CN104312453A - Preparation method of ultraviolet cured silicon-containing acrylate conductive printed adhesive - Google Patents
Preparation method of ultraviolet cured silicon-containing acrylate conductive printed adhesive Download PDFInfo
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Abstract
The invention discloses a preparation method of an ultraviolet cured silicon-containing acrylate conductive printed adhesive. The adhesive is mainly prepared by synthesizing a silicon-containing acrylate resin substrate through a one-step process based on trimethyl chlorosilane and KH-550 as main raw materials and mixing the silicon-containing acrylate resin substrate with copper powder which is used as a conductive filler after wet milling, an active diluting agent vinyl pyrrolidone (NVP), a curing agent trihydroxymethyl propane triacrylate (TMPTA), a photoinitiator and the like. The preparation method of the conductive printed adhesive disclosed by the invention is simple and easy to control in process; and the prepared conductive printed adhesive has a good demoulding performance and dry etching resistance, and can replace a conventional Pb-Sn solder as a novel environment-friendly microelectronic packaging interconnection material.
Description
Technical field
The present invention relates to a kind of preparation method impressing glue of conducting electricity, particularly relate to the preparation method of a kind of ultraviolet light polymerization silyl acrylate ester type conduction impression glue.
Background technology
Along with the development of impression matrix material, ultraviolet stamping technology is widely used gradually.Ultraviolet stamping technique uses transparent template and light polyacetylene compound, its technical process is generally: be first coated in substrate by organic for one polymers soln spray (transfer layer), the low viscosity monomer solution (embossed layer) that spin coating more on the transfer layer (or dropping) one deck is very thin, impress under certain temperature and pressure condition, after monomer is full of stencil apertures completely, UV light permeability template back surface irradiates and makes monomer polymerization, curing molding recession mould, dry etching removes remaining etch layer and transfer layer by design transfer to substrate.
In order to obtain having Hi-Fi pattern, impression glue (etch layer) should have good flow deformation ability when impressing, and can fill full stencil apertures completely under pressure to make it;
When removing film, the pattern impressed to enable oneself intactly remains, and impression glue now should have very high mechanical stability;
When impressing glue and using as mask in order to ensure that pattern can transfer to substrate by dry etching smoothly from impression glue, impression glue now also should have higher anti-dry etching ability.
But the performance index of various impression glue that oneself commercially produces at present cannot meet above-mentioned requirements, for meeting the performance index requirement of mechanical stability and anti-dry etching ability, often have higher surface energy simultaneously.Thus, in use ubiquity is easy to the technical problem occurring conductive resin and template adhesion.
" Chinese tackiness agent " August the 14th in 2005, volume the 8th phase 27-30 page disclosed one " UV radiation-curable epoxy acrylate resin conductive resin ", and its raw material and reagent are: homemade epoxy acrylic resin, industrial goods NVP (NVP), industrial goods Viscoat 295 (TMPTA), industrial goods benzoin dimethylether, chemical pure benzophenone, 200 order copper powders, industrial goods Silane coupling reagent KH-570 and analytical pure ethylenediamine tetraacetic acid (EDTA);
Its main technological steps is: plate copper powder wet grinding in planetary ball mill being become 1-10 micron; Photosensitive resin is obtained with epoxy acrylic resin, NVP, TMPTA, benzoin dimethylether and benzophenone Homogeneous phase mixing; Again the copper powder of above-mentioned process is mixed with photosensitive resin, obtained conductive resin." after isotropy, solidification, resistivity can reach 1.3 × 10 to obtained conductive resin
-3ou Mu ㎝, shearing resistance can reach 1.3MPa.
But, this UV radiation-curable epoxy acrylate resin conductive resin, because its matrix uses pure organic epoxy acrylic resin, thus there is higher surface energy, the introducing of this higher surface energy material component, inevitably by causing its finished product conduction impression glue must have higher viscosity, in moulding process, be easy to the problem occurring adhesion between template and impression glue.
Due to template in moulding process and the gluing company of impression, on the one hand, constrain the raising of impression quality, very difficult acquisition has Hi-Fi imprinted pattern; On the other hand, when this adhesion phenomenon is serious, even may cause the damage of template, thus constrain the lifting of template impression quantity, and then cause unit to impress high expensive.
For solving the technical problem easily occurring conductive resin and template adhesion in moulding process, often template can only be modified, to improving the antiblocking ability of template by means of using the antisticking agent had compared with low surface energy.But effect is unsatisfactory in the actual use procedure of this method, repeatedly repeatedly impression after, impression glue can release property deterioration.Particularly, when forming high-aspect ratio pattern, the contact area between template and impression glue increases, and the normal phenomenon occurring impression glue and template adhesion, causes pattern and occur defect.
Therefore, develop the polymkeric substance with better impression performance and impress glue to meet the technical requirements of high quality impression, improve impression quality further, oneself becomes the developing direction impressing glue technology.
Summary of the invention
The object of the invention is to, the preparation method that a kind of ultraviolet light polymerization silyl acrylate ester type conducts electricity impression glue is provided, its preparation technology is simple, and obtained impression glue has the features such as viscosity is low, strong and good, the anti-dry etching ability of demolding performace is good with the adhesive power of base plate.
The technical scheme that the present invention is adopted for achieving the above object is, a kind of preparation method of ultraviolet light polymerization silyl acrylate ester type conduction impression glue, is characterized in that, comprise the following steps:
The first step, the preparation process of conductive filler material copper powder:
Adopt wet ball grinding process copper powder, in copper powder, add dehydrated alcohol as medium, carry out ball milling with planetary ball mill under nitrogen protection, grinding 20h, obtain in pearly-lustre look, flake copper that particle diameter is 1-10 micron;
The dilution heat of sulfuric acid being 5% by above-mentioned flake copper concentration washs three times, then washes three times, after filtration with dehydrated alcohol, adds coupling agent, puts into vacuum drying oven fast, drying for standby in filter residue;
Second step, the step of synthesis acrylate containing silicone resin matrix:
By mass fraction, by 163 parts of trimethylchlorosilanes and 62 parts of silane resin acceptor kh-550 mixing, and in 30min, evenly drip the mixing solutions of the deionized water of 40.8 parts and the methyl alcohol of 48 parts, be stirred to evenly; Temperature of reaction controls lower than 50 DEG C;
Continue under room temperature to stir 12h, after organic phase being washed to neutrality, drying, underpressure distillation removing low-boiling-point substance obtains crude product;
Again under 2mmHg, above-mentioned crude product is carried out rectifying, collect the cut of 112-116 DEG C, obtain acrylate containing silicone resin matrix;
3rd step, the preparation process of ultraviolet light polymerization silyl acrylate ester type conduction impression glue:
Using obtained acrylate containing silicone resin matrix as basic resin, with reactive thinner NVP, Viscoat 295, mix in the ratio of mass fraction 1-2: 1-2: 3, add benzoin dimethylether or benzophenone as light trigger simultaneously, and be uniformly mixed, obtained photosensitive resin;
The add-on of above-mentioned benzoin dimethylether or benzophenone is the 1-2% of basic resin, reactive thinner NVP and Viscoat 295 gross weight;
Again copper powder and the photosensitive resin ratio uniform by weight 1-5: 1 is mixed, to obtain final product.
The technique effect that technique scheme is directly brought is, by introducing silicone ingredients mode in resin matrix, effectively reduces the surface energy of resin matrix, and then effectively reduces the viscosity of the finished product conduction impression glue.The conduction impression glue adopting above-mentioned preparation method to obtain both had had good conductivity and the stronger cohesive force to baseboard material, had lower surface energy again, thus had good demolding performace.
Reason is: silicoorganic compound have lower surface energy, utilizes it to material modification or is mixed into formula and can obtains good desired result.Because this quasi-molecule has carbochain and silicon chain two kinds of main chains, its character is similar to tensio-active agent, time on the substrate surface such as quartz, metal, silicon being coated to high surface energy, can microphase-separated be there is in multipolymer, the trend of the oriented impression glue of the polydimethylsiloxane group that surface energy is low and Air Interface enrichment, makes surface energy reduce;
And the trend of the oriented impression glue of organic group in silicoorganic compound and substrate interface enrichment, make to form good adhesive power between impression glue and ground.
Technique scheme, with trimethylchlorosilane and silane resin acceptor kh-550 for raw material, adopt " single stage method " to synthesize acrylate containing silicone resin matrix, preparation technology is simple for its resin matrix; More crucially, the organosilicon of the acrylate containing silicone resin matrix of synthesis, it not only has pliable and tough siloxane main chain, and its side chain can carry a large amount of functional group.
According to photocuring basic theories, because photocuring reaction speed is larger, during reaction, the volumetric shrinkage speed of system is much smaller than solidification rate, volumetric shrinkage has little time to reach balance, therefore a large amount of temporary additional free volume is caused, these free volumes improve the mobility of double bond and active specy, thus improve the final transformation efficiency of double bond, the polyfunctional group material of this structure formation has the fast feature with there is free volume effect of initiating stage curing speed, is thus more suitable for ultraviolet light polymerization.
Therefore, conduction impression glue prepared by preparation method of the present invention, UV-light is utilized to be cured conduction impression glue, traditional method of being heating and curing can be avoided may to cause the incomplete displacement of polymkeric substance, namely can not fill the phenomenons such as the cavity of seal completely, further ensure high-quality impression quality; And UV curing process does not need high temperature, high pressure, cheap in technique, be conducive to realizing suitability for industrialized production.
Be preferably, the weight ratio of above-mentioned copper powder and photosensitive resin is 4: 1.
The technique effect that this optimal technical scheme is directly brought is, when the weight ratio of copper powder and photosensitive resin is 4: 1, obtained conduction impression glue conductivity and shearing resistance best.
Further preferably, the raw material copper powder that the preparation of above-mentioned flake copper is used, its particle diameter is 200 orders.
The technique effect that this optimal technical scheme is directly brought is that copper powder size is less, and its surface-area is larger, and surface atom accounting is higher, and sintering temperature is lower; If but particle diameter is too little, form Large stone coacervate before sintering, then conductive resin is difficult to integral sintered, but forms dispersion block.Therefore, particle diameter is selected to be that 200 order copper powders are most suitable as raw material.
Further preferably, above-mentioned silane resin acceptor kh-550, solidifying agent Viscoat 295 and benzoin dimethylether are industrial goods; Described trimethylchlorosilane, methyl alcohol and benzophenone are chemical pure.
The technique effect that this optimal technical scheme is directly brought is, consider the cost budgeting of suitability for industrialized production, the price of the silane resin acceptor kh-550 of industrial goods, solidifying agent Viscoat 295 and benzoin dimethylether is lower, itself is also well positioned to meet the performance of product simultaneously; And for trimethylchlorosilane, methyl alcohol and benzophenone, consider the reasons such as consumption is little, purity requirement is high, preferably use the purity grade of more than chemical pure.
In sum, the preparation method of ultraviolet light polymerization silyl acrylate ester type conduction impression glue of the present invention has the features such as preparation technology is simple, production cost is low, prepared conduction impression glue had both had good conductivity and the stronger cohesive force to baseboard material, there is again lower surface energy, fully can meet the technical requirements of high-quality impression.
Accompanying drawing explanation
Fig. 1 is the test result graphic representation of the conduction impression glue resistivity that the present invention prepares;
Fig. 2 is that the massfraction of the conduction impression glue matrix resin that the present invention prepares affects test result graphic representation to conductive resin surface energy and conductive resin shearing resistance;
Fig. 3 be the present invention prepare conduction impression glue copper powder and matrix resin mass ratio to the influence curve figure of solidification rate;
The conduction impression glue light trigger of Fig. 4 prepared by the present invention is to the test result figure of solidification rate;
Fig. 5 prepared by the present invention conduction impression glue photosensitive resin formulation comparison separating force and shearing resistance affect test result figure.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail.
Illustrate: involved by present specification:
KH550: chemical name is γ-aminopropyl triethoxysilane, structural formula is NH
2cH
2cH
2cH
2si (OC
2h
5)
3);
TMPTA: chemical name is Viscoat 295, structural formula is (CH
2=CHCOOCH
2)
3-CCH
2cH
3;
NVP: chemical name is NVP, molecular formula is C
6h
9oN.
Embodiment 1:
Adopt wet ball grinding process copper powder, in copper powder, add dehydrated alcohol as medium, carry out ball milling with planetary ball mill under nitrogen protection, grinding 20h, obtain in pearly-lustre look, flake copper that particle diameter is 1-10 micron;
The dilution heat of sulfuric acid being 5% by above-mentioned flake copper concentration washs three times, then washes three times, after filtration with dehydrated alcohol, adds dispersion agent or coupling agent, puts into vacuum drying oven fast, drying for standby in filter residue;
By mass fraction, by 163 parts of trimethylchlorosilanes and 62 parts of KH-550 mixing, and in 30min, evenly drip the mixing solutions of the deionized water of 40.8 parts and the methyl alcohol of 48 parts, be stirred to evenly; Temperature of reaction controls lower than 50 DEG C;
After continuing to stir 12h under room temperature, after organic phase being washed to neutrality, drying, underpressure distillation removing low-boiling-point substance obtains crude product;
Again under 2mmHg, above-mentioned crude product is carried out rectifying, collect the cut of 112-116 DEG C, obtain acrylate containing silicone resin matrix;
Using obtained acrylate containing silicone resin matrix as basic resin, with reactive thinner NVP, Viscoat 295, mix in the ratio of mass fraction 1: 1: 3, add benzoin dimethylether as light trigger simultaneously, and be uniformly mixed, obtained photosensitive resin;
The add-on of above-mentioned benzoin dimethylether is 2% of basic resin, reactive thinner NVP and Viscoat 295 gross weight;
Again copper powder and the photosensitive resin ratio uniform by weight 4: 1 is mixed, to obtain final product.
Embodiment 2
Adopt wet ball grinding process copper powder, in copper powder, add dehydrated alcohol as medium, carry out ball milling with planetary ball mill under nitrogen protection, grinding 20h, obtain in pearly-lustre look, flake copper that particle diameter is 1-10 micron;
The dilution heat of sulfuric acid being 5% by above-mentioned flake copper concentration washs three times, then washes three times, after filtration with dehydrated alcohol, adds dispersion agent or coupling agent, puts into vacuum drying oven fast, drying for standby in filter residue;
By mass fraction, by 163 parts of trimethylchlorosilanes and 62 parts of KH-550 mixing, and in 30min, evenly drip the mixing solutions of the deionized water of 40.8 parts and the methyl alcohol of 48 parts, be stirred to evenly; Temperature of reaction controls lower than 50 DEG C;
After continuing to stir 12h under room temperature, after organic phase being washed to neutrality, drying, underpressure distillation removing low-boiling-point substance obtains crude product;
Again under 2mmHg, above-mentioned crude product is carried out rectifying, collect the cut of 112-116 DEG C, obtain acrylate containing silicone resin matrix;
Using obtained acrylate containing silicone resin matrix as basic resin, with reactive thinner NVP, Viscoat 295, mix in the ratio of mass fraction 2: 2: 3, add benzophenone as light trigger simultaneously, and be uniformly mixed, obtained photosensitive resin;
The add-on of above-mentioned benzophenone is 1% of basic resin, reactive thinner NVP and Viscoat 295 gross weight;
Again copper powder and the photosensitive resin ratio uniform by weight 4: 1 is mixed, to obtain final product.
Embodiment 3
Adopt wet ball grinding process copper powder, in copper powder, add dehydrated alcohol as medium, carry out ball milling with planetary ball mill under nitrogen protection, grinding 20h, obtain in pearly-lustre look, flake copper that particle diameter is 1-10 micron;
The dilution heat of sulfuric acid being 5% by above-mentioned flake copper concentration washs three times, then washes three times, after filtration with dehydrated alcohol, adds dispersion agent or coupling agent, puts into vacuum drying oven fast, drying for standby in filter residue;
By mass fraction, by 163 parts of trimethylchlorosilanes and 62 parts of KH-550 mixing, and in 30min, evenly drip the mixing solutions of the deionized water of 40.8 parts and the methyl alcohol of 48 parts, be stirred to evenly; Temperature of reaction controls lower than 50 DEG C;
After continuing to stir 12h under room temperature, after organic phase being washed to neutrality, drying, underpressure distillation removing low-boiling-point substance obtains crude product;
Again under 2mmHg, above-mentioned crude product is carried out rectifying, collect the cut of 112-116 DEG C, obtain acrylate containing silicone resin matrix;
Using obtained acrylate containing silicone resin matrix as basic resin, with reactive thinner NVP, Viscoat 295, mix in the ratio of mass fraction 1: 1: 2, add benzophenone as light trigger simultaneously, and be uniformly mixed, obtained photosensitive resin;
The add-on of above-mentioned benzophenone is 1% of basic resin, reactive thinner NVP and Viscoat 295 gross weight;
Again copper powder and the photosensitive resin ratio uniform by weight 4: 1 is mixed, to obtain final product.
Embodiment 4
Adopt wet ball grinding process copper powder, in copper powder, add dehydrated alcohol as medium, carry out ball milling with planetary ball mill under nitrogen protection, grinding 20h, obtain in pearly-lustre look, flake copper that particle diameter is 1-10 micron;
The dilution heat of sulfuric acid being 5% by above-mentioned flake copper concentration washs three times, then washes three times, after filtration with dehydrated alcohol, adds dispersion agent or coupling agent, puts into vacuum drying oven fast, drying for standby in filter residue;
By mass fraction, by 163 parts of trimethylchlorosilanes and 62 parts of KH-550 mixing, and in 30min, evenly drip the mixing solutions of the deionized water of 40.8 parts and the methyl alcohol of 48 parts, be stirred to evenly; Temperature of reaction controls lower than 50 DEG C;
After continuing to stir 12h under room temperature, after organic phase being washed to neutrality, drying, underpressure distillation removing low-boiling-point substance obtains crude product;
Again under 2mmHg, above-mentioned crude product is carried out rectifying, collect the cut of 112-116 DEG C, obtain acrylate containing silicone resin matrix;
Using obtained acrylate containing silicone resin matrix as basic resin, with reactive thinner NVP, Viscoat 295, mix in the ratio of mass fraction 1: 1: 2, add benzoin dimethylether as light trigger simultaneously, and be uniformly mixed, obtained photosensitive resin;
The add-on of above-mentioned benzoin dimethylether is 2% of basic resin, reactive thinner NVP and Viscoat 295 gross weight;
Again copper powder and the photosensitive resin ratio uniform by weight 4: 1 is mixed, to obtain final product.
Embodiment 5
Adopt wet ball grinding process copper powder, in copper powder, add dehydrated alcohol as medium, carry out ball milling with planetary ball mill under nitrogen protection, grinding 20h, obtain in pearly-lustre look, flake copper that particle diameter is 1-10 micron;
The dilution heat of sulfuric acid being 5% by above-mentioned flake copper concentration washs three times, then washes three times, after filtration with dehydrated alcohol, adds dispersion agent or coupling agent, puts into vacuum drying oven fast, drying for standby in filter residue;
By mass fraction, by 163 parts of trimethylchlorosilanes and 62 parts of KH-550 mixing, and in 30min, evenly drip the mixing solutions of the deionized water of 40.8 parts and the methyl alcohol of 48 parts, be stirred to evenly; Temperature of reaction controls lower than 50 DEG C;
After continuing to stir 12h under room temperature, after organic phase being washed to neutrality, drying, underpressure distillation removing low-boiling-point substance obtains crude product;
Again under 2mmHg, above-mentioned crude product is carried out rectifying, collect the cut of 112-116 DEG C, obtain acrylate containing silicone resin matrix;
Using obtained acrylate containing silicone resin matrix as basic resin, with reactive thinner NVP, Viscoat 295, mix in the ratio of mass fraction 1: 1: 3, add benzoin dimethylether as light trigger simultaneously, and be uniformly mixed, obtained photosensitive resin;
The add-on of above-mentioned benzoin dimethylether is 2% of basic resin, reactive thinner NVP and Viscoat 295 gross weight;
Again copper powder and the photosensitive resin ratio uniform by weight 2: 1 is mixed, to obtain final product.
Embodiment 6
Adopt wet ball grinding process copper powder, in copper powder, add dehydrated alcohol as medium, carry out ball milling with planetary ball mill under nitrogen protection, grinding 20h, obtain in pearly-lustre look, flake copper that particle diameter is 1-10 micron;
The dilution heat of sulfuric acid being 5% by above-mentioned flake copper concentration washs three times, then washes three times, after filtration with dehydrated alcohol, adds dispersion agent or coupling agent, puts into vacuum drying oven fast, drying for standby in filter residue;
By mass fraction, by 163 parts of trimethylchlorosilanes and 62 parts of KH-550 mixing, and in 30min, evenly drip the mixing solutions of the deionized water of 40.8 parts and the methyl alcohol of 48 parts, be stirred to evenly; Temperature of reaction controls lower than 50 DEG C;
After continuing to stir 12h under room temperature, after organic phase being washed to neutrality, drying, underpressure distillation removing low-boiling-point substance obtains crude product;
Again under 2mmHg, above-mentioned crude product is carried out rectifying, collect the cut of 112-116 DEG C, obtain acrylate containing silicone resin matrix;
Using obtained acrylate containing silicone resin matrix as basic resin, with reactive thinner NVP, Viscoat 295, mix in the ratio of mass fraction 1: 1: 3, add benzoin dimethylether as light trigger simultaneously, and be uniformly mixed, obtained photosensitive resin;
The add-on of above-mentioned benzoin dimethylether is 2% of basic resin, reactive thinner NVP and Viscoat 295 gross weight;
Again copper powder and the photosensitive resin ratio uniform by weight 3: 1 is mixed, to obtain final product.
Embodiment 7
Adopt wet ball grinding process copper powder, in copper powder, add dehydrated alcohol as medium, carry out ball milling with planetary ball mill under nitrogen protection, grinding 20h, obtain in pearly-lustre look, flake copper that particle diameter is 1-10 micron;
The dilution heat of sulfuric acid being 5% by above-mentioned flake copper concentration washs three times, then washes three times, after filtration with dehydrated alcohol, adds dispersion agent or coupling agent, puts into vacuum drying oven fast, drying for standby in filter residue;
By mass fraction, by 163 parts of trimethylchlorosilanes and 62 parts of KH-550 mixing, and in 30min, evenly drip the mixing solutions of the deionized water of 40.8 parts and the methyl alcohol of 48 parts, be stirred to evenly; Temperature of reaction controls lower than 50 DEG C;
After continuing to stir 12h under room temperature, after organic phase being washed to neutrality, drying, underpressure distillation removing low-boiling-point substance obtains crude product;
Again under 2mmHg, above-mentioned crude product is carried out rectifying, collect the cut of 112-116 DEG C, obtain acrylate containing silicone resin matrix;
Using obtained acrylate containing silicone resin matrix as basic resin, with reactive thinner NVP, Viscoat 295, mix in the ratio of mass fraction 1: 1: 3, add benzoin dimethylether as light trigger simultaneously, and be uniformly mixed, obtained photosensitive resin;
The add-on of above-mentioned benzoin dimethylether is 2% of basic resin, reactive thinner NVP and Viscoat 295 gross weight;
Again copper powder and the photosensitive resin ratio uniform by weight 5: 1 is mixed, to obtain final product.
For understanding the present invention better, existing the present invention is described in detail by reference to the accompanying drawings.
The test result graphic representation of the conduction impression glue resistivity of Fig. 1 prepared by embodiment 1-7; The massfraction of the conduction impression glue photosensitive resin of Fig. 2 prepared by embodiment 1-7 affects test result graphic representation to conductive resin surface energy and conductive resin shearing resistance; Fig. 3 prepared by embodiment 1-7 conduction impression glue copper powder and photosensitive resin mass ratio to the influence curve figure of solidification rate; The conduction impression glue light trigger of Fig. 4 prepared by embodiment 1-7 is to the test result figure of solidification rate; Fig. 5 be conduction impression glue photosensitive resin formulation comparison separating force prepared in embodiment 1-7 and shearing resistance affect test result figure.
As shown in Figure 1, when the mass ratio of copper powder and photosensitive resin is 4:1, resistivity now reaches optimum value, and when the ratio of copper powder and photosensitive resin is 4:1, can find out, resistivity is now minimum is 6.12 × 10
-4Ω .cm;
The resistivity that conduction impresses glue is relevant with the copper powder content added in conductive filler material, if the copper powder added is very few, after solidification is dry, in glue-line, conductive path connects the non-conductive or poor electric conductivity of possibility, and along with the ratio adding copper powder increases, resistivity improves gradually.
But when copper powder addition reaches certain value, resistivity can decrease, analyze because after the massfraction of copper powder increases, the content of photosensitive resin reduces, and causes the strength of joint of conduction impression glue inside to reduce, causes conductivity to be deteriorated.
As shown in Figure 2, first along with the increase of the massfraction of photosensitive resin, the increase of the siliceous composition in photosensitive resin, and the surface energy of material is less, thus conductive resin surface energy is progressively reduced, but the continuous increase of massfraction along with photosensitive resin, the degree that the conductive resin surface energy in later stage reduces tends towards stability, by Tu Ke get, the surface energy of conduction impression glue is by 30.2mJm
-2be reduced to 20.4mJm
-2.Can also find out in the drawings, along with the increase of photosensitive resin, the shearing resistance of conductive resin is also in enhancing.When matrix resin is about 25% time, shearing resistance is 1.74MPa, reaches commercialization conductive adhesive intensity.And under the massfraction of photosensitive resin at this moment, the surface energy of conductive resin and the shearing resistance value of conductive resin all can reach optimum value.
Describe the surface energy that matrix resin reduces conduction impression glue, the analysis of causes is, the surface energy of material is less.
As shown in Figure 3, when changing copper powder and photosensitive resin mass ratio, curing speed has substantial connection with the photosensitive resin in conduction impression glue and copper powder, and along with the raising of conductive filler material copper powder ratio, set time shortens gradually, when mass ratio is 4:1, set time, afterwards, the curing speed that adds of copper powder no longer increased close to being worth 33s the soonest, because, the minimizing of the probability of free radical contact between photosensitive resin.
As shown in Figure 4, benzoin dimethylether and the solidification rate of benzophenone two kinds of light triggers on conduction impression glue affect less, and the solidification rate all when addition is 2% is closest to ideal value.Analysis reason is, according to radically curing mechanism, if initiator amount is large, the free radical fragment produced in unit time is many, although solidification rate can increase, initiator amount is excessive, not only reduce the resistance to deterioration of conductive resin, be also unfavorable for the control of cost.
As shown in Figure 5, when acrylate containing silicone resin matrix is as basic resin, with reactive thinner NVP, Viscoat 295, when mixing in the ratio of mass fraction 1: 1: 3, being separated force value minimum is 13N, and shearing resistance now also reaches ideal value 1.73MPa.
Claims (4)
1. a preparation method for ultraviolet light polymerization silyl acrylate ester type conduction impression glue, is characterized in that, comprise the following steps:
The first step, the preparation process of conductive filler material copper powder:
Adopt wet ball grinding process copper powder, in copper powder, add dehydrated alcohol as medium, carry out ball milling with planetary ball mill under nitrogen protection, grinding 20h, obtain in pearly-lustre look, flake copper that particle diameter is 1-10 micron;
The dilution heat of sulfuric acid being 5% by above-mentioned flake copper concentration washs three times, then washes three times, after filtration with dehydrated alcohol, adds coupling agent, puts into vacuum drying oven fast, drying for standby in filter residue;
Second step, the step of synthesis acrylate containing silicone resin matrix:
By mass fraction, by 163 parts of trimethylchlorosilanes and 62 parts of silane resin acceptor kh-550 mixing, and in 30min, evenly drip the mixing solutions of the deionized water of 40.8 parts and the methyl alcohol of 48 parts, be stirred to evenly; Temperature of reaction controls lower than 50 DEG C;
Continue under room temperature to stir 12h, after organic phase being washed to neutrality, drying, underpressure distillation removing low-boiling-point substance obtains crude product;
Again under 2mmHg, above-mentioned crude product is carried out rectifying, collect the cut of 112-116 DEG C, obtain acrylate containing silicone resin matrix;
3rd step, the preparation process of ultraviolet light polymerization silyl acrylate ester type conduction impression glue:
Using obtained acrylate containing silicone resin matrix as basic resin, with reactive thinner NVP, Viscoat 295, mix in the ratio of mass fraction 1-2: 1-2: 3, add benzoin dimethylether or benzophenone as light trigger simultaneously, and be uniformly mixed, obtained photosensitive resin;
The add-on of above-mentioned benzoin dimethylether or benzophenone is the 1-2% of basic resin, reactive thinner NVP and Viscoat 295 gross weight;
Again copper powder and the photosensitive resin ratio uniform by weight 1-5: 1 is mixed, to obtain final product.
2. the preparation method of ultraviolet light polymerization silyl acrylate ester type conduction impression glue according to claim 1, it is characterized in that, the weight ratio of described copper powder and photosensitive resin is 4: 1.
3. the preparation method of ultraviolet light polymerization silyl acrylate ester type according to claim 1 conduction impression glue, is characterized in that, the raw material copper powder that the preparation of described flake copper is used, and its particle diameter is 200 orders.
4. the preparation method of ultraviolet light polymerization silyl acrylate ester type conduction impression glue according to claim 1, is characterized in that described silane resin acceptor kh-550, solidifying agent Viscoat 295 and benzoin dimethylether are industrial goods;
Described trimethylchlorosilane, methyl alcohol and benzophenone are chemical pure.
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| CN108834325A (en) * | 2018-08-15 | 2018-11-16 | 郑胜 | A kind of production method of one-sided circuit board |
| CN112898827A (en) * | 2021-01-27 | 2021-06-04 | 西安思摩威新材料有限公司 | Ultraviolet curing packaging ink based on silicon-oxygen side chain-containing two-dimensional acrylate monomer and use method and application thereof |
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| CN112898827A (en) * | 2021-01-27 | 2021-06-04 | 西安思摩威新材料有限公司 | Ultraviolet curing packaging ink based on silicon-oxygen side chain-containing two-dimensional acrylate monomer and use method and application thereof |
| CN112898827B (en) * | 2021-01-27 | 2022-10-18 | 西安思摩威新材料有限公司 | Ultraviolet curing packaging ink based on silicon-oxygen side chain-containing two-dimensional acrylate monomer and use method and application thereof |
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