CN103160211A - Solar crystalline silicon rod splicing glue and preparation method thereof - Google Patents

Abstract

The invention relates to a splicing adhesive for solar crystal silicon rods and a preparation method thereof, which is composed of anaerobic glue and an accelerator. The preparation method is to prepare the anaerobic glue and the accelerator respectively. Coat the accelerator on the surface, dry it, and then apply anaerobic glue, and the butt joint will be bonded quickly. On the premise of ensuring sufficient strength and toughness in the process of wafer cutting, the splicing adhesive for solar crystal silicon rods of the present invention has the characteristics of fast positioning time, convenient operation, good resistance to chemical media, and good storage stability, and will become an adhesive for industrial use. agent of choice.

Description

A kind of solar crystal silicon rod splicing adhesive and preparation method thereof

technical field

The invention relates to a splicing adhesive for solar crystal silicon rods and a preparation method thereof.

Background technique

In recent years, China's solar photovoltaic industry has developed rapidly and has become one of the few emerging industries with strong international competitiveness. The center of gravity of the industry is gradually shifting to China. The production process of solar cells in the photovoltaic industry is generally: ingot casting → square cutting → slicing → module → assembly.

At present, two-component epoxy resin glue is generally used for the splicing glue of solar crystal silicon rods. Epoxy resin glue has the advantage of high bonding strength, but at the same time has many significant disadvantages, specifically: the curing and positioning of silicon rods takes a long time, which affects the production process, and it is difficult to meet the process requirements even if a fast curing agent is used; Resin amine curing agent is poisonous, which pollutes the operating environment greatly, and operators often have adverse reactions such as irritation and allergies; the bonding strength and modulus attenuation decrease greatly in the water-based/oily cutting fluid environment; the operation is troublesome, and the ratio of group A and B Strict, the mixing must be uniform; sensitive to temperature and humidity, poor storage stability, prone to surface crust deterioration under long-term storage conditions, and even serious accidents of chip or rod drop in severe cases.

Contents of the invention

In order to solve the shortcomings of the epoxy resin stick glue used in the prior art, such as long positioning time, low strength, poor impact toughness, troublesome operation, sensitive environment moisture, and poor storage stability, the invention provides a solar crystal silicon Stick splicing glue, which has the advantages of convenient operation, fast positioning time, high bonding strength, good impact toughness, good chemical resistance, and good storage stability, which greatly improves the performance of stick glue.

The technical scheme of the present invention to solve the above-mentioned technical problems is as follows: a solar crystalline silicon rod splicing glue, which is composed of anaerobic glue and accelerator,

Wherein, the anaerobic glue is composed of the following raw materials in parts by weight: 10 to 30 parts of diluent, 20 to 80 parts of oligomer, 1 to 5 parts of coupling agent, 1 to 5 parts of oxidizing agent, and 0.2 parts of reducing agent. -0.8 parts, 0.1-0.5 parts of co-reducing agent, 0.01-0.03 parts of polymerization inhibitor; the surface accelerator is composed of the following raw materials in parts by weight: 0.1-1 part of metal organic acid salt, and 90-99.9 parts of solvent.

The beneficial effects of the present invention are: the present invention is aimed at the process and performance requirements of the special glue for splicing solar crystal silicon rods. Auxiliaries such as polymerizing agents become special anaerobic adhesives for splicing silicon rods. By adding metal organic acid salts to the surface accelerator components, the traditional toxic solvents such as acetone and chloroform are discarded, and non-toxic absolute ethanol is used as the solvent to shorten the positioning time of the cured adhesive and improve storage stability. Adhesive strength, impact toughness, improve process operability and chemical medium resistance, reduce environmental moisture sensitivity; and evaluate the performance comparison test of the anaerobic adhesive of the present invention and the traditional epoxy resin adhesive.

On the basis of the above technical solutions, the present invention can also be improved as follows.

Further, the diluent is one or a mixture of tetraethylene glycol polyacrylate, hydroxyethyl methacrylate, and 2-phenoxyethyl acrylate.

Further, the oligomer is one or a mixture of ethoxylated bisphenol A dimethacrylate (preferably the commercially available BPA2EODMA model of Changxing Chemical Company), bisphenol A epoxy acrylate, and polyurethane diester.

Further, the oxidizing agent is one or more of benzoyl peroxide, cumene hydroperoxide, and tert-butyl peroxybenzoate.

Further, the reducing agent is one or a combination of triethylamine, N,N-dimethylaniline, and triethanolamine; the co-reducing agent is insoluble saccharin.

Further, the polymerization inhibitor is one or a mixture of 1,4-naphthoquinone, hydroquinone and p-benzoquinone.

Further, the coupling agent is (2,3-epoxypropyl)propyltrimethoxysilane A-187.

Further, the surface accelerator is one or a combination of ferrocene ethanol solution, copper acetate ethanol solution, copper isooctanoate ethanol solution, and copper acetylacetonate ethanol solution.

The technical solution of the present invention to solve the above-mentioned technical problems is as follows: a method for preparing solar crystalline silicon rod splicing glue, comprising the following steps:

(1) Prepare anaerobic glue and surface accelerator respectively:

1) Add 20-80 parts by weight of oligomer, 10-30 parts of diluent, and 0.01-0.03 parts of polymerization inhibitor into the mixer and mix evenly, then add 0.2-0.8 parts by weight of reducing agent, 0.1-0.5 parts of co-reducing agent, heating first, then stirring, then cooling down to room temperature, then adding 1-5 parts by weight of coupling agent, stirring again, and then vacuumizing to obtain the obtained The anaerobic glue of the splicing glue for solar crystalline silicon rods;

2) Add 0.1-1 part by weight of metal-organic acid powder and 90-99.9 parts of solvent into a mixer and stir until the mixture is uniform, and the surface accelerator for the solar crystal silicon rod splicing glue is obtained.

(2) When in use, the surface of the silicon rod to be bonded is coated with a surface accelerator, dried, and then coated with anaerobic glue, and the butt joint is quickly bonded. It can be positioned in about 10 seconds, and the wafer can be cut after curing.

On the basis of the above technical solutions, the present invention can also be improved as follows.

Further, in step 1), the temperature after the heating is 40-60°C.

Further, in step 1), the stirring process conditions are: stirring for 0.3-1 hour under the conditions of rotation speed of 500-1000 rpm and revolution speed of 5-8 rpm.

Further, in step 1), the time for stirring again is 0.5 to 1.5 hours; the process conditions for vacuuming are: vacuuming for 5 to 15 minutes to make the vacuum degree to -0.1 to -0.08 MPa.

Further, in step 2), the stirring process conditions are as follows: stirring for 0.2-1 hour under the condition that the rotation speed is 200-500 revolutions/minute and the revolution speed is 5-8 revolutions/minute.

The beneficial effects of the present invention are: the solar crystalline silicon rod splicing glue of the present invention can significantly improve the workpiece positioning time, Improve bonding strength and impact toughness, improve storage stability, process operability and resistance to chemical media, and reduce environmental moisture sensitivity.

Detailed ways

The principles and features of the present invention are described below, and the examples given are only used to explain the present invention, and are not intended to limit the scope of the present invention.

Example 1

Accurately weigh the following raw materials: 67 parts of ethoxylated bisphenol A dimethacrylate, 15 parts of tetraethylene glycol polyacrylate, and 0.02 parts of 1,4-naphthoquinone, add them into a double planetary power mixing mixer and mix evenly , then add 0.5 parts of N,N-dimethylaniline and 0.3 parts of saccharin, and heat up to 40°C. Under the condition that the rotation speed of the double planetary power mixer is 500 rpm and the revolution speed is 8 rpm, Mechanically stir for 0.5 hours to completely dissolve, then quickly cool down to room temperature, add 3 parts of benzoyl peroxide, and then add 2 parts of A-187 coupling agent, stir for 1 hour, then vacuum for 10 minutes, and the vacuum degree reaches - 0.1 MPa. After discharging, the anaerobic glue solution for splicing solar crystal silicon rods of the present invention is obtained, which is packaged and placed for use.

Accurately weigh the components of the surface accelerator as follows: add 0.2 parts of copper isooctanoate powder by weight and 99.8 parts of absolute ethanol as a solvent, and add them to a double planetary power mixer for mixing, and the rotation speed of the double planetary power mixer is 300 rpm /min, under the condition that the revolution speed is 5 revs/min, mechanically stir for 0.5 hour, discharge, promptly obtain the accelerant of splicing glue of solar crystal silicon rod of the present invention, pack and place for use.

Example 2

Accurately weigh the following raw materials: 60 parts of bisphenol A epoxy acrylate, 20 parts of ethoxylated bisphenol A dimethacrylate, 10 parts of hydroxyethyl methacrylate, 0.02 parts of hydroquinone and add double planetary power Mix evenly in the mixing mixer, then add 0.2 parts of triethylamine and 0.1 parts of saccharin, heat up to 60°C, under the condition that the rotation speed of the double planetary power mixing mixer is 500 rpm and the revolution speed is 8 rpm, Mechanically stir for 0.5 hours to completely dissolve, then quickly cool down to room temperature, add 2 parts of cumene hydroperoxide, and then add 1 part of A-187 coupling agent, stir for 1 hour, then vacuumize for 10 minutes, and the vacuum degree reaches -0.08MPa. After discharging, the anaerobic glue solution for splicing solar crystal silicon rods of the present invention is obtained, which is packaged and placed for use.

Accurately weigh the components of the surface accelerator as follows: add 0.8 parts of butyl ferrocene and 99.2 parts of absolute ethanol as a solvent and mix them in a double planetary power mixer, and the rotation speed of the double planetary power mixer is 300 revolutions per minute, under the condition of a revolution speed of 5 revolutions per minute, mechanically stirred for 0.5 hours, and discharged to obtain the accelerant for splicing glue for solar crystalline silicon rods of the present invention, which is packaged and placed for use.

Example 3

Accurately weigh the following raw materials: 10 parts of ethoxylated bisphenol A dimethacrylate, 20 parts of polyurethane modified diester acrylate, 30 parts of 2-phenoxyethyl acrylate, 0.01 part of p-benzoquinone Mix evenly in the power mixing mixer, then add 0.8 parts of triethanolamine and 0.5 parts of saccharin, and heat up to 50°C. Under the condition that the rotation speed of the double planetary power mixing mixer is 500 rpm and the revolution speed is 8 rpm, Mechanically stir for 0.5 hours to completely dissolve, then quickly cool down to room temperature, add 1 part of tert-butyl peroxybenzoate, and then add 4 parts of A-187 coupling agent, stir for 1 hour, then vacuum for 10 minutes, the vacuum degree to -0.06MPa. After discharging, the anaerobic glue solution for splicing solar crystal silicon rods of the present invention is obtained, which is packaged and placed for use.

Accurately weigh the components of the surface accelerator as follows: 1 part of copper acetate powder and 99 parts of absolute ethanol as a solvent are mixed in a double planetary power mixer, and the rotation speed of the double planetary power mixer is 300 rpm. Minutes, under the condition of a revolution speed of 5 rpm, mechanically stirred for 0.5 hours, and discharged, the accelerator for splicing glue for solar crystal silicon rods of the present invention was obtained, which was packaged and placed for use.

Example 4

Accurately weigh the following raw materials: 80 parts of bisphenol A epoxy acrylate, 20 parts of 2-phenoxyethyl acrylate, 0.03 parts of 1,4-naphthoquinone, add them into a double planetary power mixer and mix evenly, then add 0.6 part of triethylamine, 0.4 part of saccharin, heat up to 45 ° C, under the condition that the rotation speed of the double planetary power mixing mixer is 500 rpm and the revolution speed is 8 rpm, mechanically stir for 0.5 hours to completely dissolve, Then cool down to room temperature quickly, add 5 parts of cumene hydroperoxide, and then add 5 parts of A-187 coupling agent, stir for 1 hour, and then vacuumize for 10 minutes to -0.05MPa. After discharging, the anaerobic glue solution for splicing solar crystal silicon rods of the present invention is obtained, which is packaged and placed for use.

Accurately weigh the components of the surface accelerator as follows: add 0.6 parts of copper acetylacetonate powder by weight and 99.4 parts of absolute ethanol as a solvent into a double planetary power mixer for mixing, and the rotation speed of the double planetary power mixer is 300 rpm /min, under the condition that the revolution speed is 5 revs/min, mechanically stir for 0.5 hour, discharge, promptly obtain the accelerant of splicing glue of solar crystal silicon rod of the present invention, pack and place for use.

In the above embodiments 1 to 4, when the process is used, the surface of the silicon rod to be bonded is coated with an accelerator, dried, and then coated with anaerobic glue, docking, bonding, positioning, curing, and wafer cutting.

Comparative Example 1

Traditional epoxy resin adhesive formula, accurately weigh the following raw materials: 55 parts of bisphenol A epoxy resin, 20 parts of carboxyl-terminated nitrile rubber CTBN toughened epoxy resin, 20 parts of active silica powder, 3 parts of nano-calcium carbonate , 2 parts of fumed silica, 0.2 parts of KH-560 coupling agent, add the above-mentioned raw materials into the double planetary power mixer in turn, vacuumize to -0.1MPa, at the rotation speed of 1000 rpm, the revolution speed of 8 Under the condition of revolutions per minute, stir mechanically for 2 hours, and mix evenly to obtain component A of the epoxy resin adhesive, which is packaged and placed for use.

Accurately weigh the components of the curing agent as follows: 65 parts of GPM800 epoxy curing agent, 13 parts of 650# polyamide curing agent, and 22 parts of calcium carbonate. MPa, under the condition that the rotation speed is 1000 rpm and the revolution speed is 8 rpm, mechanically stir for 2 hours and mix evenly to obtain the B component of the epoxy resin adhesive, which is packaged and placed for use.

Component A and component B of the epoxy resin adhesive obtained in Comparative Example 1 were weighed in a weight ratio of 1:1, mixed, coated, positioned, cured, and then wafers were cut.

The performance of the solar crystalline silicon rod splicing glue of the present invention is tested by the following test.

The steps of the test method are:

With the solar crystalline silicon rod splicing glue obtained in each embodiment of Examples 1 to 4, when testing, the surface of the adherend is coated with an accelerator, dried, and then coated with 8-10 grams of anaerobic glue, butt joint, Positioning, curing, and performance testing.

Component A and component B of the epoxy resin adhesive obtained in Comparative Example 1 were mixed at a weight ratio of 1:1, and 8-10 grams of the mixed glue was weighed, docked, positioned, cured, and then performance tested.

The test of test embodiment 1 shear strength:

Above-mentioned embodiment 1-4 and existing traditional epoxy resin adhesive are carried out comparative test, according to standard GB/T 6329-1996 test.

Test Example 2 Impact Strength Test:

Above-mentioned embodiment 1-4 and existing traditional epoxy resin adhesive are carried out comparative test, according to standard GB/T 2571-1995 test.

The test of test embodiment 3 positioning time:

The above-mentioned Examples 1-4 and the existing traditional epoxy resin adhesives were compared and tested according to the standard ASTM 5363-1997. Steel M8 bolts and nuts degreased with acetone are used as test objects at room temperature.

Test Example 4 Storage Stability Test

100 g of the above-mentioned components of Examples 1-4 and existing traditional epoxy resin adhesives are poured into a 200 ml glass beaker, and then placed in a constant temperature and humidity chamber at a temperature of 25° C. and a relative humidity of 50 % environment, leave it open for 15 days, and observe the change of the glue.

Test Example 5 Medium Resistance Performance Test

The components of the above-mentioned Examples 1-4 and the existing traditional epoxy resin adhesive are bonded to the M10 steel block according to the specified requirements. After positioning, place it at room temperature for 24 hours, and soak it in 200# solvent oil at 70°C. 24 hours, test its compressive shear strength, test standard reference Q/SH 114-2009 standard implementation.

The test results are shown in Table 1.

Table 1 Test results

From the above results, it can be seen that a solar crystalline silicon rod splicing glue of the present invention has better mechanical properties than the existing traditional epoxy resin glue, especially higher impact toughness, and simultaneously improves storage stability and durability. Chemical media properties. Moreover, the positioning time of the newly invented silicon rod splicing glue is faster, which greatly improves the work efficiency, and can fully meet the requirements of fast positioning and bonding in the cutting process of solar crystal silicon.

The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included in the protection of the present invention. within range.

Claims (10)

1. a sun power crystalline silicon rod splicing glue, is characterized in that, is comprised of anaerobic gelatin and promotor;

Wherein, described anaerobic gelatin is comprised of each raw material of following parts by weight: 10 ~ 30 parts of thinners, and 20 ~ 80 parts of oligopolymers, 1 ~ 5 part of coupling agent, 1 ~ 5 part, oxygenant, 0.2 ~ 0.8 part of reductive agent helps 0.1 ~ 0.5 part of reductive agent, 0.01 ~ 0.03 part of stopper;

Described surface promoter is comprised of each raw material of following parts by weight: 0.1 ~ 1 part of metal organic acid salt, 90 ~ 99.9 parts of solvents.

2. sun power crystalline silicon rod splicing glue according to claim 1, is characterized in that, described thinner is a kind of or several mixing arbitrarily in the many acrylate of tetraethylene-glycol, hydroxyethyl methylacrylate, 2-phenoxyethyl acrylate.

3. sun power crystalline silicon rod splicing glue according to claim 1, is characterized in that, described oligopolymer is a kind of or several mixing arbitrarily in ethoxyquin bisphenol a dimethacrylate, bisphenol A epoxy acrylate, urethane dibasic acid esters.

4. sun power crystalline silicon rod splicing glue according to claim 1, is characterized in that, described coupling agent is (2,3-epoxypropyl) propyl trimethoxy silicane; Described oxygenant is a kind of or several mixing arbitrarily in benzoyl peroxide, isopropyl benzene hydroperoxide, peroxidized t-butyl perbenzoate; Described reductive agent is a kind of or several mixing arbitrarily in triethylamine, DMA, trolamine; The described reductive agent that helps is saccharin insoluble; Described stopper is 1,4-naphthoquinone or Resorcinol.

5. sun power crystalline silicon rod splicing glue according to claim 1, is characterized in that, described surface promoter is a kind of or several mixing arbitrarily in ferrocene ethanolic soln, neutralized verdigris ethanolic soln, isocaprylic acid copper ethanolic soln.

6. the preparation method of a sun power crystalline silicon rod splicing glue, is characterized in that, comprises the following steps:

1) preparation process of the anaerobic gelatin of described sun power crystalline silicon rod splicing glue is: be that the oligopolymer of 20～80 parts, the thinner of 10～30 parts, the stopper of 0.01～0.03 part add in stirrer and mix with parts by weight, add again parts by weight be 0.2～0.8 part reductive agent, 0.1～0.5 part help reductive agent, first heating, stir again, then the cooling room temperature of being down to, adding parts by weight is the coupling agent of 1～5 part again, again stir, and then vacuumize, namely get the anaerobic gelatin of described sun power crystalline silicon rod splicing glue;

2) preparation process of the surface promoter of described sun power crystalline silicon rod splicing glue is: be the metal organic acid powder of 0.1～1 part with parts by weight, the solvent of 90～99.9 parts, add in stirrer and stir, to mixing, namely get the surface promoter of described sun power crystalline silicon rod splicing glue.

7. preparation method according to claim 6, is characterized in that, in step 1), the temperature after described heating is 40～60 ℃.

8. preparation method according to claim 6, is characterized in that, in step 1), the processing condition of described stirring are: be 500～1000 rev/mins at rotational velocity, revolution speed is under the condition of 5～8 rev/mins, to stir 0.3～1 hour.

9. preparation method according to claim 6, is characterized in that, in step 1), the described time of again stirring is 0.5～1.5 hour; The described processing condition that vacuumize are: vacuumize 5～15 minutes, make vacuum tightness to-0.1～-0.08MPa.

10. preparation method according to claim 6, is characterized in that, in step 2) in, the processing condition of described stirring are: be 200～500 rev/mins at rotational velocity, revolution speed is under the condition of 5～8 rev/mins, to stir 0.2～1 hour.