene label material and preparation method thereof |
| WO2022141462A1 (en) * | 2020-12-31 | 2022-07-07 | Upm Raflatac Oy | Sealing label with disinfecting properties |
| CN113122166A (en) * | 2021-04-19 | 2021-07-16 | 黑龙江大学 | Composite antibacterial pressure-sensitive adhesive composition and preparation method thereof |
| CN113122166B (en) * | 2021-04-19 | 2023-10-20 | 黑龙江大学 | Composite antibacterial pressure-sensitive adhesive composition and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106327994B (en) | 2018-07-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106327994A (en) | Antimicrobial sealing label capable of being torn and stuck for plurality of times and preparation method and application of antimicrobial sealing label | |
| US11590255B2 (en) | Rubber-based soft gel skin adhesives | |
| US9416221B2 (en) | Biodegradable terpolymers and terpolymer blends as pressure-sensitive adhesives | |
| US9783699B2 (en) | Laminates and articles comprising a block copolymer coating comprising polyorganosiloxane and polyolefin | |
| US20090123569A1 (en) | Coverage indicating technology for skin sealants using tannates | |
| TW201031435A (en) | Indicators for detecting the presence of metabolic byproducts from microorganisms | |
| KR100228004B1 (en) | Bactericidal pressure=sensitive adhesive and production thereof, and pressure-sensitive adhesive product and application thereof | |
| TW200911868A (en) | Amine-based epoxy resin hardener, gas barrier epoxy resin composition containing the same, coating, and adhesive for laminating | |
| MX2009002155A (en) | Color changing skin sealant with co-acid trigger. | |
| EP1245617A1 (en) | Film selectively permeable to carbon dioxide and food packaging film comprising the same | |
| CN107890583A (en) | Adhesive containing chlorhexidine gluconate | |
| WO2019222092A1 (en) | High performance adhesives; methods of making; and use | |
| PT1890731E (en) | Method for producing an antimicrobial coating on a technical surface | |
| CN109701069A (en) | A kind of antibacterial tissue adhesive and preparation method thereof | |
| CN105765020A (en) | Self-adhesion-type adhesive tape | |
| CN101502697A (en) | Sanitary moisture paper tissue and preparation method thereof | |
| CN106459702A (en) | Adhesive sealing composition | |
| JP2001342435A (en) | Coating agent and antimicrobial sheet | |
| Songtipya et al. | A novel natural rubber pressure sensitive adhesive patch amended with cinnamon oil for preserving bakery product | |
| CN106361496B (en) | Breathable medical adhesive tape and its preparation process | |
| CN102343111A (en) | Adhesive patch and patch preparation | |
| WO2019088199A1 (en) | Antibacterial material and freshness keeping material | |
| WO2004016686A1 (en) | Composition containing aminated polysaccharide and film made thereof having selective carbon dioxide permeability | |
| CN110591602B (en) | Heat-sealing cover material glue for medical plastic uptake box | |
| JP2002220312A (en) | Antimicrobial coating material and antimicrobial sheet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |