CN105542665A - Preparation method of ultraviolet curable adhesive - Google Patents
Preparation method of ultraviolet curable adhesive Download PDFInfo
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- CN105542665A CN105542665A CN201510884784.3A CN201510884784A CN105542665A CN 105542665 A CN105542665 A CN 105542665A CN 201510884784 A CN201510884784 A CN 201510884784A CN 105542665 A CN105542665 A CN 105542665A
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- polyisoprene rubber
- liquid polyisoprene
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- ultraviolet light
- light curing
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Abstract
The invention aims to provide a preparation method of an ultraviolet curable adhesive. The preparation method consists of: a) firstly reacting liquid polyisoprene rubber with maleic anhydride to obtain a liquid polyisoprene rubber graft; b) then reacting the liquid polyisoprene rubber graft with hydroxyl-containing acrylic ester and an oxidizing agent to obtain a colorless and transparent optical liquid polyisoprene rubber prepolymer; and c) preparing the optical liquid polyisoprene rubber prepolymer into a colorless and transparent ultraviolet curable adhesive.
Description
Technical field
The present invention relates to liquid ultraviolet light curing adhesive, and the preparation method and application of this tackiness agent; More specifically, the present invention relates to a kind of can the preparation method and application of water white transparency liquid rubber tackiness agent of ultraviolet light polymerization, be mainly used in electron trade.
Background technology
Ultraviolet light curing adhesive is a kind of environment-friendly and energy-efficient tackiness agent, now in many industrial circle successful Application, especially more general in the application of electron trade, as projection screen assembling, indicating meter is assembled, the aspects such as optics assembling, be usually used in the bonding of associated electrical optical element, the use of water white transparency ultraviolet light curing adhesive, make traditional resistive touch screen gradually replace by capacitive touch screen, be applied to mobile phone, panel computer, during the display equipments such as digital camera, there is speed of response faster, resolving power is higher, the features such as multiple point touching can be realized, promote the dramatic change of electron trade.
Usually, for the tackiness agent that optical electron element is bonding, should certain performance characteristics be had, as; Water white transparency, high transmission rate, high refractive index, low cure shrinkage, high-temp resisting high-humidity resisting, color inhibition, cold-hot impact etc.Prior art mainly uses acrylic resin oligopolymer and reactive thinner to be mixed with optic-solidified adhesive; but this technology mainly exists, and cure shrinkage is high, the problem of high-temp resisting high-humidity resisting difference; especially the situation of wet fastness difference; efficient provide protection can cannot be played to institute's gluing of surfaces; thus reduce the life cycle of element, affect the work-ing life of electronic product.The major cause producing problems is that the structural performance of matrix resin has conclusive effect to the performance of tackiness agent after solidification, and acrylic resin oligopolymer self has relevant functional limitation, although also have correlation technique by carrying out modification to acrylate, namely, other monomer or polymkeric substance received on the molecular chain of acrylate, utilizes their performance advantage to make up the performance deficiency of acrylate.Although these class methods have certain effect, but still cannot tackle the problem at its root, and the most effective settling mode is replaced completely by acrylate.Selected by the present invention is that photo curable liquid polyisoprene rubber oligopolymer is as matrix resin, due to its backbone molecule compound with regular structure, therefore, solidification post-shrinkage ratio is low, strong to the barrier of steam, simultaneously, rubber oligomer itself has the performance characteristics that specific refractory power is high, the rear hardness of solidification is little, be very suitable for electron trade Photocurable adhesive, and self photocurable, effectively avoid the appearance of small molecules transport phenomena, and the usage quantity of acrylate can be reduced to greatest extent, the overall performance of cured article is significantly promoted.
Summary of the invention
The present invention is exactly for the problems referred to above, provides a kind of preparation method of ultraviolet light curing adhesive, and cure shrinkage is low, the performance characteristics of high-temp resisting high-humidity resisting excellence to make it possess.
For realizing above-mentioned purpose of the present invention, the present invention adopts following technical scheme, the preparation method of ultraviolet light curing adhesive of the present invention.
A) first liquid polyisoprene rubber and maleic anhydride are obtained by reacting liquid polyisoprene rubber grafts;
B) then this liquid polyisoprene rubber grafts and hydroxy acryl acid ester and oxidant reaction are obtained water white optical liquid polyisoprene rubber prepolymer;
C) finally water white transparency ultraviolet cured adhesive is prepared into optical liquid polyisoprene rubber prepolymer prepared by described method;
(1) preparation of liquid polyisoprene rubber grafts: liquid polyisoprene rubber, solvent and maleic anhydride are mixed according to mass ratio 1: 1-1.5: 0.015-0.05, under the effect of catalyzer, the consumption of catalyzer is the 1%-4% of liquid polyisoprene rubber quality, after control terminates, gained solution to be poured in precipitation agent and rapid stirring 30min, pour out supernatant liquid and discard, lower floor is desolventized, obtains liquid polyisoprene rubber grafts;
(2) preparation of optical liquid polyisoprene rubber prepolymer: by liquid polyisoprene rubber grafts, solvent and hydroxy acryl acid ester are according to 1: 1-1.5: 0.1-0.3 mixing, under catalyzer and stopper exist, the consumption of catalyzer is the 2%-4% of liquid polyisoprene rubber grafts quality, the consumption of stopper is 0.5% of hydroxy acryl acid ester quality, adding with liquid polyisoprene rubber grafts mass ratio is in the solution the oxygenant of 1: 1, controlling temperature of reaction is react 0.5h under the condition of 90 DEG C, gained solution to be poured in precipitation agent and rapid stirring 30min, pour out supernatant liquid and discard, lower floor is desolventized, obtain water white optical liquid polyisoprene rubber prepolymer,
(3) ultraviolet cured adhesive is made up of the raw material of following mass parts: the optical liquid polyisoprene rubber prepolymer of 50-80 part, the difunctionality reactive thinner of 5-35 part, the polyfunctionality reactive thinner of 10-30 part, the light trigger of 2-8 part, the oxidation inhibitor of 0-2 part.
As the preferred embodiment of this programme, described hydroxy acryl acid ester is the one in senecioate-hydroxyl ethyl ester (HEA), methacrylic acid-beta-hydroxy ethyl ester (HEMA), senecioate-hydroxypropyl acrylate (HPA), methacrylic acid-β-hydroxypropyl acrylate (HPMA).
As the preferred embodiment of this programme, described catalyzer is the one in sodium methylate, potassium hydroxide, sodium hydroxide, tosic acid, particular methanol sodium.
As the preferred embodiment of this programme, described stopper is the one in Resorcinol, para benzoquinone, p methoxy phenol, p-ten.-butylcatechol, preferred Resorcinol.
As the preferred embodiment of this programme, described reaction conditions is temperature of reaction 88-92 DEG C, the reaction times is 3-6h.
As the preferred embodiment of this programme, described difunctionality reactive thinner is 1,6-hexanediyl ester (HDDA), 1,6-hexanediol dimethacrylate (HDDMA), two contracting/tripropylene glycol diacrylates (DPGDA/TPGDA), in two contracting/triethylene Glycol diacrylates (DEGDA/TEGDA), a kind of or several arbitrarily mixture of (DEGDMA/TEGDMA) in two contracting/triethylene Glycol dimethacrylates.
As the preferred embodiment of this programme; described light trigger is 2-hydroxy-2-methyl-1-phenyl-acetone (1173); 1-hydroxy-cyclohexan benzoylformaldoxime (184); 2; mixtures a kind of or several arbitrarily in 4,6-trimethylbenzoy-dipheny phosphine oxide (TPO).
The invention has the beneficial effects as follows: possess that cure shrinkage is low, the performance characteristics of high-temp resisting high-humidity resisting excellence.
Embodiment
The preparation method of a kind of ultraviolet light curing adhesive of the present invention is:
Embodiment 1
100g liquid polyisoprene rubber, 100g dimethylbenzene and 1.5g maleic anhydride are dropped in round-bottomed flask successively, setting temperature of reaction is 75 DEG C and starts heated and stirred, after temperature-stable to design temperature, add 1g dibenzoyl peroxide, after reaction 4h gained solution to be poured in 243g acetone and rapid stirring, pour out supernatant liquid, vacuumize at 65 DEG C, obtain liquid polyisoprene rubber grafts.
By 100g liquid polyisoprene rubber grafts, 100g dimethylbenzene drops in round-bottomed flask, 0.5g Resorcinol and 10g senecioate-hydroxyl ethyl ester are fully dissolved and add in flask, setting temperature of reaction is 90 DEG C and starts heated and stirred, after temperature-stable to design temperature, add 2g sodium methylate, upper solution is gone out with 400 order filter-cloth filterings after reaction 5h, add 100g concentration be the aqueous hydrogen peroxide solution of 50% and constantly stir, 0.5h is reacted under controlling the condition of temperature of reaction 90 DEG C, gained solution to be poured in 468g acetone and rapid stirring 30min, pour out supernatant liquid, vacuumize at 65 DEG C, obtain optical liquid polyisoprene rubber prepolymer.
50g optical liquid polyisoprene rubber, 20gTPGDA, 21.5gTMPTA, 8g1173 and 0.5g1076 are added successively and be uniformly mixed.
The technological process of embodiment 2 ~ 8 is identical with embodiment 1, and actual conditions parameter is in table 1.
The product obtained to each step of embodiment 1 ~ 4 and finished product carry out performance test, comprise the acid number of liquid polyisoprene rubber grafts, the esterification yield of optical liquid polyisoprene rubber prepolymer, the performance of the viscosity of ultraviolet cured adhesive, specific refractory power, cure shrinkage, high-temp resisting high-humidity resisting.
Test currently available products in accordance with the following methods and do performance test, test result and embodiment 1 ~ 4 are contrasted, concrete data are in table 2.
Existing for 70g optical cement 1,10gHDDA, 15gTMPTA, 4.5g1173 and 0.5g1076 are added successively and be uniformly mixed.
Existing for 65g optical cement 2,5gHDDA, 10gTPGDA, 15gPETA, 4g1173 and 1g1141 are added successively and be uniformly mixed.
Table 1 (1), liquid polyisoprene rubber grafts.
Table 1 (2), optical liquid polyisoprene rubber prepolymer:
Table 1 (3), ultraviolet cured adhesive:
Described testing method is as follows:
Acid number: take 2g sample and 50g dimethylbenzene, heating makes sample dissolution, then sodium hydroxide-ethanol the standardized solution of 0.05mol/L is added, reflux at 90 DEG C 1h, phenolphthalein indicator is added after cooling, with 0.05mol/L hydrochloric acid-Virahol standardized solution is counter drops to terminal, calculate according to the following formula:
Wherein:
The acid number of A-sample, mgNaOH/g;
The volume of the sodium hydroxide consumed during V1-titration-ethanol standardized solution, mL;
The volume of the hydrochloric acid consumed during V2-titration-Virahol standardized solution, mL;
The concentration of C1-sodium hydroxide-ethanol standardized solution, mol/L;
The concentration of C2-hydrochloric acid-Virahol standardized solution, mol/L
The quality of m-sample, g.
Esterification yield: according to aforesaid method test acid number, calculate according to following formula:
Wherein:
The acid number of A1-liquid polyisoprene rubber grafts, mgNaOH/g;
The acid number of A2-optical liquid polyisoprene rubber prepolymer, mgNaOH/g.
Viscosity: use NDJ-1 rotational viscosimeter, probe temperature 38 DEG C.
Specific refractory power: use Abbe refractometer to test.
Cure shrinkage: ultraviolet light polymerization glue and the density of solidifying rear solid film before measuring solidification respectively, utilize formulae discovery to draw, that is, cure shrinkage=((solid film density-glue density) × 100)/solid film density.
Hot and humid: the change of the specific refractory power in the environmental test chamber of 85 DEG C of 85% high humidity after resident 1000h.
Table 2, performance test and contrast:
As seen from the above table, compared with prior art, it is low that the present invention has cure shrinkage, the performance characteristics of high-temp resisting high-humidity resisting excellence, can be widely used in the bonding of electronic component.
To those skilled in the art, obviously the invention is not restricted to the details of above-mentioned one exemplary embodiment, and when not deviating from spirit of the present invention or essential characteristic, the present invention can be realized in other specific forms.Therefore, no matter from which point, all should embodiment be regarded as exemplary, and be nonrestrictive, scope of the present invention is limited by claims instead of above-mentioned explanation, and all changes be therefore intended in the implication of the equivalency by dropping on claim and scope are included in the present invention.
The above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technical scheme of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.
Claims (8)
1. a preparation method for ultraviolet light curing adhesive, is characterized in that:
A) first liquid polyisoprene rubber and maleic anhydride are obtained by reacting liquid polyisoprene rubber grafts;
B) then this liquid polyisoprene rubber grafts and hydroxy acryl acid ester and oxidant reaction are obtained water white optical liquid polyisoprene rubber prepolymer;
C) method of water white transparency ultraviolet cured adhesive is finally prepared into optical liquid polyisoprene rubber prepolymer prepared by described method;
(1) preparation of liquid polyisoprene rubber grafts: liquid polyisoprene rubber, solvent and maleic anhydride are mixed according to mass ratio 1: 1-1.5: 0.015-0.05, under the effect of catalyzer, the consumption of catalyzer is the 1%-4% of liquid polyisoprene rubber quality, control certain reaction conditions, after end, gained solution to be poured in precipitation agent and rapid stirring 30min, pour out supernatant liquid and discard, lower floor's solid is desolventized, obtains liquid polyisoprene rubber grafts;
(2) preparation of optical liquid polyisoprene rubber prepolymer: by liquid polyisoprene rubber grafts, solvent and hydroxy acryl acid ester are according to 1: 1-1.5: 0.1-0.3 mixing, under catalyzer and stopper exist, the consumption of catalyzer is the 2%-4% of liquid polyisoprene rubber grafts quality, the consumption of stopper is 0.5% of hydroxy acryl acid ester quality, control certain reaction conditions, by certain filtration condition, solution is filtered after reaction terminates, adding with liquid polyisoprene rubber grafts mass ratio is in the solution the oxygenant of 1: 1, controlling temperature of reaction is react 0.5h under the condition of 90 DEG C, gained solution to be poured in precipitation agent and rapid stirring 30min, pour out supernatant liquid and discard, lower floor's solid is desolventized, obtain water white optical liquid polyisoprene rubber prepolymer,
(3) ultraviolet cured adhesive is made up of the raw material of following mass parts: the optical liquid polyisoprene rubber prepolymer of 50-80 part, the difunctionality reactive thinner of 5-35 part, the polyfunctionality reactive thinner of 10-30 part, the light trigger of 2-8 part, the oxidation inhibitor of 0-2 part.
2. the preparation method of a kind of ultraviolet light curing adhesive according to claim 1, is characterized in that: described hydroxy acryl acid ester is the one in senecioate-hydroxyl ethyl ester (HEA), methacrylic acid-beta-hydroxy ethyl ester (HEMA), senecioate-hydroxypropyl acrylate (HPA), methacrylic acid-β-hydroxypropyl acrylate (HPMA).
3. the preparation method of a kind of ultraviolet light curing adhesive according to claim 1, is characterized in that: described catalyzer is the one in sodium methylate, potassium hydroxide, sodium hydroxide, tosic acid, particular methanol sodium.
4. the preparation method of a kind of ultraviolet light curing adhesive according to claim 1, is characterized in that: described stopper is the one in Resorcinol, para benzoquinone, p methoxy phenol, p-ten.-butylcatechol, preferred Resorcinol.
5. the preparation method of a kind of ultraviolet light curing adhesive according to claim 1, is characterized in that: described reaction conditions is temperature of reaction 88-92 DEG C, the reaction times is 3-6h.
6. the preparation method of a kind of ultraviolet light curing adhesive according to claim 1, it is characterized in that: described difunctionality reactive thinner is 1,6-hexanediyl ester (HDDA), 1,6-hexanediol dimethacrylate (HDDMA), two contracting/tripropylene glycol diacrylates (DPGDA/TPGDA), in two contracting/triethylene Glycol diacrylates (DEGDA/TEGDA), a kind of or several arbitrarily mixture of (DEGDMA/TEGDMA) in two contracting/triethylene Glycol dimethacrylates.
7. the preparation method of a kind of ultraviolet light curing adhesive according to claim 1, it is characterized in that: described polyfunctionality reactive thinner is Viscoat 295 (TMPTA), trimethylolpropane trimethacrylate (TMPTMA), pentaerythritol triacrylate (PETA), tetramethylol methane tetraacrylate (PETTA), diacid trimethylolpropane tetra-acrylate (DTEMPTTA), a kind of or several arbitrarily mixture of (DPHA) in double pentaerythritol methacrylate.
8. the preparation method of a kind of ultraviolet light curing adhesive according to claim 1; it is characterized in that: described light trigger is 2-hydroxy-2-methyl-1-phenyl-acetone (1173); 1-hydroxy-cyclohexan benzoylformaldoxime (184); 2; mixtures a kind of or several arbitrarily in 4,6-trimethylbenzoy-dipheny phosphine oxide (TPO).
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| CN201510884784.3A CN105542665A (en) | 2015-12-07 | 2015-12-07 | Preparation method of ultraviolet curable adhesive |
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| CN201510884784.3A CN105542665A (en) | 2015-12-07 | 2015-12-07 | Preparation method of ultraviolet curable adhesive |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108047399A (en) * | 2018-02-12 | 2018-05-18 | 濮阳林氏化学新材料股份有限公司 | A kind of industrialized process for preparing of acrylic ester grafted polyisoprene |
| CN108276932A (en) * | 2018-03-14 | 2018-07-13 | 深圳市库泰克电子材料技术有限公司 | A kind of dual cure UV glue stick for low-surface-energy material bonding |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04356545A (en) * | 1991-06-01 | 1992-12-10 | Kuraray Co Ltd | Organic polymer composition containing inorganic filler |
| CN103974826A (en) * | 2011-12-08 | 2014-08-06 | 日本化药株式会社 | Optical member, ultraviolet curable resin composition, and cured product |
| CN104334344A (en) * | 2012-01-13 | 2015-02-04 | 日本化药株式会社 | Optical member, and ultraviolet-curable adhesive used in production of same |
-
2015
- 2015-12-07 CN CN201510884784.3A patent/CN105542665A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04356545A (en) * | 1991-06-01 | 1992-12-10 | Kuraray Co Ltd | Organic polymer composition containing inorganic filler |
| CN103974826A (en) * | 2011-12-08 | 2014-08-06 | 日本化药株式会社 | Optical member, ultraviolet curable resin composition, and cured product |
| CN104334344A (en) * | 2012-01-13 | 2015-02-04 | 日本化药株式会社 | Optical member, and ultraviolet-curable adhesive used in production of same |
Non-Patent Citations (1)
| Title |
|---|
| 马金红 等: "UV固化液体聚异戊二烯橡胶改性物的合成", 《江西师范大学学报（自然科学版）》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108047399A (en) * | 2018-02-12 | 2018-05-18 | 濮阳林氏化学新材料股份有限公司 | A kind of industrialized process for preparing of acrylic ester grafted polyisoprene |
| CN108276932A (en) * | 2018-03-14 | 2018-07-13 | 深圳市库泰克电子材料技术有限公司 | A kind of dual cure UV glue stick for low-surface-energy material bonding |
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