CN102093929B

CN102093929B - Method for recycling solar polyethylene glycol (PEG)-based recycling cutting liquid and cutting liquid prepared on basis of method

Info

Publication number: CN102093929B
Application number: CN200910200317.9A
Authority: CN
Inventors: 于昊; 宫勇; 兰育辉
Original assignee: Anji Microelectronics Shanghai Co Ltd
Current assignee: Anji Microelectronics Shanghai Co Ltd
Priority date: 2009-12-11
Filing date: 2009-12-11
Publication date: 2014-02-26
Anticipated expiration: 2029-12-11
Also published as: CN102093929A

Abstract

The invention relates to a method for recycling solar polyethylene glycol (PEG)-based recycling cutting liquid and cutting liquid prepared on the basis of the method. The method comprises a step of adding a dispersant, a cationic surfactant, a defoamer, a chelating reagent and a metal corrosion inhibitor into the PEG-based recycling cutting liquid. The PEG-based recycling cutting liquid can be completely used; the stability of the PEG-based recycling cutting liquid is improved; SiC is better dispersed; and the prepared mortar has high dispersibility and redispersibility.

Description

The cutting liquid that solar PE G base reclaims cutting liquid recycling method and obtains based on this method

Technical field

The present invention relates to the sun power cutting liquid that solar PE G base reclaims cutting liquid recycling method and obtains based on this method

Background technology

Solar silicon wafers cutting be generally use that hardness is high, granularity is little and the silicon carbide micro-powder of centralized particle diameter as main Cutting Medium, for silicon carbide micro-powder is uniformly dispersed in working angles, take away in time the huge heat of friction producing in working angles simultaneously, conventionally need first carbonization micro mist to be joined in cutting liquid according to a certain percentage, and fully disperse, be configured to be used further to silicon chip cutting after uniform and stable cutting mortar.Use silicon carbide micro-powder as medium in solar silicon wafers line cutting process, whole mechanism is to make silicon carbide micro-powder particle impact continuously and healthily silicon rod surface, utilize rigid characteristic and the sharp water caltrop of silicon-carbide particle that silicon rod is progressively blocked, this process can be accompanied by larger heat of friction and discharge, and the broken silicon-carbide particle and the silicon grain that due to the collision between silicon-carbide particle and silicon rod and friction, produce also will be sneaked in cutting system simultaneously.For fear of the cut silicon chip of opening, cut the impact that system temperature raises and warpage is occurred and its surface is affected its smooth finish by particle over-mastication in small, broken bits, must manage to take in time cutting heat and crushed particles out of cutting system, therefore the Main Function of cutting liquid is to make mortar have good mobility, silicon-carbide particle can be uniform and stable in cutting system dispersion, cutting force field action with uniform and stable in the high-speed motion of steel wire is surperficial in silicon rod, take away in time cutting heat and crushed particles, guarantee the surface quality of silicon chip simultaneously.

Whole cutting process has proposed high requirement and technological standard to the quality of solar silicon wafers cutting liquid.Because solar silicon wafers cutting liquid is good by wetting property, it is strong and be the compound that major ingredient generates to polyoxyethylene glycol (PEG) base or oil base that silicon carbide class abrasive material has a good dispersing characteristic that row cuts ability, thereby the characteristic of property of polyoxyethylene glycol (PEG) plays a part can not be substituted to the course of processing of silicon chip cutting fluid itself and silicon chip.

Along with reshuffling and the continuous decrease of profit of solar silicon wafers cutting industry, the silicon chip cutting enterprise production control process of coincidentally beginning to fight, the board reducing production costs.Be exactly the most directly to the cutting liquid in three large auxiliary materials and the recycling of silicon carbide micro-powder.Owing to passing through the recycling to waste mortar, the cost that can make cutting liquid and silicon carbide micro-powder is 15-35% at least, so following three to five years, the market share that reclaims liquid and recovery sand also will have significantly and rise, the market demand that finally reclaims liquid is expected to reach 50000-70000 ton.

But the recovery of present domestic recovery liquid also exists a lot of problems with use.Such as the recovery levels of recovery producer is uneven, the quality that reclaims liquid is unstable, in recovery liquid, macrobead silicon is residual, metal content is higher etc., this has just caused enterprise to account for the 30%-50% of whole cutting liquid usage quantity in the ratio of using recovery liquid to cut, and there will be cutting unstable, and dirty sheet appears in silicon chip, the transformation efficiency of rear road device, electrical property and degradation problem under the life-span.

Summary of the invention

The object of the invention is to reclaim in order to solve the cutting of PEG base solar unstable that liquid exists in cutting process, contain amount of metal too high, cause silicon chip yield low, the low conversion rate that occurs the caused back end device of dirty sheet, the problems such as the life-span is short, realize 100% and utilize PEG base cutting recovery liquid to cut.Provide the cutting of a kind of PEG of use base to reclaim liquid and carry out the new solar silicon wafers cutting liquid generating under the method for solar silicon wafers cutting and the method.

The invention provides a kind of PEG base cutting and reclaim the control method of liquid, the weight percent of the conditioning agent of telling is:

A) liquid 80%～98% is reclaimed in the cutting of PEG base

B) dispersion agent 0.1%～10%

C) cats product 0.1%～10%

D) defoamer 0.1%～3%

E) intercalating agent 0.1%～5%

F) metal corrosion inhibitor 0.1%～3%

It is business-like recovery liquid on the market that liquid is reclaimed in the cutting of PEG base that the present invention mentions.

In the present invention, described dispersion agent refers to vinylformic acid, methylpropanoic acid acid, ethylacrylic acid, olefin sulfonic acid, styrene sulfonic acid, maleic anhydride, alkyl propenyloxy group sulfonic acid, the composition of one or more of the homopolymer that one or more monomeric units in acrylamido sulfonic acid obtain or multipolymer; Wherein the molecular weight of polymkeric substance is 800-5000, and wherein preferred molecular weight is 1000-3000, most preferably 1200-2000.

In the present invention, described cats product, is selected from chlorination stearyl dimethyl benzyl ammonium, one or more in Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH and benzyltrimethylammonium hydroxide.

In the present invention, described defoamer, is preferably selected from one or more in polymethyl siloxane, PES-4, poly-propyl-siloxane, poly-butyl siloxanes, polymethy ethylsiloxane and polydimethylsiloxane.

In the present invention, described intercalating agent is selected from benzotriazole, as one or more in the corrosion inhibitors such as benzotriazole, methyl benzotriazazole or 4-carboxy benzotriazole.

In the present invention, described metal corrosion inhibitor, is preferably selected from phenols, as phenol, 1, and 2-dihydroxyl phenol, pyrocatechol, Nickel thiolates, para hydroxybenzene phenol or pyrogallol etc.; Carboxylic-acid, as phenylformic acid, para-amino benzoic acid (PABA), phthalic acid (PA) or gallic acid (GA), Whitfield's ointment, citric acid etc.; Carboxylic acid esters, as methyl p-aminobenzoate, Methyl Benzene-o-dicarboxylate or Tenox PG etc.; Anhydrides, as one or more in diacetyl oxide or caproic anhydride etc.

The problem that the present invention exists according to present market PEG base cutting recovery liquid, in order better to solve the sun power cutting liquid of PEG base, reclaim stability in use and the ratio of liquid, guarantee that cutting effect is better, further reduce costs, according to the cutting of different PEG bases, reclaim liquid, add dispersion agent, cats product, defoamer, intercalating agent, metal corrosion inhibitor improves the stability that liquid is reclaimed in the cutting of reclaiming PEG base, can 100% uses, better disperse SiC, the mortar of configuration has good dispersiveness and redispersibility.

Embodiment

Table 1 embodiment 1～10

Embodiment

Liquid is reclaimed in the cutting of PEG base

Dispersion agent

Tensio-active agent

Defoamer

Intercalating agent

Metal corrosion inhibitor

1

96.5% reclaims liquid

Polymaleic anhydride 1200,1.0%

Tetramethylammonium hydroxide, 1.8%

Polymethyl siloxane, 0.3%

Benzotriazole, 0.2%

Phenol, 0.2%

2

95.1% reclaims liquid

Vinylformic acid-Sipacril 2739OF 1000,1.6%

Tetraethyl ammonium hydroxide, 2.6%

PES-4,0.3%

Methyl benzotriazazole, 0.3%

Phenylformic acid, 0.1%

3

94.6% reclaims liquid

Ethylacrylic acid-maleic anhydride copolymer-1 000,1.6%

TPAOH, 2.8%

Polymethyl siloxane, 0.2%; PES-4,0.2%

Benzotriazole, 0.3%

Gallic acid, 0.15%, Whitfield's ointment, 0.15%

4

95.9% reclaims liquid

Olefin sulfonic acid-styrene sulfonic acid copolymer-1 400,1.0%

Chlorination stearyl dimethyl benzyl ammonium, 1.0%; Tetramethylammonium hydroxide, 1.0%

Poly-propyl-siloxane, 0.3%

4-carboxy benzotriazole, 0.4%

Nickel thiolates, 0.2% para hydroxybenzene phenol, 0.2%

5

90.4% reclaims liquid

Vinylformic acid-alkyl propene sulfonic acid multipolymer 800,4%

TBAH, 4.8%

Poly-butyl siloxanes, 0.2%

Benzotriazole, 0.2%; Methyl benzotriazazole, 0.2%

Para-amino benzoic acid, 0.1%; Diacetyl oxide, 0.1%

6

80% reclaims liquid

Polyacrylamide base sulfonic acid 800,10%

Benzyltrimethylammonium hydroxide 8%

Polymethy ethylsiloxane 0.5%

Benzotriazole, 0.3%

1,2-dihydroxyl phenol 0.6%, pyrocatechol 0.6%

7

98% reclaims liquid

Acrylic acid-maleic anhydride copolymer 5000,0.1%

Tetramethylammonium hydroxide 0.1%

Polydimethylsiloxane, 0.4%

4-carboxy benzotriazole 0.2, benzotriazole 0.2%

Pyrogallol 0.5%, phthalic acid 0.5%

8

81.8% reclaims liquid

Polyacrylic acid 800,6%

Tetramethylammonium hydroxide 10%

Poly-butyl siloxanes, 0.1%

Benzotriazole, 0.1%

Tenox PG 1%, citric acid 1%

9

84.5% reclaims liquid

Polymaleic anhydride 1000,3%

Tetramethylammonium hydroxide 4.4#

Polydimethylsiloxane, 3%

Methyl benzotriazazole, 5%

Methyl Benzene-o-dicarboxylate, 0.1%

10

92.6% reclaims liquid

Ethylacrylic acid-maleic anhydride copolymer-1 000,2.4%

TBAH 3.2%

Polymethy ethylsiloxane 0.8%

Benzotriazole, 0.2%

Methyl p-aminobenzoate 0.4%, caproic anhydride 0.4%

Effect embodiment

Use embodiment 1,3,4,10 and new cutting liquid on the market, PEG base reclaims liquid, and using SiC is the configuration of cutting mortar at 53: 47 in cutting liquid and SiC ratio, compares.

Table 2 the present invention and market cutting liquid and recovery liquid preparation cutting mortar ratio are

	Standing 1 day SiC height	Standing 3 days SiC height	Standing 7 days SiC height	Again rock SiC height
					Embodiment 1	6.2cm	5.2cm	3.6cm	SiC is dispersed in cutting liquid again
Embodiment 3	6cm	5.0cm	3.2cm	SiC is dispersed in cutting liquid again
					Embodiment 4	6cm	5.0cm	3.1cm	SiC is dispersed in cutting liquid again
Embodiment 10	5.8cm	5.1cm	3.0cm	SiC is dispersed in cutting liquid again
					The new cutting liquid in market	4.6cm	2.9cm	1.8cm	1.8
Liquid is reclaimed in market	4.4cm	2.9cm	1.6cm	1.6

Claims

1. a solar PE G base reclaims the recycling method of cutting liquid, it is characterized in that, described method comprises: to the cutting of PEG base, reclaim in liquid and add dispersion agent, cats product, defoamer, intercalating agent and metal corrosion inhibitor, the quality percentage composition that liquid is reclaimed in wherein said PEG base cutting is 80%～98%, the quality percentage composition of described dispersion agent is 0.1%～10%, the quality percentage composition of described cats product is 0.1%～10%, the quality percentage composition of described defoamer is 0.1%～3%, the quality percentage composition of described intercalating agent is 0.1%～5%, the quality percentage composition of described metal corrosion inhibitor is 0.1%～3%, described dispersion agent is by vinylformic acid, methylpropanoic acid acid, ethylacrylic acid, olefin sulfonic acid, styrene sulfonic acid, maleic anhydride, alkyl propenyloxy group sulfonic acid, the composition of one or more of the homopolymer that one or more monomeric units in acrylamido sulfonic acid obtain or multipolymer, the molecular weight of described homopolymer or multipolymer is 800-5000, described cats product is selected from chlorination stearyl dimethyl benzyl ammonium, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, one or more in TBAH and benzyltrimethylammonium hydroxide, described defoamer is selected from polymethyl siloxane, PES-4, poly-propyl-siloxane, poly-butyl siloxanes, one or more in polymethy ethylsiloxane and polydimethylsiloxane, described intercalating agent is selected from benzotriazole, one or more in methyl benzotriazazole and 4-carboxy benzotriazole, described metal corrosion inhibitor is selected from phenols, carboxylic-acid, one or more in carboxylic acid esters and anhydrides.

2. method as claimed in claim 1, is characterized in that, the molecular weight of described homopolymer or multipolymer is 1000-3000.

3. method as claimed in claim 2, is characterized in that, the molecular weight of described homopolymer or multipolymer is 1200-2000.

4. method as claimed in claim 1, is characterized in that, described phenols is selected from phenol, 1, one or more in 2-dihydroxyl phenol, pyrocatechol, Nickel thiolates, para hydroxybenzene phenol and pyrogallol; Described carboxylic acid is selected from phenylformic acid, para-amino benzoic acid, phthalic acid, gallic acid, Whitfield's ointment and citric acid; Described carboxylicesters is methyl p-aminobenzoate, Methyl Benzene-o-dicarboxylate and/or Tenox PG; Described acid anhydrides is diacetyl oxide and/or caproic anhydride.

5. the new solar silicon wafers cutting liquid being configured to by method as described in claim 1～4 any one.