CN106497497A - Antiacid peelable glue and its preparation method and application - Google Patents
Antiacid peelable glue and its preparation method and application Download PDFInfo
- Publication number
- CN106497497A CN106497497A CN201610883725.9A CN201610883725A CN106497497A CN 106497497 A CN106497497 A CN 106497497A CN 201610883725 A CN201610883725 A CN 201610883725A CN 106497497 A CN106497497 A CN 106497497A
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- Prior art keywords
- antiacid
- peelable glue
- acrylate
- glass
- oligomer
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Classifications
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
Abstract
The present invention relates to a kind of antiacid peelable glue and preparation method thereof, belongs to chemical material technical field, the antiacid peelable glue is mainly prepared from by the raw material of following weight part ratio：45～70 parts of oligomer, 25～55 parts of activated monomer, 3～10 parts of light trigger, 0.1～10 part of auxiliary agent；Wherein, the oligomer is at least one in urethane acrylate and PBAA ester；The activated monomer is at least one in monofunctional acrylates' ester, bifunctional acrylate and multi-functional acrylate.The antiacid peelable glue of the present invention has the advantage that：Wire mark applying glue, process is simple can be coated to different size glass surface；And configuration of surface is good, UV light rapid curings are suitable for batch processing；Bonding force is strong, and CNC back edges will not be tilted or be peeled off, and be resistant to HF, HCl and H2SO4；Hot-water soak is peeled off, low cost.In the hf resi stant protection of the secondary hardening processing procedure that can be widely used for safety glass, cover-plate glass, touch-control glass and simple glass.
Description
Technical field
The present invention relates to chemical material technical field, more particularly to a kind of antiacid peelable glue and preparation method thereof and should
With.
Background technology
Generally, the theoretical strength of glass is up to more than 10000MPa, but the practical application intensity of glass is very low, not enough reason
By the 1% of intensity, slightly it is impacted in actual use, it is possible to crack or defect, so as to cause under strength of glass
Drop.In order to solve the above problems, it is one of main method of strengthens glass, also known as secondary hardening to carry out acid treatment to glass
(the last two), its principle are chemical reaction occurs with acid solution with glass surface, and the micro-crack of glass surface is processed, so as to
Improve strength of glass.The conventional acid of acid treatment process now is hydrofluoric acid (HF), hydrofluoric acid and hydrochloric acid (HCl) or sulfuric acid (H2SO4)
Mixed acid.During acid treatment, the glass contacted with acid can be corroded, and need thus for region to be processed is not required to
Protected.
On market, common way is, in big glass-cutting into after little glass, using CNC (Computer Numerical
Control, Numeric Control Technology) sander polishes to glass edge, then glass upper and lower surface be covered with peelable blue gel or
Antiacid film, with HF or mixed acid to polishing after glass edge be etched (secondary hardening), alkali lye moves back film or manual demoulding.
The mode that peelable blue gel or antiacid film are directly fitted after using curing molding, fits cumbersome, by screen size and type
Face is limited, and relatively costly, and inconvenient with membrane removal or not environmentally defect.
Content of the invention
It is based on this, it is necessary to for the problems referred to above, there is provided a kind of antiacid peelable glue, using the peelable glue, wire mark can be passed through
UV light rapid curing after applying glue, with strong to glass bonding force, CNC can be crossed, be resistant to HF or mixed acid, can hot-water soak peel off
The characteristics of.
A kind of antiacid peelable glue, is mainly prepared from by the raw material of following weight part ratio：
The oligomer is at least one in urethane acrylate and PBAA ester；
The activated monomer is monofunctional acrylates' ester, bifunctional acrylate and multi-functional acrylate
In at least one.
Wherein in one embodiment, the peelable glue is mainly prepared from by the raw material of following weight portion：
Wherein in one embodiment, monofunctional acrylates' ester is isobornyl methacrylate, acrylic acid is different
Norbornene ester or 3,3,5- trimethyl-cyclohexane acrylate；
The bifunctional acrylate is Tricyclodecane Dimethanol diacrylate, tripropylene glycol diacrylate
Ester or 1,6 hexanediol diacrylate；
The multi-functional acrylate is trimethylolpropane trimethacrylate, two-trimethylolpropane tris acrylic acid
Ester or ethoxyquin trimethylolpropane trimethacrylate.
Wherein in one embodiment, the light trigger is at least one in free radical photo-initiation.
Wherein in one embodiment, the free radical photo-initiation is 2- hydroxy-2-methyl -1- phenyl -1- acetone, 1-
Hydroxy-cyciohexyl Benzophenone, 2,4,6- trimethylbenzoy-dipheny phosphine oxides, double (2,4,6- trimethylbenzoyls)
At least one in phenyl phosphine oxide, 2,4,6- tri-methyl benzophenones and 4- methyl benzophenones.
Wherein in one embodiment, the auxiliary agent is adhesion promoter, defoamer, wetting agent, levelling agent and antioxygen
At least one in agent.
Wherein in one embodiment, the adhesion promoter be γ-glycidyl ether oxygen propyl trimethoxy silicane,
Gamma-aminopropyl-triethoxy-silane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl
Triethoxysilane and at least one of N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane；
The defoamer is silicone defoamer；
The wetting agent is modified dimethyl silicone polymer；
The levelling agent is silicone levelling agent；
The antioxidant is Hinered phenols antioxidant.
The bright preparation method for also disclosing above-mentioned antiacid peelable glue of this law, it is characterised in that comprise the following steps：
Preheating：The oligomer is preheated；
Hot mixing：Preheating temperature is kept, the activated monomer is added, makes the oligomer be dissolved completely in the activity single
In body, mixed glue solution is obtained；
Mixing：Stop heating, add the light trigger and auxiliary agent, stir under waste heat, obtain final product.
Wherein in one embodiment, in the preheating step, the oligomer is heated to 45-60 DEG C and is preheated.
It is preferred that 50-55 DEG C.
The bright application for also disclosing above-mentioned antiacid peelable glue in the peracid strengthening of glass is processed of this law.
Compared with prior art, the invention has the advantages that：
A kind of antiacid peelable glue of the present invention, can be substituted for peelable blue gel or antiacid film, in acid treatment (the last two) mistake
In journey can protective glass do not corroded by HF.Also, the occupation mode of the peelable glue is to be uniformly coated on to need to protect by wire mark
Glass surface, UV light rapid curings, through glass CNC polish and bubble acid treatment after, glue-line is peeled off using hot-water soak.
Therefore, the antiacid peelable glue has the advantage that：Wire mark applying glue, process is simple can be to different size glass surface
It is coated, is not affected by glass size and shape；After wire mark can quick froth breaking, configuration of surface is good；UV light rapid curings, are suitable for
Batch processing, efficiently；Strong to glass bonding force, CNC processing procedures back edge will not be tilted or be peeled off, and be resistant to HF, HCl and H2SO4Deng many
Plant acid；Hot-water soak is peelable, environmental protection；/ 10th of low cost, about peelable blue gel.
During the antiacid peelable glue can be used for safety glass, cover-plate glass, touch-control glass and simple glass secondary hardening
Hf resi stant protection, have the advantages that having wide range of applications.
Specific embodiment
For the ease of understanding the present invention, the present invention will be described more fully below.But, the present invention can be with perhaps
How different forms is realizing, however it is not limited to embodiment described herein.On the contrary, the purpose for providing these embodiments is to make
Understanding to the disclosure is more thorough comprehensive.
Unless otherwise defined, all of technology used herein and scientific terminology and the technical field for belonging to the present invention
The implication that technical staff is generally understood that is identical.The term for being used in the description of the invention herein is intended merely to description tool
The purpose of the embodiment of body, it is not intended that of the invention in limiting.
The be suitable for glass of antiacid peelable glue of the present invention includes safety glass, cover-plate glass, touch-control glass and common
Glass, includes quartz glass and sapphire glass by material point.The color of the antiacid peelable glue is usually water white transparency, can be slightly
Aobvious milky white.The coating method of the antiacid peelable glue is wire mark.The curing mode of the antiacid peelable glue is UV photocurings.
Embodiment 1
A kind of antiacid peelable glue, is water white transparency UV photocuring products, by being prepared from raw material：
Oligomer：Common 66.11g.
Urethane acrylate 66.11g.
Activated monomer：Common 28.44g.
Monofunctional acrylates' ester, isobornyl acrylate (IBOA) 9.48g,
Multi-functional acrylate, trimethylolpropane trimethacrylate 9.48g,
Multi-functional acrylate, ethoxyquin trimethylolpropane trimethacrylate 9.48g.
Light trigger：Common 3.8g.
2- hydroxy-2-methyls-phenylacetone -1 3.8.
Auxiliary agent：Common 1.65g.
Adhesion promoter (γ-methacryloxypropyl) 0.95g,
Defoamer (silicone defoamer, model 6632) 0.3g,
Levelling agent (silicone levelling agent, model SIVEL 5525) 0.2g,
Antioxidant (hydroquinones) 0.2g.
The antiacid peelable glue of the present embodiment, is prepared by the following method and obtains：
First, preheat.
The oligomer is preheated.Specific as follows：
66.11g oligomer urethane acrylate is put in coppers, 55 DEG C are heated to.
2nd, hot mixing.
Keeping temperature is 55 DEG C, adds activated monomer while stirring, makes oligomer be dissolved completely in activated monomer (simple function
Activated monomer isobornyl acrylate (IBOA) 9.48g of group's acrylate, three hydroxyl of activated monomer of multi-functional acrylate
Propane tri 9.48g, the activated monomer ethoxyquin trimethylolpropane tris acrylic acid of multi-functional acrylate
Ester 9.48g) in, obtain mixed glue solution.
3rd, mix.
Stop heating, (2- hydroxy-2-methyls--1 3.8g of phenylacetone, adhesive force promote to add light trigger and auxiliary agent
Agent (γ-methacryloxypropyl) 0.95g, defoamer (SIVEL 6632) 0.3g, levelling agent
(SIVEL 5525) 0.2g, antioxidant (hydroquinones) 0.2g), it is stirred until homogeneous in the waste heat high speed of previous step；Vacuumize,
Packing, you can obtain water white antiacid peelable glue.
Above-mentioned antiacid peelable glue is carried out performance test, as a result as follows：
The viscosity of the antiacid peelable glue is about 8800cps, and density is 1.072g/cm3；After wire mark can quick froth breaking, surface
Form is good；Solidification energy is 1000mj/cm2, after solidification, hardness is about 68D；Can cross CNC, cross HF (8%HF+8%HCl, 30 DEG C,
Without peeling off without tilting after 8min), 80 DEG C of hot-water soak 8min can be completely stripped, and be specifically shown in table 1 below.
Embodiment 2
A kind of antiacid peelable glue, is water white transparency UV photocuring products, by being prepared from raw material：
Oligomer：Common 47.11g.
PBAA ester 47.11g.
Activated monomer：Common 47.44g.
Monofunctional acrylates' ester, isobornyl acrylate (IBOA) 18.98g,
Bifunctional acrylate, Tricyclodecane Dimethanol diacrylate 18.98g
Multi-functional acrylate, ethoxyquin trimethylolpropane trimethacrylate 9.48g.
Light trigger：Common 3.8g.
2- hydroxy-2-methyls-phenylacetone -1 3.8.
Auxiliary agent：Common 1.65g.
Adhesion promoter (γ-methacryloxypropyl) 0.95g,
Defoamer (silicone defoamer, model 6632) 0.3g,
Levelling agent (silicone levelling agent, model SIVEL 5525) 0.2g,
Antioxidant (hydroquinones) 0.2g.
The antiacid peelable glue of the present embodiment, is prepared by the following method and obtains：
First, preheat.
The oligomer is preheated.Specific as follows：
47.11g oligomer PBAAs ester is put in coppers, 55 DEG C are heated to.
2nd, hot mixing.
Keeping temperature is 55 DEG C, adds activated monomer while stirring, makes oligomer be dissolved completely in activated monomer (simple function
Activated monomer isobornyl acrylate (IBOA) 18.98g of group's acrylate, three ring of activated monomer of bifunctional acrylate
Decane Dimethanol Diacrylate 18.98g, the activated monomer ethoxyquin trimethylolpropane tris propylene of multi-functional acrylate
Acid esters 9.48g) in, obtain mixed glue solution.
3rd, mix.
Stop heating, (2- hydroxy-2-methyls--1 3.8g of phenylacetone, adhesive force promote to add light trigger and auxiliary agent
Agent (γ-methacryloxypropyl) 0.95g, defoamer (SIVEL 6632) 0.3g, levelling agent
(SIVEL 5525) 0.2g, antioxidant (hydroquinones) 0.2g), it is stirred until homogeneous in the waste heat high speed of previous step；Vacuumize,
Packing, you can obtain water white antiacid peelable glue.
Above-mentioned antiacid peelable glue is carried out performance test, as a result as follows：
The viscosity of the antiacid peelable glue is about 20550cps, and density is 0.969g/cm3；After wire mark can quick froth breaking, surface
Form is good；Solidification energy is 700-1000mj/cm2, after solidification, hardness is about 40D；Can cross CNC, cross HF (8%HF+8%HCl,
30 DEG C, 8min) after without peeling off without tilting, 80 DEG C of hot-water soak 10min can be completely stripped, and be specifically shown in table 1 below.
Comparative example 1
A kind of antiacid peelable glue, essentially identical with the peelable glue of embodiment 2, and the preparation method preparation with reference to embodiment 2
Obtain, differ only in：
The activated monomer ethoxyquin trimethylolpropane trimethacrylate of multi-functional acrylate replaces with trihydroxy methyl
Propane tri methylol triacrylate.
Comparative example 2
A kind of antiacid peelable glue, essentially identical with the peelable glue of embodiment 2, and the preparation method preparation with reference to embodiment 2
Obtain, differ only in：
Without γ-methacryloxypropyl and other silane, because of adhesive force NG, (not meeting will
Ask), in CNC can monoblock peel off, not CNC directly steep acid also can monoblock come off.
Comparative example 3
A kind of antiacid peelable glue, essentially identical with the peelable glue of embodiment 2, and the preparation method preparation with reference to embodiment 2
Obtain, differ only in：
Polybutadiene-acrylate replaces with epoxy acrylate or polyester acrylate, and in CNC, edge can collapse
Bad, not CNC directly steep sorrel also can monoblock peel off.
Embodiment
The peelable glue that above-described embodiment and comparative example are prepared carries out performance test after wire mark, and method is as follows：
Viscosity：25 DEG C of viscosity, standard《GB/T 22314-2008 plastics epoxy resin viscosity determining procedures》.
Proportion：25 DEG C, standard《GB/T 15223-2008 plastic liquids resin determines density with bottle method》.
Hardness：23 ± 2 DEG C, standard《GB/T 2411-2008 plastics and hard rubber determine identation hardness (Shao using hardometer
Family name's hardness)》.
CNC：Polished using spark bistrique, rotating speed 1000r/min is rinsed with high-velocity flow after mill, the glue of glass edge
Water will not be peeled off (corrugation, tilting) and be OK.
Bubble acid：8min is soaked in 30 DEG C of 8%HF+8%HCl mixed acid solutions, rinses back edge without wrinkling, stick up with water
Rise or come off as OK.
Hot water is peeled off：Splitting time refers to immersion (can be aided with ultrasonic oscillation to accelerate to peel off), glue in 80 DEG C of hot water
Can monoblock or the time that all peels off.
Test result is as follows：
1. the performance test results of table
In from the above as can be seen that embodiment of the present invention 1-2 antiacid peelable glue, can after wire mark applying glue UV light
Rapid curing, with strong to glass bonding force, CNC can be crossed, be resistant to HF or mixed acid, can hot-water soak the characteristics of peel off, energy
Enough it is applied to glass acid treatment secondary hardening process.And the peelable glue of comparative example 1-3, its effect is poor.
Each technical characteristic of embodiment described above arbitrarily can be combined, for making description succinct, not to above-mentioned reality
Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, the scope of this specification record is all considered to be.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more concrete and detailed, but simultaneously
Therefore can not be construed as limiting the scope of the patent.It should be pointed out that for one of ordinary skill in the art
Say, without departing from the inventive concept of the premise, some deformations and improvement can also be made, these belong to the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be defined by claims.
Claims (10)
1. a kind of antiacid peelable glue, it is characterised in that be mainly prepared from by the raw material of following weight part ratio：
The oligomer is at least one in urethane acrylate and PBAA ester；
The activated monomer is in monofunctional acrylates' ester, bifunctional acrylate and multi-functional acrylate
At least one.
2. antiacid peelable glue according to claim 1, it is characterised in that the main raw material by following weight portion prepare and
Into：
3. antiacid peelable glue according to claim 1, it is characterised in that monofunctional acrylates' ester is metering system
Sour isobornyl thiocyanoacetate, isobornyl acrylate or 3,3,5- trimethyl-cyclohexane acrylate；
The bifunctional acrylate be Tricyclodecane Dimethanol diacrylate, tri (propylene glycol) diacrylate or
1,6 hexanediol diacrylate；
The multi-functional acrylate be trimethylolpropane trimethacrylate, two-trimethylolpropane trimethacrylate or
Ethoxyquin trimethylolpropane trimethacrylate.
4. antiacid peelable glue according to claim 3, it is characterised in that the light trigger is in free radical photo-initiation
At least one.
5. antiacid peelable glue according to claim 4, it is characterised in that the free radical photo-initiation is 2- hydroxyl -2-
Methyl isophthalic acid-phenyl -1- acetone, 1- hydroxy-cyciohexyl Benzophenones, 2,4,6- trimethylbenzoy-dipheny phosphine oxides, double
In (2,4,6- trimethylbenzoyls) phenyl phosphine oxide, 2,4,6- tri-methyl benzophenones and 4- methyl benzophenones extremely
Few one kind.
6. the antiacid peelable glue according to any one of claim 1-5, it is characterised in that the auxiliary agent is that adhesive force promotes
At least one in agent, defoamer, wetting agent, levelling agent and antioxidant.
7. antiacid peelable glue according to claim 6, it is characterised in that the adhesion promoter is γ-glycidol
Ether oxygen propyl trimethoxy silicane, gamma-aminopropyl-triethoxy-silane, γ-methacryloxypropyl trimethoxy silane,
- γ-aminopropyltrimethoxysilane is at least for γ-methacryloxypropyl and N- (β-aminoethyl)
A kind of；
The defoamer is silicone defoamer；
The wetting agent is modified dimethyl silicone polymer；
The levelling agent is silicone levelling agent；
The antioxidant is Hinered phenols antioxidant.
8. the preparation method of the antiacid peelable glue described in any one of claim 1-7, it is characterised in that comprise the following steps：
Preheating：The oligomer is preheated；
Hot mixing：Preheating temperature is kept, the activated monomer is added, is made the oligomer be dissolved completely in the activated monomer
In, obtain mixed glue solution；
Mixing：Stop heating, add the light trigger and auxiliary agent, stir under waste heat, obtain final product.
9. the preparation method of antiacid peelable glue according to claim 8, it is characterised in that in the preheating step, by institute
State oligomer and be heated to 45-60 DEG C and preheated.
10. application of the antiacid peelable glue described in any one of claim 1-7 in the peracid strengthening of glass is processed.
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