CN1887972A - Nanometer SiO2 modifying process of ultraviolet ray cured adhesive - Google Patents
Nanometer SiO2 modifying process of ultraviolet ray cured adhesive Download PDFInfo
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- CN1887972A CN1887972A CN 200610052461 CN200610052461A CN1887972A CN 1887972 A CN1887972 A CN 1887972A CN 200610052461 CN200610052461 CN 200610052461 CN 200610052461 A CN200610052461 A CN 200610052461A CN 1887972 A CN1887972 A CN 1887972A
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Abstract
The present invention discloses nanometer SiO2 modifying process of UV ray cured adhesive. The long chain polyether silane coupler in the general expression of (R1O)3SiCH2CH2CH2O(CH2CH2O)a(CH2CH(CH3)O)bC=OC(R2)=CH2 is first used in surface modifying SiO2 of grain size of 5-50 nm inside isopropyl alcohol dispersing medium; the obtained composite pre-polymer is then mixed with epoxy acrylate, hydroxyethyl methacrylate or hydroxypropyl methacrylate, trimethylopropane-3ethoxyl -triacrylic ester, acrylic cid or acrylate with acid functional radical, photoiniitator, KH570, triethanolamine and maleic acid through stirring to obtain the UV adhesive product. The present invention has improved SiO2 dispersivity and stability, and the UV adhesive product has greatly raised adhesion performance.
Description
Technical field
The present invention relates to fine chemical product development research field, specifically, the present invention relates to a kind of long-chain polyether type silane coupler modified Nano SiO
2The method of (silicon-dioxide).
Background technology
UV-light (UV) curing technology is a kind of new green technology that twentieth century was developed since the sixties, and it is meant that liquid-phase system carries out polymerization, crosslinked and solidified process in moment through ultraviolet radiation.The advantage that it is unique: (1) fast setting; Several seconds even just can be cured as cured coating film hard, wear-resisting and attractive in appearance, excellent product performance less than one second; (2) energy-and time-economizing; Do not need extra drying plant, be fit to continuous production, can increase substantially production efficiency; (3) low or solvent-free release; (4) equipment volume is little, invests low; (5) solidification value is low and curing speed is fast.
As one of product the most commonly used in the UV solidify material, the UV cured adhesive meets " 4E " principle, promptly economical (Economy), the energy (Energy), ecological (Ecology), efficient (Efficiency).Be in particular in: single component, easy to use; Curing speed is fast, can finish curing in general several seconds to tens of seconds, helps realizing automatic production, raises labour productivity; Solidification value is low, saves the energy, and room temperature is promptly curable.Continuous expansion along with the ultraviolet photo-curing cementing agent application, Xiang Guan research is also deep day by day therewith, the function of ultraviolet photo-curing cementing agent is segmentation again and again also, can be used for bonding various material, be applicable to different fields, simultaneously in the market of tackiness agent shared ratio also in further expansion.
UV cured adhesive prescription mainly is made up of light trigger, performed polymer, reactive monomer etc., also can add various auxiliary agents such as sensitizing agent, softening agent, stablizer, tackifier, oxidation inhibitor, flow agent, protective agent as required, the adding of different auxiliary agents has very big influence to the concrete use properties of tackiness agent.Wherein, performed polymer is the main component of UV cured adhesive, the size of its structure and molecular weight all affects hardness, snappiness, Joint strength, resistance to medium and the persistence etc. of product, and the kind of its speed of response and molecular weight, functionality and functional group has much relations; And in the UV cured adhesive, reactive monomer had both been participated in the system curing cross-linked directly, was used as the thinner of high molecular performed polymer again, the viscosity that tackiness agent is had be convenient to construct.
Nanometer SiO
2Owing to have intensive small-size effect or volume effect, surface effects etc., quantum size effect and macro quanta tunnel effect etc., thereby show many peculiar character.Can improve hardness, Young's modulus of material etc. as breaking tenacity height, good toughness, when high temperature resistant, nano combined, and thermal expansivity, thermal conductivity, heat-shock resistance are exerted an influence.Thereby in fields such as rubber, coating, medicine, tackiness agent, used widely with its superior stability, reinforcement, thickening property and thixotropy; But general in concrete application facet, all need nanometer SiO
2Carry out to improve its use properties in matrix material after the modification.
Handle nanometer SiO in existing chemical modification
2Study of surfaces and application facet, silane coupling agent are class properties-correcting agent commonly used, and (Y can be Cl, OCH to the Si-Y key that it has
3, OC
2H
5Deng) can with SiO
2The Si-OH key on surface carries out chemical condensation reaction, makes SiO
2The surface is transformed into lipophilicity from wetting ability.Nanometer SiO through modification
2Because surface hydroxyl is replaced by organic group, between particle mutually agglomeration reduce, thereby can be evenly and stably be dispersed in organic solvent and the polymeric matrix.
Tradition is usually used in nanometer SiO
2Modified silane coupler is mainly vinyltriethoxysilane, gamma-methyl allyl acyloxypropyl trimethoxysilane, aminocarbonyl propyl triethoxyl silane etc., and these coupling agents are for improving nanometer SiO
2The lipophilicity on surface promotes nanometer SiO
2And the consistency between organic solvent and polymkeric substance are basic reduces SiO
2Reuniting all has certain effect, but above-mentioned coupling agent, because its molecular chain is short, can not be to SiO
2Particle effectively wraps up, so nanometer SiO
2Particle is in organic matrix, particularly in organic solvent with in the ultraviolet photo-curing cementing agent matrix resins such as urethane acrylate, epoxy acrylate, also exist the part agglomeration, can not well be disperseed, influenced its application performance in ultraviolet photo-curing cementing agent; Using the bonding use properties of adhesive products on glass, metal series material that method of the present invention obtains improves greatly.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of method of the nanometer SiO2 modification that is used for ultraviolet photo-curing cementing agent newly is provided.
The objective of the invention is to be achieved through the following technical solutions a kind of nanometer SiO that is used for UV-light assimilation tackiness agent
2The method of modification may further comprise the steps:
(1) be (R with general formula
1O)
3SiCH
2CH
2CH
2O (CH
2CH
2O)
a(CH
2CH (CH
3) O)
bC=OC (R
2)=CH
2Long-chain siloxanes coupling agent, to the SiO of particle diameter in 5～50nm scope
2The Virahol dispersion liquid carries out surface modification, obtains modification SiO
2/ Virahol dispersion liquid; Long-chain end in the described long-chain siloxanes coupling agent molecule has acrylic double bond, and the centre is a polyether segment, and wherein, a, b are arbitrary numerical value in 0～50 scope, R
1Be methyl or ethyl, R
2Be hydrogen atom or methyl; SiO in the described Virahol dispersion liquid
2Content is 10～30%; The modified-reaction temperature is 40～70 ℃, and the modified-reaction time is 4～8h, and coupling agent is at SiO
2Addition in the Virahol dispersion liquid is 5～20%;
(2) with the modification SiO that obtains in the step (1)
2/ Virahol dispersion liquid and urethane acrylate or epoxy acrylate, acetone solvent are pressed 0.5～10%, 5～40%, 50～90% mass ratio blend, and ultra-sonic dispersion 10～30min is at 30～60 ℃ of following stirring heating 3～6h, to promote SiO
2The dispersion of particle in urethane acrylate or epoxy acrylate, pressure reducing and steaming acetone and isopropanol solvent obtain SiO then
2/ urethane acrylate or SiO
2The compound performed polymer of/epoxy acrylate;
(3) with the SiO that obtains in the step (2)
2/ urethane acrylate or SiO
2Compound performed polymer, epoxy acrylate, hydroxyethyl methylacrylate or the Rocryl 410 of/epoxy acrylate, TriMethylolPropane(TMP)-3 ethoxylations-triacrylate, vinylformic acid or acid functional groups acrylate, 1173 light triggers, KH570, trolamine, toxilic acid mix by 20～60%, 0～25%, 0～30%, 0～8%, 0～15%, 0.5～3%, 0.5～1.5%, 0.5～1.5%, 0.2～1.0% mass ratio, obtain the UV tackiness agent after stirring.
Further, in the described step (1), described nanometer SiO
2The modified-reaction temperature is 40～60 ℃, and the reaction times is 4～6h.
Further, in the described step (2), described SiO
2The mass ratio of/Virahol dispersion liquid, urethane acrylate or epoxy acrylate, acetone solvent is 1～5%: 8～25%: 70～90%.
The invention has the beneficial effects as follows that the present invention utilizes silane oxygen groups in its molecule to SiO earlier
2Nanoparticle carries out modification, utilizes polymeric matrix generation chemical reactions such as enoyl-that coupling agent long-chain end has and urethane acrylate, epoxy acrylate again, promotes nanometer SiO
2Consistency with organic matrix.And the polyether segment in the coupling agent then can play nanometer SiO
2Parcel, the effect of surface modification, promote nanometer SiO
2Dispersiveness in organic matrix improves nanometer SiO greatly
2In organic solvent with ultraviolet photo-curing cementing agent matrixes such as urethane acrylate, epoxy acrylate in dispersiveness and stability, and keep good dispersiveness in the resin after curing, thereby tackiness agent played good toughness reinforcing, enhancement.Make bonding use properties such as the mechanical property etc. of prepared tackiness agent on glass, metal series material improve a lot, products obtained therefrom viscosity is lower simultaneously, and set time is very short.
Description of drawings
Fig. 1 is a tensile shear strength test sample synoptic diagram;
Fig. 2 is inhomogeneous pull strength specimen synoptic diagram;
Fig. 3 is unmodified nanometer SiO
2Particle disperses synoptic diagram in UV glue sample;
Fig. 4 is KH570 modified Nano SiO
2Particle disperses synoptic diagram in UV glue sample;
Fig. 5 is that molecular weight is 600 MAPETES modified Nano SiO
2Particle disperses synoptic diagram in UV glue sample.
Embodiment
Describe the present invention in detail with embodiment with reference to the accompanying drawings below, purpose of the present invention and effect will be more obvious.
Concrete steps of the present invention are: (1) is (R with general formula
1O)
3SiCH
2CH
2CH
2O (CH
2CH
2O)
a(CH
2CH (CH
3) O)
bC=OC (R
2)=CH
2Novel long-chain siloxanes coupling agent, the long-chain end in its molecule has acrylic double bond, the centre is a polyether segment, wherein, a, b=0～50, R
1Be methyl, ethyl, R
2Be hydrogen atom, methyl, to the SiO of particle diameter in 5～50nm scope
2The Virahol dispersion liquid carries out surface modification; SiO in the aqueous isopropanol
2Content is 5～30%; 40～70 ℃ of modified-reaction temperature, modified-reaction time 4～8h, coupling agent is at SiO
2The add-on of aqueous isopropanol is 5～20%; (2) with the modification SiO that obtains in the step (1)
2/ Virahol dispersion liquid, urethane acrylate or epoxy acrylate, acetone solvent are pressed 0.5～10%, 5～40%, 50～90% mass ratio blend, ultra-sonic dispersion 10～30min, and 30～60 ℃ of following stirring heating 3～6h are to promote SiO
2The dispersion of particle in urethane acrylate or epoxy acrylate, reaction finishes back pressure reducing and steaming acetone and isopropanol solvent; (3) with the SiO that obtains in the step (2)
2/ urethane acrylate or SiO
2The compound performed polymer of/epoxy acrylate is that 0～15%, 1173 light triggers 0.5～3%, KH570 0.5～1.5%, trolamine 0.5～1.5%, toxilic acid 0.2～1.0% mix by mass ratio 20～60%, epoxy acrylate 0～25%, hydroxyethyl methylacrylate or Rocryl 410 0～30%, TriMethylolPropane(TMP) (3 ethoxylation) triacrylate 0～8%, vinylformic acid or acid functional groups acrylate, be the UV tackiness agent that obtains after stirring, products obtained therefrom will keep in Dark Place.
Nanometer SiO in step among the present invention (1) isopropanol solvent
2Preferred modified-reaction condition is: temperature of reaction is 50～60 ℃, reaction times 4～6h; SiO in the preferred aqueous isopropanol
2Content is 10～30%, and coupling agent agent add-on is 5～15%, and general formula is (R
1O)
3SiCH
2CH
2CH
2O (CH
2CH
2O)
a(CH
2CH (CH
3) O)
bC=OC (R
2)=CH
2Silane coupling agent can be CH by general formula
2=CHCH
2O (CH
2CH
2O)
a(CH
2CH (CH
3) O)
bThe allyl polyether of H and general formula are HSi (OR
1)
3, CH
2=C (R
2) C=OCl is through the preparation of the addition of silicon hydrogen, esterification; Also can propose Molecular Structure Design, provide by relevant coupling agent manufacturer according to oneself, wherein, a, b=0～50, R
1Be methyl, ethyl, R
2Be hydrogen atom, methyl.
SiO in the step among the present invention (2)
2The preferred mass ratio of/Virahol dispersion liquid, urethane acrylate or epoxy acrylate, acetone solvent is 1～5%, 8～25%, 70～90%, preferred dispersion condition is: ultrasonic time is 15～30min, 40～60 ℃ of following stirring heating 4～6h.
1173 light triggers described in the step among the present invention (3) are 2-hydroxyl-aminomethyl phenyl propane-1-ketone, and KH570 is γ-(methacryloxypropyl) propyl trimethoxy silicane.
The glue that utilizes the present invention to configure is coated on sheet glass through the acetone wiping (on 75 * 35 * 12mm) equably, then with two steel discs through the acetone wiping (100 * 25 * 2mm) be overlapped on above, as shown in Figure 1, place then that the 8cm place is cured processing under the 300W ultraviolet lamp.Sample after the curing is placed more than 16 hours down at 25 ℃, carries out tension test then on the Zwick/Roll universal testing machine, gets maximum stretching force Pmax.Probe temperature: 25 ℃, draw speed: 10mm/min.Tensile shear strength is calculated as follows: tensile shear strength (MPa) τ=P
Max/ S, S refers to bond area.
Stipulate with reference to U.S. Mil-A-8331/14164, at two glass (wide glue that utilizes gained of the present invention of 75 * 35 * 10mm) one ends coating 5mm with the acetone wiping, with two sheet glass by specification Fig. 2 overlap joint, 2min is solidified at the 8cm place under the 300W ultraviolet lamp then.Sample after the curing is placed down more than 16 hours at 25 ℃, in the enterprising line bend test of Zwick/Roll universal testing machine, gets peak pressure Pmax then.Probe temperature: 25 ℃, press down speed 2mm/min.Inhomogeneous pull strength is calculated as follows: inhomogeneous pull strength (kN/m), Rm=P
Max/ L, L refer to the width of glass, L=35mm among the present invention.
Utilize nanometer SiO provided by the invention
2Method of modifying can greatly improve nanometer SiO
2Dispersiveness in ultraviolet photo-curing cementing agent matrix resins such as organic dispersion medium, urethane acrylate, epoxy acrylate and stability, and the good dispersiveness of maintenance in the resin after curing, its dispersion situation can characterize by transmission electron microscope, specifically sees accompanying drawing 3.
Utilize the modified Nano SiO that obtains among the present invention
2Be applied in the ultraviolet photo-curing cementing agent prescription, outward appearance, viscosity that not only can make product etc. is improved, adhesive products is improved a lot in the mechanical property aspect glass, the metal series material bonding, at room temperature time several seconds is interior with regard to curable drying, can get dry channel by shortening equipment, cut down the consumption of energy greatly, enhance productivity.
According to step of the present invention, at first to SiO
2Particle carries out chemical modification, SiO in initial size is 5～50nm scope
2Content is in 15% the Virahol dispersion liquid, add molecular weight respectively and be 600,800,1200 the poly-alkoxyl group triethoxyl silane (MAPETES) of methacryloxy, KH570 it is carried out chemical modification, the coupling agent add-on is 10%, modification temperature is controlled at 40～60 ℃, and modification time is controlled at 4～6h; The modification SiO of gained
2Aqueous isopropanol is designated as Si-1, Si-2, Si-3, Si-4 respectively, and the sample after the modification characterizes SiO in the Virahol by analysis through transmission electron microscope, grain
2Size about 5～50nm, good dispersion, and do not have agglomeration and take place.
Will be among the embodiment mainly with MAPETES modification SiO
2The Si-1 of gained, Si-2, three kinds of samples of Si-3 come other content of the present invention is further specified, and purpose of the present invention and effect will be more obvious, but the present invention is not limited by following examples.
To specify in order better the present invention being made, to have investigated earlier in the embodiment of the invention and do not add SiO
2The effect of the UV glue of particle is designated as contrast sample 1; Then again respectively to the SiO of non-modified
2, with the SiO of KH570 modification
2The effect of the prescription of particle in UV glue is investigated, and the UV glue of preparation is designated as contrast sample 2, contrast sample 3 respectively.
Embodiment 1
Add 2.5%Si-1,15% urethane acrylate, 87.5% acetone in Glass Containers respectively, blend is back ultra-sonic dispersion 15min well, and 60 ℃ of following stirring heating 6h are to promote SiO
2The dispersion of particle in urethane acrylate, then pressure reducing and steaming acetone and isopropanol solvent; Then with the SiO that obtains
2The compound performed polymer of/urethane acrylate by 60%, Rocryl 410 20%, TriMethylolPropane(TMP) (3 ethoxylation) triacrylate 5%, acid functional groups acrylate 10%, 1173 light triggers 2%, KH570 be 1%, the mass ratio of trolamine 1.5%, toxilic acid 0.5% mixes, the sample of the gained that stirs is the water white transparency shape; But sample places under the 300W ultraviolet lamp 8cm place completely solidified in 5 seconds; Solidify SiO in the sample of back
2Particle disperses synoptic diagram to see Fig. 5, and other The performance test results sees Table 1.
Embodiment 2
Add 2.5%Si-2,15% urethane acrylate, 87.5% acetone in Glass Containers respectively, blend is back ultra-sonic dispersion 15min well, and 60 ℃ of following stirring heating 6h are to promote SiO
2The dispersion of particle in urethane acrylate, after reaction finishes, pressure reducing and steaming acetone and isopropanol solvent; 40% the SiO that will obtain then
2The compound performed polymer of/urethane acrylate by 40%, epoxy acrylate 20%, Rocryl 410 20%, TriMethylolPropane(TMP) (3 ethoxylation) triacrylate 5%, acid functional groups acrylate 10%, 1173 light triggers 2.5%, KH570 be 1%, the mass ratio of trolamine 1.0%, toxilic acid 0.5% mixes, the sample of the gained that stirs is the water white transparency shape; But sample places under the 300W ultraviolet lamp 8cm place completely solidified in 5 seconds; Other The performance test results sees Table 1.
Embodiment 3
Add 2.5%Si-3,15% epoxy acrylate, 87.5% acetone in Glass Containers respectively, blend is back ultra-sonic dispersion 30min well, and 60 ℃ of following stirring heating 4h are to promote SiO
2The dispersion of particle in epoxy acrylate, after the end, pressure reducing and steaming acetone and isopropanol solvent; Then with the SiO that obtains
2The compound performed polymer of/epoxy acrylate by 80%, Rocryl 410 10%, TriMethylolPropane(TMP) (3 ethoxylation) triacrylate 5%, 1173 light triggers 2.5%, KH570 be 1%, the mass ratio of trolamine 1.0%, toxilic acid 0.5% mixes, the sample of the gained that stirs is the water white transparency shape; But sample places under the 300W ultraviolet lamp 8cm place completely solidified in 5 seconds; Other The performance test results sees Table 1.
Embodiment 4
Add 5%Si-3,15% epoxy acrylate, 80% acetone in Glass Containers respectively, blend is back ultra-sonic dispersion 30min well, and 60 ℃ of following stirring heating 7h are to promote SiO
2The dispersion of particle in urethane acrylate, after the end, pressure reducing and steaming acetone and isopropanol solvent; Then with the SiO that obtains
2The compound performed polymer of/epoxy acrylate by 40%, urethane acrylate 20%, Rocryl 410 20%, hydroxyethyl methylacrylate 5%, vinylformic acid 5%, TriMethylolPropane(TMP) (3 ethoxylation) triacrylate 5%, 1173 light triggers 2%, KH570 be 1.5%, the mass ratio of trolamine 1.0%, toxilic acid 0.5% mixes, the sample of the gained that stirs is the water white transparency shape; But sample places under the 300W ultraviolet lamp 8cm place completely solidified in 8 seconds; Other The performance test results sees Table 1.
Embodiment 5
Add 5%Si-1,15% epoxy acrylate, 80% acetone in Glass Containers respectively, blend is back ultra-sonic dispersion 30min well, and 60 ℃ of following stirring heating 4h are to promote SiO
2The dispersion of particle in urethane acrylate, after the end, pressure reducing and steaming acetone and isopropanol solvent; Then with the SiO that obtains
2The compound performed polymer of/epoxy acrylate by 20%, urethane acrylate 20%, Rocryl 410 30%, hydroxyethyl methylacrylate 10%, acid functional groups acrylate 10%, TriMethylolPropane(TMP) (3 ethoxylation) triacrylate 10%, 1173 light triggers 2.5%, KH570 be 1%, the mass ratio of trolamine 1.0%, toxilic acid 0.5% mixes, the sample of the gained that stirs is the water white transparency shape; But sample places under the 300W ultraviolet lamp 8cm place completely solidified in 3 seconds; Other The performance test results sees Table 1.
Embodiment 6
Add 5%Si-2,15% epoxy acrylate, 80% acetone in Glass Containers respectively, blend is back ultra-sonic dispersion 30min well, and 60 ℃ of following stirring heating 7h are to promote SiO
2The dispersion of particle in urethane acrylate, after the end, pressure reducing and steaming acetone and isopropanol solvent; Then with the SiO that obtains
2The compound performed polymer of/epoxy acrylate by 30%, urethane acrylate 30%, Rocryl 410 20%, hydroxyethyl methylacrylate 5%, acid functional groups acrylate 5%, TriMethylolPropane(TMP) (3 ethoxylation) triacrylate 5%, 1173 light triggers 2.5%, KH570 be 1%, the mass ratio of trolamine 1.0%, toxilic acid 0.5% mixes, the sample of the gained that stirs is the water white transparency shape; But sample places under the 300W ultraviolet lamp 8cm place completely solidified in 5 seconds; Other The performance test results sees Table 1.
Embodiment 7
Add 5%Si-2,15% epoxy acrylate, 87.5% acetone in Glass Containers respectively, blend is back ultra-sonic dispersion 30min well, and 60 ℃ of following stirring heating 7h are to promote SiO
2The dispersion of particle in urethane acrylate, after the end, pressure reducing and steaming acetone and isopropanol solvent; Then with the SiO that obtains
2The compound performed polymer of/epoxy acrylate by 20%, urethane acrylate 30%, Rocryl 410 10%, hydroxyethyl methylacrylate 20%, TriMethylolPropane(TMP) (3 ethoxylation) triacrylate 5%, acid functional groups acrylate 10%, 1173 light triggers 2.5%, KH570 be 1%, the mass ratio of trolamine 1.0%, toxilic acid 0.5% mixes, the sample of the gained that stirs is the water white transparency shape; But sample places under the 300W ultraviolet lamp 8cm place completely solidified in 7 seconds; Other The performance test results sees Table 1.
Contrast sample 1
Epoxy acrylate 30%, Rocryl 410 20%, TriMethylolPropane(TMP) (3 ethoxylation) triacrylate 5%, acid functional groups acrylate 10%, 1173 light triggers 2% with urethane acrylate 30%, 30%, KH570 is 1%, trolamine 1.5%, toxilic acid 0.5% mass ratio mix, and the sample of the gained that stirs is the water white transparency shape; But sample places under the 300W ultraviolet lamp 8cm place completely solidified in 5 seconds, and other The performance test results sees Table 1.
Contrast sample 2
In Glass Containers, add 2.5% SiO respectively
2Virahol dispersion liquid (SiO
2Content is 15%), 15% urethane acrylate, 87.5% acetone, blend is back ultra-sonic dispersion 15min well, 60 ℃ of following stirring heating 6h are to promote SiO
2The dispersion of particle in urethane acrylate, then pressure reducing and steaming acetone and isopropanol solvent; Then with the SiO that obtains
2Compound performed polymer (the SiO of/urethane acrylate
2Content 2.5%) by 60%, Rocryl 410 20%, TriMethylolPropane(TMP) (3 ethoxylation) triacrylate 5%, acid functional groups acrylate 10%, 1173 light triggers 2%, KH570 be 1%, the mass ratio of trolamine 1.5%, toxilic acid 0.5% mixes, the sample of the gained that stirs is the water white transparency shape; But sample places under the 300W ultraviolet lamp 8cm place completely solidified in 15 seconds; Solidify SiO in the sample of back
2Particle disperses synoptic diagram to see Fig. 3, and other The performance test results sees Table 1.
Contrast sample 3
Add 2.5% Si-4,15% urethane acrylate, 87.5% acetone in Glass Containers respectively, blend is back ultra-sonic dispersion 15min well, and 60 ℃ of following stirring heating 6h are to promote SiO
2The dispersion of particle in urethane acrylate, then pressure reducing and steaming acetone and isopropanol solvent; Then with the SiO that obtains
2Compound performed polymer (the SiO of/urethane acrylate
2Content 2.5%) by 60%, Rocryl 410 20%, TriMethylolPropane(TMP) (3 ethoxylation) triacrylate 5%, acid functional groups acrylate 10%, 1173 light triggers 2%, KH570 be 1%, the mass ratio of trolamine 1.5%, toxilic acid 0.5% mixes, the sample of the gained that stirs is the water white transparency shape; But sample places under the 300W ultraviolet lamp 8cm place completely solidified in 10 seconds; Solidify SiO in the sample of back
2Particle disperses synoptic diagram to see Fig. 4, and other The performance test results sees Table 1.Table 1 Example formulations gained UV glue properties of sample test result
| Test event | Viscosity (cp) | Transmitance (%) | Tensile shear strength (MPa) | Inhomogeneous pull strength (kN/m) |
| Embodiment 1 | 900 | 94.9 | 24.2 | 31.2 |
| Embodiment 2 | 1870 | 97.2 | 27.2 | 28.7 |
| Embodiment 3 | 3480 | 93.2 | 29.8 | 22.5 |
| Embodiment 4 | 3321 | 93.7 | 28.4 | 26.9 |
| Embodiment 5 | 620 | 98.7 | 22.1 | 27.5 |
| Embodiment 6 | 2450 | 96.4 | 25.4 | 29.7 |
| Embodiment 7 | 810 | 97.2 | 21.8 | 27.1 |
| Contrast sample 1 | 1450 | 97.4 | 16.1 | 20.4 |
| Contrast sample 2 | 2840 | 91.7 | 20.8 | 23.1 |
| Contrast sample 3 | 2720 | 92.4 | 21.9 | 23.3 |
The foregoing description is used for the present invention that explains, rather than limits the invention, and in the protection domain of spirit of the present invention and claim, any modification and change to the present invention makes all fall into protection scope of the present invention.
Claims (3)
1, a kind of nanometer SiO that is used for ultraviolet photo-curing cementing agent
2The method of modification is characterized in that, may further comprise the steps:
(1) be (R with general formula
1O)
3SiCH
2CH
2CH
2O (CH
2CH
2O)
a(CH
2CH (CH
3) O)
bC=OC (R
2)=CH
2Long-chain siloxanes coupling agent, to the SiO of particle diameter in 5～50nm scope
2The Virahol dispersion liquid carries out surface modification, obtains modification SiO
2/ Virahol dispersion liquid; Long-chain end in the described long-chain siloxanes coupling agent molecule has acrylic double bond, and the centre is a polyether segment, and wherein, a, b are arbitrary numerical value in 0～50 scope, R
1Be methyl or ethyl, R
2Be hydrogen atom or methyl; SiO in the described Virahol dispersion liquid
2Content is 10～30%; The modified-reaction temperature is 40～70 ℃, and the modified-reaction time is 4～8h, and coupling agent is at SiO
2Addition in the Virahol dispersion liquid is 5～20%.
(2) with the modification SiO that obtains in the step (1)
2/ Virahol dispersion liquid and urethane acrylate or epoxy acrylate, acetone solvent are pressed 0.5～10%, 5～40%, 50～90% mass ratio blend, and ultra-sonic dispersion 10～30min is at 30～60 ℃ of following stirring heating 3～6h, to promote SiO
2The dispersion of particle in urethane acrylate or epoxy acrylate, pressure reducing and steaming acetone and isopropanol solvent obtain SiO then
2/ urethane acrylate or SiO
2The compound performed polymer of/epoxy acrylate.
(3) with the SiO that obtains in the step (2)
2/ urethane acrylate or SiO
2Compound performed polymer, epoxy acrylate, hydroxyethyl methylacrylate or the Rocryl 410 of/epoxy acrylate, TriMethylolPropane(TMP)-3 ethoxylations-triacrylate, vinylformic acid or acid functional groups acrylate, 1173 light triggers, KH570, trolamine, toxilic acid mix by 20～60%, 0～25%, 0～30%, 0～8%, 0～15%, 0.5～3%, 0.5～1.5%, 0.5～1.5%, 0.2～1.0% mass ratio, obtain the UV tackiness agent after stirring.
2. a kind of nanometer SiO that is used for ultraviolet photo-curing cementing agent according to claim 1
2The method of modification is characterized in that, in the described step (1), and described nanometer SiO
2The modified-reaction temperature is 40～60 ℃, and the reaction times is 4～6h.
3. a kind of nanometer SiO that is used for ultraviolet photo-curing cementing agent according to claim 1
2The method of modification is characterized in that, in the described step (2), and described SiO
2The mass ratio of/Virahol dispersion liquid, urethane acrylate or epoxy acrylate, acetone solvent is 1～5%: 8～25%: 70～90%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610052461A CN100584894C (en) | 2006-07-14 | 2006-07-14 | Nanometer SiO2 modifying process of ultraviolet ray cured adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610052461A CN100584894C (en) | 2006-07-14 | 2006-07-14 | Nanometer SiO2 modifying process of ultraviolet ray cured adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1887972A true CN1887972A (en) | 2007-01-03 |
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