CN109096947A - A kind of pressure sensitive adhesive - Google Patents
A kind of pressure sensitive adhesive Download PDFInfo
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- CN109096947A CN109096947A CN201810943339.3A CN201810943339A CN109096947A CN 109096947 A CN109096947 A CN 109096947A CN 201810943339 A CN201810943339 A CN 201810943339A CN 109096947 A CN109096947 A CN 109096947A
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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
- C09J103/00—Adhesives based on starch, amylose or amylopectin or on their derivatives or degradation products
- C09J103/02—Starch; Degradation products thereof, e.g. dextrin
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
-
- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a kind of pressure sensitive adhesives, belong to pressure sensitive adhesive technical field.The present invention makes stick by oneself with systems such as peach gum, humic acid, sticky rice juices, humic acid therein is the mixture containing the functional groups such as carboxyl and phenolic hydroxyl group, it can provide weak acid environment effect, active group such as carboxyl, aldehyde radical can play the role of bridge joint during the bonding process, promote adhesion strength further；The present invention is with monofunctional poly glycol monomethyl ether for long suspended chain, it is introduced into the made polyurethane compositions of compounded mix, so that its internal soft and hard segments microphase separation degree reduces, cocoanut shell is crushed, acidleach, steam blasting, it ferments with gelatin, casein, lactobacillus bulgaricus etc., improves the adhesion strength and toughness of this pressure sensitive adhesive system.The present invention solves the problems, such as the adhesion strength of common pressure sensitive adhesive, poor toughness at present.
Description
Technical field
The invention belongs to pressure sensitive adhesive technical fields, and in particular to a kind of pressure sensitive adhesive.
Background technique
Adhesive tape mainly by substrate and is coated on one or two surface of substrate and is coated with one layer of sticker and constitutes, and passes through
Bond is formed between adhesion agent molecule and article surface molecule on base material, so that adhesive tape only adheres to the surface of article
On.It is divided by function, adhesive tape can be divided into high temperature gummed tape, pressure sensitive adhesive tape, insulating tape, specialty tape, cross cutting adhesive tape etc..Its
In pressure sensitive adhesive tape refer to using pressure sensitive adhesive that as sticker, be commonly called as Pressure sensitive adhesive tape, having can be easily when using smaller pressure
Adhesion effect can be played in adhesion, short time, and is not easy to remain on the article adhered after removing, and patch is staggered the time and can also be repaired again
Just, the advantages that rear glue surface adhesive performance will not subside substantially is used for multiple times, therefore pressure sensitive adhesive tape is in packaging, printing, automobile, family
The industries such as electricity, electronics, medical treatment, aviation, building and telecommunication equipment are used widely.
However adherence of the rubber pressure-sensitive adhesive in PET base material show always it is poor, it is well known that it is permanent to realize
Fixed or protecting effect does not require nothing more than rubber pressure-sensitive adhesive with good initial adhesion power and cohesive force, while requiring rubber
Type pressure sensitive adhesive cannot remain in and be attached on article surface from having good fissility when being attached article sur-face peeling,
If therefore adherence of the rubber pressure-sensitive adhesive in PET base material is poor, the fissility that will lead to rubber pressure-sensitive adhesive is poor.It is existing
Technology is general using first passing through sided corona treatment in advance to PET base material in order to improve the fissility of the adhesive tape, then that rubber-type is pressure-sensitive
Glue is coated in PET base material, although in a short time, rubber pressure-sensitive adhesive has good adhesion strength to PET base material, is passed through
The storage of a period of time, the adhesion strength between PET base material and rubber pressure-sensitive adhesive still still can weaken significantly, and then cause
By adhesive tape from be attached removed on article surface when, more or less rubber pressure-sensitive adhesive, which remains in, to be attached on article surface,
Cause to pollute to be fixed or protection the article that is attached, therefore essential solution is obviously unable to using preparatory corona treatment process
The certainly poor problem of adherence of the glue-type pressure sensitive adhesive in PET base material.
A kind of new efficient pressure-sensitive adhesive composition being made of the graft copolymer mutually separated is disclosed at present, it is described
Graft copolymer is by having polymer pendant groups the part such as polystyrene or polyacrylate or poly- (methyl) propylene that are grafted with it
Acid esters main chain composition, is the viscose properties for improving itself using various types of pressure sensitive adhesives that graft polymerization method obtains,
However pressure sensitive adhesive is prepared using graft polymerization method, crosslink density is unable to reach the adhesion demand of pressure sensitive adhesive, poor toughness, production cost
It is extremely high.Therefore a kind of adhesion strength and the strong pressure sensitive adhesive of toughness need to be developed.
Summary of the invention
The technical problems to be solved by the invention: it aiming at the problem that adhesion strength, the poor toughness of current common pressure sensitive adhesive, improves
A kind of pressure sensitive adhesive.
In order to solve the above technical problems, the present invention is using technical solution as described below:
A kind of pressure sensitive adhesive, including following component: 7 ~ 15 parts of wetting agents, 0.1 ~ 0.4 part of paraffin, 3 ~ 7 parts of naphthenic oils, 2 ~ 5 parts of antioxygens
Agent, 15 ~ 30 portions of self-control sticks, further includes: 20 ~ 35 parts of compounded mixs, 12 ~ 20 parts of fermentation products.
The preparation method of the compounded mix, includes the following steps:
(1) taking polyethylene glycol monomethyl ether is passed through nitrogen protection, polyethyleneglycol is added in 100 ~ 110 DEG C, vacuum drying processing
The pyridine mixing of the acetic anhydride, poly glycol monomethyl ether quality 8 ~ 15% of methyl ether quality 12 ~ 20%, heating, heating stirring reaction obtain
Pre-composition, in mass ratio 10:1:1 ~ 3 take pre-composition, maleic anhydride, adjuvant mixing, in 200 ~ 210 DEG C, are stirred to react, out
Material, obtains base-material；
(2) according to the mass fraction, 30 ~ 50 parts of base-materials, 20 ~ 30 parts of styrene, 20 ~ 30 parts of water, 2 ~ 5 parts of initiators, 0.3 ~ 0.7 are taken
Part stannous octoate, 8 ~ 15 parts of dimethyl silicone polymers, 8 ~ 15 parts of mix monomers, 4 ~ 8 parts of isocyanates, first 40 ~ 55 DEG C take base-material,
Styrene, isocyanates, water, are stirred, and mix monomer, initiator, dimethyl silicone polymer, stannous octoate is added in heating
Mixing, shearing dispersion, heating, heat preservation stand to get compounded mix.
Adjuvant in the step (1): 3:1 ~ 2 take cottonseed oil, linoleic acid mixing to get adjuvant in mass ratio.
Initiator in the step (2): potassium peroxydisulfate, sodium peroxydisulfate, any one in ammonium persulfate.
Mix monomer in the step (2): 1 ~ 3:1:1 in mass ratio takes acrylic acid, acrylic acid hydroxy alkyl ester, methyl-prop
Olefin(e) acid Arrcostab mixes to get mix monomer.
The preparation of the fermentation product: in 55 ~ 70 DEG C, according to parts by weight, 8 ~ 15 parts of pretreatment coconut husks are successively taken
Grain, 4 ~ 8 parts of gelatin, 2 ~ 5 parts of caseins, 2 ~ 5 parts of lactobacillus bulgaricus liquid, 300 ~ 500 parts of water, first will pretreatment coconut husk particle,
Gelatin, water mixing, stirring, heat preservation are stood, heating, and casein and lactobacillus bulgaricus liquid is added in heating stirring, closed, in 28 ~
32 DEG C, shaking table oscillation, fermented and cultured obtains fermentation material, fermentation material is taken to sterilize, and must sterilize material, and sterilizing material is taken to adjust pH, and filtering takes
Filter vacuum is concentrated to get fermentation product.
The pretreatment coconut husk particle: taking coconut husk in pulverizing and sieving, and takes sieving particle 1:10 in mass ratio ~ 15 that HCl is added
Solution is mixed, and filtering takes filter residue to dry, and steam blasting obtains bursting charge, takes bursting charge microwave treatment to get pretreatment coconut palm
Shell particle.
The self-control stick: in 45 ~ 60 DEG C, take peach gum 1:1 ~ 3:10 in mass ratio that urea is added, water is mixed, mistake
Filter, takes filter residue 5:0.1 in mass ratio ~ 0.3 that dehydrated alcohol mixing is added, and zirconium oxide ball milling is added by ball 20 ~ 30:1 of material mass ratio
Pearl, ball milling obtain ball milling material, take ball milling material 1:3 ~ 6:2 in mass ratio that sticky rice juice, humic acid mixing is added, take out in 55 ~ 70 DEG C
It is evaporated in vacuo to get self-control stick.
The antioxidant: 5 ~ 8:1 in mass ratio takes tert-butylhydroquinone, pentaerythrite mixing to get antioxidant.
The wetting agent: 5:1 ~ 3 take cetyl trimethylammonium bromide, laureth sodium sulfovinate mixed in mass ratio
It closes to get wetting agent.
The present invention is compared with other methods, and advantageous effects are:
(1) present invention makes stick by oneself with systems such as peach gum, humic acid, sticky rice juices, and humic acid therein is containing carboxyl and phenolic hydroxyl group etc.
The mixture of functional group, it is possible to provide weak acid environment effect generates chelation with calcium ion, the zinc ion in sticky rice juice, increases
Strong internal connecting forces, in addition, humic acid reaches raising pressure sensitive colloid in combination with the abundant organic matter generated in fermentation product
The effect of system and the interface compatibility of gummed paper, wherein active group such as carboxyl, aldehyde radical can play the role of bridge joint during the bonding process,
The small-molecule substance for further increasing the generation after product degrades to the adhesive property of gummed paper, and humic acid, peach gum, can soak
Agent effect under further penetrate into inside gummed paper microvoid, in conjunction with other compositions in system after, in micro hole structure
" glue nail " structure is formed, promotes adhesion strength further；
(2) present invention introduces the made polyurethane compositions of compounded mix with monofunctional poly glycol monomethyl ether for long suspended chain
In, so that its internal soft and hard segments microphase separation degree reduces, intermolecular hydrogen bonding effect enhancing enhances its colloid inner Join power,
Viscosity component and other ingredients to this system provide the main body frame with high tenacity, to reach the adhesiveness of enhancing pressure sensitive adhesive
And the effect of toughness, cocoanut shell is crushed, acidleach, steam blasting so that partial lignin, hemicellulose be able to decompose,
Microwave treatment moisture sub-resonance mixes its internal pentosan, is then sent out with gelatin, casein, lactobacillus bulgaricus etc.
Ferment generates a large amount of organic matters, in conjunction with the naphthenic oil cooperation for making glutinous agent, good polyurethane compatibility by oneself, is greatly improved pressure-sensitive
The adhesion strength and toughness of colloid system.
Specific embodiment
It makes the preparation of stick by oneself: in 45 ~ 60 DEG C of water-bath, taking peach gum 1:1 ~ 3:10 in mass ratio that urea, deionized water is added
Mixing stirs 25 ~ 50min with 400 ~ 600r/min, and filtering takes filter residue to be added in ball grinder 5:0.1 in mass ratio ~ 0.3 anhydrous
Ethyl alcohol mixing is added zirconium oxide ball milling pearl by ball 20 ~ 30:1 of material mass ratio and obtains ball with 300 ~ 500r/min, 30 ~ 50min of ball milling
Abrasive material takes ball milling material 1:3 ~ 6:2 in mass ratio that sticky rice juice, humic acid mixing is added, is stirred 1 with 300 ~ 500r/min revolving speed
~ 3h vacuumizes be evaporated to original volume 30 ~ 45% in 55 ~ 70 DEG C to get self-control stick.
Wetting agent: 5:1 ~ 3 take cetyl trimethylammonium bromide, the mixing of laureth sodium sulfovinate in mass ratio, i.e.,
Obtain wetting agent.
Antioxidant: 5 ~ 8:1 in mass ratio takes tert-butylhydroquinone, pentaerythrite mixing to get antioxidant.
Initiator: potassium peroxydisulfate, sodium peroxydisulfate, any one in ammonium persulfate.
Mix monomer: 1 ~ 3:1:1 in mass ratio takes acrylic acid, acrylic acid hydroxy alkyl ester, alkyl methacrylate mixing,
Up to mix monomer.
Adjuvant: 3:1 ~ 2 take cottonseed oil, linoleic acid mixing to get adjuvant in mass ratio.
Pretreatment coconut husk particle: taking coconut husk to crushed 80 meshes in pulverizer, and sieving particle 1:10 ~ 15 in mass ratio is taken to add
Entering the HCl solution mixing of concentration 0.1mol/L, 20 ~ 45min is stirred with 400 ~ 600r/min, filtering takes filter residue after natural drying,
In steam blasting device, with 0.1 ~ 1.6MPa steam blasting pressure, 10 ~ 350 DEG C of center housing temperatures, material water quality ratio is 1:20 ~ 30,
Steam blasting is carried out, bursting charge is obtained, takes bursting charge in 10 ~ 15min of 400W microwave treatment to get pretreatment coconut husk particle.
The preparation method of compounded mix, includes the following steps:
(1) taking polyethylene glycol monomethyl ether after being evacuated to 0.3 ~ 0.7kPa dehydration and drying processing, 3 ~ 5h, is moved in 100 ~ 110 DEG C
40 ~ 60 DEG C of reaction kettles are passed through nitrogen protection, and acetic anhydride, the poly glycol monomethyl ether of poly glycol monomethyl ether quality 12 ~ 20% is added
The pyridine of quality 8 ~ 15% mixes, and is warming up to 190 ~ 210 DEG C, and under the conditions of 300 ~ 500r/min, heating stirring reacts 4 ~ 6h, obtains
Pre-composition, in mass ratio 10:1:1 ~ 3 take pre-composition, maleic anhydride, adjuvant mixing, in 200 ~ 210 DEG C, with 200 ~ 400r/
Min is stirred to react 4 ~ 6h, and discharging obtains base-material；
(2) according to the mass fraction, 30 ~ 50 parts of base-materials, 20 ~ 30 parts of styrene, 20 ~ 30 parts of water, 2 ~ 5 parts of initiators, 0.3 ~ 0.7 are taken
Part stannous octoate, 8 ~ 15 parts of dimethyl silicone polymers, 8 ~ 15 parts of mix monomers, 4 ~ 8 parts of isocyanates, first 40 ~ 55 DEG C take base-material,
Styrene, isocyanates, water pour into batch mixer, after being stirred 20 ~ 40min with 300 ~ 500r/min revolving speed, it is warming up to 60 ~
75 DEG C, mix monomer, initiator, dimethyl silicone polymer, stannous octoate mixing is added, is sheared and is dispersed with 2000 ~ 3000r/min
1 ~ 3h is warming up to 80 ~ 95 DEG C, and heat preservation stands 1 ~ 3h to get compounded mix.
The preparation of fermentation product: in 55 ~ 70 DEG C, according to parts by weight, successively taking 8 ~ 15 parts of pretreatment coconut husk particles, 4 ~
8 parts of gelatin, 2 ~ 5 parts of caseins, 2 ~ 5 parts of lactobacillus bulgaricus liquid, 300 ~ 500 parts of water, first will pretreatment coconut husk particle, gelatin,
Water is mixed in reaction kettle, stirs 40 ~ 60min with 400 ~ 600r/min, and heat preservation stands 1 ~ 3h, is warming up to 75 ~ 90 DEG C, with 300 ~
Under 500r/min speed conditions, after 45 ~ 60min of heating stirring, it is transferred to fermentor, then casein and Bao Jiali are added into fermentor
Sub- lactobacillus liquid, subsequent sealed fermenting tank, with the oscillation of 180 ~ 220r/min shaking table, fermented and cultured 4 ~ 6 days, must be sent out in 28 ~ 32 DEG C
Ferment material takes fermentation material in 121 DEG C of 20 ~ 35min of sterilizing, and must sterilize material, takes the sodium bicarbonate that sterilizing material mass fraction is 15% molten
Liquid adjusts pH to neutrality, filtering, and filter vacuum is taken to be concentrated into the 20 ~ 35% of original volume to get fermentation product.
A kind of pressure sensitive adhesive, according to the mass fraction, including following component: 7 ~ 15 parts of wetting agents, 0.1 ~ 0.4 part of paraffin, 3 ~ 7 parts
Naphthenic oil, 2 ~ 5 parts of antioxidants, 15 ~ 30 parts of self-control sticks, 20 ~ 35 parts of compounded mixs, 12 ~ 20 parts of fermentation products.
A kind of preparation method of pressure sensitive adhesive, includes the following steps:
(1) according to the mass fraction, 7 ~ 15 parts of wetting agents, 0.1 ~ 0.4 part of paraffin, 3 ~ 7 parts of naphthenic oils, 2 ~ 5 parts of antioxidants, 15 are taken
~ 30 parts of self-control sticks, 20 ~ 35 parts of compounded mixs, 12 ~ 20 parts of fermentation products；
(2) prior to 30 ~ 45 DEG C, take wetting agent, paraffin, naphthenic oil, antioxidant, compounded mix, in reaction kettle mix, with
400 ~ 600r/min, 20 ~ 40min of magnetic agitation is warming up to 50 ~ 65 DEG C, self-control stick, fermentation product mixing is added, with 2000
~ 3000r/min 40 ~ 60min of magnetic agitation is evaporated in vacuo to original volume 15 ~ 30% to get pressure sensitive adhesive in 60 ~ 80 DEG C.
Embodiment 1
It makes the preparation of stick by oneself: in 45 DEG C of water-bath, taking peach gum 1:1:10 in mass ratio that urea, deionized water mixing is added, with
400r/min stirs 25min, and filtering takes filter residue that dehydrated alcohol mixing is added in ball grinder 5:0.1 in mass ratio, by ball material quality
Zirconium oxide ball milling pearl is added than 20:1, ball milling material is obtained with 300r/min ball milling 30min, ball milling material 1:3:2 in mass ratio is taken to be added
Sticky rice juice, humic acid mixing, are stirred 1h with 300r/min revolving speed, vacuumized in 55 DEG C be evaporated to the 30% of original volume to get
Make stick by oneself.
Wetting agent: 5:1 in mass ratio take cetyl trimethylammonium bromide, laureth sodium sulfovinate mixing to get
Wetting agent.
Antioxidant: 5:1 in mass ratio takes tert-butylhydroquinone, pentaerythrite mixing to get antioxidant.
Initiator: potassium peroxydisulfate.
Mix monomer: 1:1:1 in mass ratio takes acrylic acid, acrylic acid hydroxy alkyl ester, alkyl methacrylate mixing, i.e.,
Obtain mix monomer.
Adjuvant: 3:1 in mass ratio takes cottonseed oil, linoleic acid mixing to get adjuvant.
Pretreatment coconut husk particle: taking coconut husk to crushed 80 meshes in pulverizer, and sieving particle 1:10 in mass ratio is taken to be added
The HCl solution of concentration 0.1mol/L mixes, and stirs 20min with 400r/min, filtering takes filter residue after natural drying, quick-fried in steam
Breaking device, with 0.1MPa steam blasting pressure, 10 DEG C of center housing temperatures, material water quality ratio is 1:20, carries out steam blasting, obtains explosion
Material takes bursting charge in 400W microwave treatment 10min to get pretreatment coconut husk particle.
The preparation method of compounded mix, includes the following steps:
(1) taking polyethylene glycol monomethyl ether after being evacuated to 0.3kPa dehydration and drying processing 3h, moves to 40 DEG C of reaction kettles in 100 DEG C
It is passed through nitrogen protection, the pyridine of acetic anhydride, poly glycol monomethyl ether quality 8% that poly glycol monomethyl ether quality 12% is added is mixed
It closes, is warming up to 190 DEG C, under the conditions of 300r/min, heating stirring reacts 4h, obtains pre-composition, 10:1:1 in mass ratio takes premix
Object, maleic anhydride, adjuvant mixing, in 200 DEG C, are stirred to react 4h with 200r/min, discharge, obtain base-material；
(2) according to the mass fraction, 30 parts of base-materials, 20 parts of styrene, 20 parts of water, 2 parts of initiators, 0.3 part of stannous octoate, 8 parts are taken
Dimethyl silicone polymer, 8 parts of mix monomers, 4 parts of isocyanates, it is mixed that 40 DEG C of elder generation takes base-material, styrene, isocyanates, water to pour into
In material machine, after being stirred 20min with 300r/min revolving speed, 60 DEG C are warming up to, mix monomer, initiator, poly dimethyl is added
Siloxanes, stannous octoate mixing shear dispersion 1h with 2000r/min, are warming up to 80 DEG C, heat preservation stands 1h to get compounded mix.
The preparation of fermentation product: in 55 DEG C, according to parts by weight, successively taking 8 parts of pretreatment coconut husk particles, 4 parts of gelatin,
2 parts of caseins, 2 parts of lactobacillus bulgaricus liquid, 300 parts of water will first pre-process coconut husk particle, gelatin, water and mix in reaction kettle, with
400r/min stirs 40min, and heat preservation stands 1h, is warming up to 75 DEG C, under 300r/min speed conditions, after heating stirring 45min,
It is transferred to fermentor, then casein and lactobacillus bulgaricus liquid are added into fermentor, subsequent sealed fermenting tank, in 28 DEG C, with
The oscillation of 180r/min shaking table, fermented and cultured 4 days, obtains fermentation material, takes fermentation material in 121 DEG C of sterilizing 20min, must sterilize material, take and go out
The sodium bicarbonate solution that bacterium material mass fraction is 15% adjusts pH to neutrality, and filtering takes filter vacuum to be concentrated into original volume
20% to get fermentation product.
A kind of pressure sensitive adhesive, according to the mass fraction, including following component: 7 parts of wetting agents, 0.1 part of paraffin, 3 parts of naphthenic oils, 2
Part antioxidant, 15 parts of self-control sticks, 20 parts of compounded mixs, 12 parts of fermentation products.
A kind of preparation method of pressure sensitive adhesive, includes the following steps:
(1) according to the mass fraction, take 7 parts of wetting agents, 0.1 part of paraffin, 3 parts of naphthenic oils, 2 parts of antioxidants, 15 portions of self-control sticks,
20 parts of compounded mixs, 12 parts of fermentation products；
(2) prior to 30 DEG C, take wetting agent, paraffin, naphthenic oil, antioxidant, compounded mix, in reaction kettle mix, with 400r/
Min magnetic agitation 20min is warming up to 50 DEG C, self-control stick, fermentation product mixing is added, with 2000r/min magnetic agitation
40min is evaporated in vacuo to original volume in 60 DEG C 15% to get pressure sensitive adhesive.
Embodiment 2
It makes the preparation of stick by oneself: in 50 DEG C of water-bath, taking peach gum 1:2:10 in mass ratio that urea, deionized water mixing is added, with
500r/min stirs 40min, and filtering takes filter residue that dehydrated alcohol mixing is added in ball grinder 5:0.2 in mass ratio, by ball material quality
Zirconium oxide ball milling pearl is added than 25:1, ball milling material is obtained with 400r/min ball milling 40min, ball milling material 1:4:2 in mass ratio is taken to be added
Sticky rice juice, humic acid mixing, are stirred 2h with 400r/min revolving speed, vacuumized in 60 DEG C be evaporated to the 35% of original volume to get
Make stick by oneself.
Wetting agent: 5:2 in mass ratio take cetyl trimethylammonium bromide, laureth sodium sulfovinate mixing to get
Wetting agent.
Antioxidant: 6:1 in mass ratio takes tert-butylhydroquinone, pentaerythrite mixing to get antioxidant.
Initiator: sodium peroxydisulfate.
Mix monomer: 2:1:1 in mass ratio takes acrylic acid, acrylic acid hydroxy alkyl ester, alkyl methacrylate mixing, i.e.,
Obtain mix monomer.
Adjuvant: 3:1.5 in mass ratio takes cottonseed oil, linoleic acid mixing to get adjuvant.
Pretreatment coconut husk particle: taking coconut husk to crushed 80 meshes in pulverizer, and sieving particle 1:13 in mass ratio is taken to be added
The HCl solution of concentration 0.1mol/L mixes, and stirs 35min with 500r/min, filtering takes filter residue after natural drying, quick-fried in steam
Breaking device, with 0.9MPa steam blasting pressure, 250 DEG C of center housing temperatures, material water quality ratio is 1:25, carries out steam blasting, obtains quick-fried
Broken material takes bursting charge in 400W microwave treatment 13min to get pretreatment coconut husk particle.
The preparation method of compounded mix, includes the following steps:
(1) taking polyethylene glycol monomethyl ether after being evacuated to 0.4kPa dehydration and drying processing 4h, moves to 50 DEG C of reaction kettles in 105 DEG C
It is passed through nitrogen protection, the pyridine of acetic anhydride, poly glycol monomethyl ether quality 12% that poly glycol monomethyl ether quality 18% is added is mixed
It closes, is warming up to 200 DEG C, under the conditions of 400r/min, heating stirring reacts 5h, obtains pre-composition, 10:1:2 in mass ratio takes premix
Object, maleic anhydride, adjuvant mixing, in 205 DEG C, are stirred to react 5h with 300r/min, discharge, obtain base-material；
(2) according to the mass fraction, 40 parts of base-materials, 25 parts of styrene, 25 parts of water, 4 parts of initiators, 0.5 part of stannous octoate, 12 parts are taken
Dimethyl silicone polymer, 12 parts of mix monomers, 6 parts of isocyanates, it is mixed that 45 DEG C of elder generation takes base-material, styrene, isocyanates, water to pour into
In material machine, after being stirred 30min with 400r/min revolving speed, 68 DEG C are warming up to, mix monomer, initiator, poly dimethyl is added
Siloxanes, stannous octoate mixing shear dispersion 2h with 2500r/min, are warming up to 89 DEG C, heat preservation stands 2h to get compounded mix.
The preparation of fermentation product: in 65 DEG C, according to parts by weight, 12 parts of pretreatment coconut husk particles are successively taken, 6 parts bright
Glue, 4 parts of caseins, 4 parts of lactobacillus bulgaricus liquid, 400 parts of water first mix pretreatment coconut husk particle, gelatin, water in reaction kettle
It closes, 50min is stirred with 500r/min, heat preservation stands 2h, is warming up to 80 DEG C, under 400r/min speed conditions, heating stirring
After 50min, it is transferred to fermentor, then casein and lactobacillus bulgaricus liquid, subsequent sealed fermenting tank, in 29 are added into fermentor
DEG C, with the oscillation of 200r/min shaking table, fermented and cultured 5 days, fermentation material is obtained, takes fermentation material in 121 DEG C of sterilizing 25min, must sterilize material,
The sodium bicarbonate solution that sterilizing material mass fraction is 15% is taken to adjust pH to neutrality, filtering takes filter vacuum to be concentrated into original volume
28% to get fermentation product.
A kind of pressure sensitive adhesive, according to the mass fraction, including following component: 12 parts of wetting agents, 0.3 part of paraffin, 5 parts of naphthenic oils, 4
Part antioxidant, 20 parts of self-control sticks, 28 parts of compounded mixs, 18 parts of fermentation products.
A kind of preparation method of pressure sensitive adhesive, includes the following steps:
(1) according to the mass fraction, take 12 parts of wetting agents, 0.3 part of paraffin, 5 parts of naphthenic oils, 4 parts of antioxidants, 18 portions of self-control sticks,
28 parts of compounded mixs, 18 parts of fermentation products；
(2) prior to 35 DEG C, take wetting agent, paraffin, naphthenic oil, antioxidant, compounded mix, in reaction kettle mix, with 500r/
Min magnetic agitation 50min is warming up to 55 DEG C, self-control stick, fermentation product mixing is added, with 2500r/min magnetic agitation
50min is evaporated in vacuo to original volume in 70 DEG C 20% to get pressure sensitive adhesive.
Embodiment 3
It makes the preparation of stick by oneself: in 60 DEG C of water-bath, taking peach gum 1:3:10 in mass ratio that urea, deionized water mixing is added, with
600r/min stirs 50min, and filtering takes filter residue that dehydrated alcohol mixing is added in ball grinder 5:0.3 in mass ratio, by ball material quality
Zirconium oxide ball milling pearl is added than 30:1, ball milling material is obtained with 500r/min ball milling 50min, ball milling material 1:6:2 in mass ratio is taken to be added
Sticky rice juice, humic acid mixing, are stirred 3h with 500r/min revolving speed, vacuumized in 70 DEG C be evaporated to the 45% of original volume to get
Make stick by oneself.
Wetting agent: 5:3 in mass ratio take cetyl trimethylammonium bromide, laureth sodium sulfovinate mixing to get
Wetting agent.
Antioxidant: 8:1 in mass ratio takes tert-butylhydroquinone, pentaerythrite mixing to get antioxidant.
Initiator: ammonium persulfate.
Mix monomer: 3:1:1 in mass ratio takes acrylic acid, acrylic acid hydroxy alkyl ester, alkyl methacrylate mixing, i.e.,
Obtain mix monomer.
Adjuvant: 3:2 in mass ratio takes cottonseed oil, linoleic acid mixing to get adjuvant.
Pretreatment coconut husk particle: taking coconut husk to crushed 80 meshes in pulverizer, and sieving particle 1:15 in mass ratio is taken to be added
The HCl solution of concentration 0.1mol/L mixes, and stirs 45min with 600r/min, filtering takes filter residue after natural drying, quick-fried in steam
Breaking device, with 1.6MPa steam blasting pressure, 350 DEG C of center housing temperatures, material water quality ratio is 1:30, carries out steam blasting, obtains quick-fried
Broken material takes bursting charge in 400W microwave treatment 15min to get pretreatment coconut husk particle.
The preparation method of compounded mix, includes the following steps:
(1) taking polyethylene glycol monomethyl ether after being evacuated to 0.7kPa dehydration and drying processing 5h, moves to 60 DEG C of reaction kettles in 110 DEG C
It is passed through nitrogen protection, the pyridine of acetic anhydride, poly glycol monomethyl ether quality 15% that poly glycol monomethyl ether quality 20% is added is mixed
It closes, is warming up to 210 DEG C, under the conditions of 500r/min, heating stirring reacts 6h, obtains pre-composition, 10:1:3 in mass ratio takes premix
Object, maleic anhydride, adjuvant mixing, in 210 DEG C, are stirred to react 6h with 400r/min, discharge, obtain base-material；
(2) according to the mass fraction, 50 parts of base-materials, 30 parts of styrene, 30 parts of water, 5 parts of initiators, 0.7 part of stannous octoate, 15 parts are taken
Dimethyl silicone polymer, 15 parts of mix monomers, 8 parts of isocyanates, it is mixed that 55 DEG C of elder generation takes base-material, styrene, isocyanates, water to pour into
In material machine, after being stirred 40min with 500r/min revolving speed, 75 DEG C are warming up to, mix monomer, initiator, poly dimethyl is added
Siloxanes, stannous octoate mixing shear dispersion 3h with 3000r/min, are warming up to 95 DEG C, heat preservation stands 3h to get compounded mix.
The preparation of fermentation product: in 70 DEG C, according to parts by weight, 15 parts of pretreatment coconut husk particles are successively taken, 8 parts bright
Glue, 5 parts of caseins, 5 parts of lactobacillus bulgaricus liquid, 500 parts of water first mix pretreatment coconut husk particle, gelatin, water in reaction kettle
It closes, 60min is stirred with 600r/min, heat preservation stands 3h, is warming up to 90 DEG C, under 500r/min speed conditions, heating stirring
After 60min, it is transferred to fermentor, then casein and lactobacillus bulgaricus liquid, subsequent sealed fermenting tank, in 32 are added into fermentor
DEG C, with the oscillation of 220r/min shaking table, fermented and cultured 6 days, fermentation material is obtained, takes fermentation material in 121 DEG C of sterilizing 35min, must sterilize material,
The sodium bicarbonate solution that sterilizing material mass fraction is 15% is taken to adjust pH to neutrality, filtering takes filter vacuum to be concentrated into original volume
35% to get fermentation product.
A kind of pressure sensitive adhesive, according to the mass fraction, including following component: 15 parts of wetting agents, 0.4 part of paraffin, 7 parts of naphthenic oils, 5
Part antioxidant, 30 parts of self-control sticks, 35 parts of compounded mixs, 20 parts of fermentation products.
A kind of preparation method of pressure sensitive adhesive, includes the following steps:
(1) according to the mass fraction, take 15 parts of wetting agents, 0.4 part of paraffin, 7 parts of naphthenic oils, 5 parts of antioxidants, 30 parts of self-controls viscous
Agent, 35 parts of compounded mixs, 20 parts of fermentation products；
(2) prior to 45 DEG C, take wetting agent, paraffin, naphthenic oil, antioxidant, compounded mix, in reaction kettle mix, with 600r/
Min magnetic agitation 40min is warming up to 65 DEG C, self-control stick, fermentation product mixing is added, with 3000r/min magnetic agitation
60min is evaporated in vacuo to original volume in 80 DEG C 30% to get pressure sensitive adhesive.
Comparative example 1: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that lacking fermentation product.
Comparative example 2: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that lacking compounded mix.
Comparative example 3: the pressure sensitive adhesive of Wuxi City company production.
Embodiment is surveyed with pressure sensitive adhesive obtained by comparative example according to GB/T528-2009, GB/T22235-2008 standard
Examination, test result are as shown in table 1.
Table 1:
| Test item | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Peeling force gf/25mm | 6.98 | 6.52 | 6.76 | 6.12 | 6.24 | 3.38 |
| Cohesive force gf/25mm | 871.7 | 859.6 | 864.3 | 834.5 | 839.1 | 568.6 |
| Elongation at break % | 601 | 592 | 595 | 576 | 584 | 451 |
In summary, pressure sensitive adhesive of the invention is more preferable compared to commercial product effect, is worth promoting.
Claims (10)
1. a kind of pressure sensitive adhesive, according to the mass fraction, including following component: 7 ~ 15 parts of wetting agents, 0.1 ~ 0.4 part of paraffin, 3 ~ 7 parts of rings
Alkane oil, 2 ~ 5 parts of antioxidants, 15 ~ 30 portions of self-control sticks, which is characterized in that further include: 20 ~ 35 parts of compounded mixs, 12 ~ 20 parts
Fermentation product.
2. a kind of pressure sensitive adhesive according to claim 1, which is characterized in that the preparation method of the compounded mix, including it is as follows
Step:
(1) taking polyethylene glycol monomethyl ether is passed through nitrogen protection, polyethyleneglycol is added in 100 ~ 110 DEG C, vacuum drying processing
The pyridine mixing of the acetic anhydride, poly glycol monomethyl ether quality 8 ~ 15% of methyl ether quality 12 ~ 20%, heating, heating stirring reaction obtain
Pre-composition, in mass ratio 10:1:1 ~ 3 take pre-composition, maleic anhydride, adjuvant mixing, in 200 ~ 210 DEG C, are stirred to react, out
Material, obtains base-material；
(2) according to the mass fraction, 30 ~ 50 parts of base-materials, 20 ~ 30 parts of styrene, 20 ~ 30 parts of water, 2 ~ 5 parts of initiators, 0.3 ~ 0.7 are taken
Part stannous octoate, 8 ~ 15 parts of dimethyl silicone polymers, 8 ~ 15 parts of mix monomers, 4 ~ 8 parts of isocyanates, first 40 ~ 55 DEG C take base-material,
Styrene, isocyanates, water, are stirred, and mix monomer, initiator, dimethyl silicone polymer, stannous octoate is added in heating
Mixing, shearing dispersion, heating, heat preservation stand to get compounded mix.
3. a kind of pressure sensitive adhesive according to claim 2, which is characterized in that the adjuvant in the step (1): 3:1 in mass ratio ~
2 take cottonseed oil, linoleic acid mixing to get adjuvant.
4. a kind of pressure sensitive adhesive according to claim 2, which is characterized in that the initiator in the step (2): potassium peroxydisulfate,
Any one in sodium peroxydisulfate, ammonium persulfate.
5. a kind of pressure sensitive adhesive according to claim 2, which is characterized in that the mix monomer in the step (2): in mass ratio
1 ~ 3:1:1 takes acrylic acid, acrylic acid hydroxy alkyl ester, alkyl methacrylate mixing to get mix monomer.
6. a kind of pressure sensitive adhesive according to claim 1, which is characterized in that the preparation of the fermentation product: in 55 ~ 70 DEG C,
According to parts by weight, 8 ~ 15 parts of pretreatment coconut husk particles, 4 ~ 8 parts of gelatin, 2 ~ 5 parts of caseins, 2 ~ 5 parts of bulgarian milk bars are successively taken
Bacterium solution, 300 ~ 500 parts of water will first pre-process coconut husk particle, gelatin, water and mix, and stirring, heat preservation is stood, and heat up, heating stirring,
Casein and lactobacillus bulgaricus liquid is added, closed, in 28 ~ 32 DEG C, shaking table oscillation, fermented and cultured obtains fermentation material, takes fermentation material
Sterilizing, must sterilize material, and sterilizing material is taken to adjust pH, and filtering takes filter vacuum to be concentrated to get fermentation product.
7. a kind of pressure sensitive adhesive according to claim 6, which is characterized in that the pretreatment coconut husk particle: take coconut husk in crushing
Sieving takes sieving particle 1:10 in mass ratio ~ 15 that HCl solution is added and is mixed, and filtering takes filter residue to dry, steam blasting obtains
Bursting charge takes bursting charge microwave treatment to get pretreatment coconut husk particle.
8. a kind of pressure sensitive adhesive according to claim 1, which is characterized in that the self-control stick: in 45 ~ 60 DEG C, take peach gum by
Urea is added in mass ratio 1:1 ~ 3:10, water is mixed, filtering, takes filter residue 5:0.1 in mass ratio ~ 0.3 that dehydrated alcohol is added mixed
It closes, zirconium oxide ball milling pearl is added by ball 20 ~ 30:1 of material mass ratio, ball milling obtains ball milling material, takes ball milling material 1:3 ~ 6:2 in mass ratio
Sticky rice juice, humic acid mixing is added, vacuumizes evaporation in 55 ~ 70 DEG C to get self-control stick.
9. a kind of pressure sensitive adhesive according to claim 1, which is characterized in that the antioxidant: 5 ~ 8:1 in mass ratio takes special fourth
Base hydroquinone, pentaerythrite mixing are to get antioxidant.
10. a kind of pressure sensitive adhesive according to claim 1, which is characterized in that the wetting agent: 5:1 ~ 3 take 16 in mass ratio
Alkyl trimethyl ammonium bromide, the mixing of laureth sodium sulfovinate are to get wetting agent.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110003726A (en) * | 2019-02-25 | 2019-07-12 | 马小良 | A kind of high compatible rubber interleaving agent |
| CN110357483A (en) * | 2019-06-12 | 2019-10-22 | 李珍莲 | A kind of efficient cracking resistance cement soundness agent |
| CN110982446A (en) * | 2019-12-18 | 2020-04-10 | 江门新时代胶粘科技有限公司 | Water-soluble adhesive tape and preparation method and application thereof |
| CN111087971A (en) * | 2019-12-25 | 2020-05-01 | 常州万博金属构件厂 | Pressure-sensitive adhesive for masking tape |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006160931A (en) * | 2004-12-09 | 2006-06-22 | Nippon Starch Chemical Co Ltd | Processed starch obtained by using reducing agent and oxidizing agent and method for producing the same |
| CN106118531A (en) * | 2016-07-19 | 2016-11-16 | 仇颖超 | A kind of preparation method of coir fibre element modified acroleic acid ester pressure-sensitive |
| CN107236490A (en) * | 2017-06-28 | 2017-10-10 | 常州杰轩纺织科技有限公司 | A kind of preparation method of high temperature resistant pressure sensitive adhesive |
| CN107556963A (en) * | 2016-07-01 | 2018-01-09 | 吴明辉 | A kind of ultraviolet photo-curing pressure sensitive adhesive |
-
2018
- 2018-08-17 CN CN201810943339.3A patent/CN109096947B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006160931A (en) * | 2004-12-09 | 2006-06-22 | Nippon Starch Chemical Co Ltd | Processed starch obtained by using reducing agent and oxidizing agent and method for producing the same |
| CN107556963A (en) * | 2016-07-01 | 2018-01-09 | 吴明辉 | A kind of ultraviolet photo-curing pressure sensitive adhesive |
| CN106118531A (en) * | 2016-07-19 | 2016-11-16 | 仇颖超 | A kind of preparation method of coir fibre element modified acroleic acid ester pressure-sensitive |
| CN107236490A (en) * | 2017-06-28 | 2017-10-10 | 常州杰轩纺织科技有限公司 | A kind of preparation method of high temperature resistant pressure sensitive adhesive |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110003726A (en) * | 2019-02-25 | 2019-07-12 | 马小良 | A kind of high compatible rubber interleaving agent |
| CN110357483A (en) * | 2019-06-12 | 2019-10-22 | 李珍莲 | A kind of efficient cracking resistance cement soundness agent |
| CN110982446A (en) * | 2019-12-18 | 2020-04-10 | 江门新时代胶粘科技有限公司 | Water-soluble adhesive tape and preparation method and application thereof |
| CN111087971A (en) * | 2019-12-25 | 2020-05-01 | 常州万博金属构件厂 | Pressure-sensitive adhesive for masking tape |
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