JP2001240850A - Dispersing agent for abrasive grain for polishing and slurry for polishing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dispersing agent for abrasive grain for polishing and a slurry for polishing, improved in abrasive rate and effect for preventing occurrence of fine flaws. SOLUTION: This slurry for polishing comprises the dispersing agent for abrasive grain, composed of a non-alkylphenol type polyether compound and an inorganic rust preventing agent, in which surface tension of 1% aqueous solution at 25 deg.C is 20 to 40 dyne/cm and disperse stability of abrasive grain is >=1.3 times compared with a case when only water is used, abrasive grain and water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an abrasive dispersant for polishing and a polishing slurry. More specifically, the present invention relates to a dispersant for abrasive grains and a slurry for polishing when polishing a silicon wafer, glass, or the like.

[0002]

2. Description of the Related Art Conventionally, as a method of polishing the surface of a silicon wafer or glass, abrasive grains made of alumina or the like having an average particle diameter of 0.1 to 50 .mu.m and being dispersed between upper and lower rotating platens are dispersed. A method in which a slurry in which a dispersant, an organic rust inhibitor such as an alkanolamine and the like and water are mixed is continuously supplied and polished is used. What is required at this time is to improve the polishing rate, reduce fine scratches on the polished surface, and prevent rust on the polishing machine. As a dispersant for the abrasive grains, an alkylphenol-type nonionic surfactant (alkylphenol ethylene oxide Adduct) has been used.

[0003]

However, an alkylphenol-type nonionic surfactant is not sufficient in terms of polishing rate and reduction of scratches. Further, when these surfactants are released into the environment, they may cause environmental hormones due to biodegradation. There is a concern that the substance may be converted to a substance having an action, and it is not preferable to use the substance in a large amount. In order to solve these problems, a combination of a nonionic surfactant and an inorganic rust inhibitor has been proposed, but the grinding speed is not sufficient.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to obtain a polishing abrasive dispersant having a high processing speed and less scratching without using an alkylphenol-type nonionic surfactant. The present inventors have found that the above problems can be solved by a combination of a polyether compound that gives a specific surface tension and dispersion stability of abrasive grains and an inorganic rust preventive agent, and the present invention has been achieved.

That is, the present invention comprises a polyether compound (A) and an inorganic rust inhibitor (B), and the surface tension of a 100-fold water diluent at 25 ° C. is 20 to 40 dyne / c.
m, wherein the dispersion stability of the abrasive grains is 1.3 times or more as compared with the case of using only ion-exchanged water, the abrasive grain dispersant (I) for polishing and the dispersant (I) for polishing, Abrasive (D)
And a polishing slurry comprising water.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The surface tension specified in the present invention is a value measured by a Wilhelmy surface tensiometer,
For example, it is measured with an automatic surface tensiometer manufactured by Kyowa Interface Chemical Co., Ltd. The dispersion stability of the abrasive grains specified in the present invention is a water diluent 100 times the abrasive grain dispersant for polishing [1 part by weight of dispersant (I) is diluted with ion-exchanged water to 100 parts by weight]. A slurry obtained by mixing silicon carbide abrasive grains having an average particle diameter of 10 μm (for example, C # 400 manufactured by Fujimi Incorporated Co., Ltd.) to a concentration of 20% by weight was placed in a 100-ml graduated cylinder with a stopcock having a diameter of 2.8 cm and a height of 24 cm.
Take 0 ml, shake up and down 30 times in 1 minute at 25 ° C., mix well, and allow to stand.
It is measured by measuring the time required to descend mm.

The non-alkylphenol type polyether compound (A) of the present invention is blended with an inorganic rust inhibitor (B), and if necessary, a chelating agent, a pH adjuster, a preservative,
When an antifoaming agent, water, etc. are added to make an abrasive dispersant,
The surface tension at 25 ° C. of the water dilution of 00 times is 20 to 4
Those which show 0 dyne / cm and achieve a dispersion stability of the abrasive grains of 1.3 times or more as compared with the case of using only water are used.
Preferred examples of (A) include those comprising the following (a-1) and / or (a-2). (A-1): a non-alkylphenol-type nonionic surfactant comprising one or a mixture of two or more compounds represented by the following general formula (1) Z-[｛(AO) n / (EO) m｝ R ¹ P (1) (wherein, R ¹ is an alkyl group having 1 to 18 carbon atoms, 2 carbon atoms)
An acyl group or a hydrogen atom having from 24 to 24; Z is a residue of a p-valent alcohol having 1 to 6 carbon atoms; A is an alkylene group having 3 to 4 carbon atoms; E is an ethylene group; p n
Are positive integers averaging 10 to 200; p m
Is an integer of 0 or 1 or more with an average of 1 to 300; {(AO) n / (EO) m} represents a block or random addition form. (A-2): derived from a polyoxyalkylene polyol having a number average molecular weight of 2,000 to 25,000 and an organic polyisocyanate, and having a weight average molecular weight of 10,000 to
A polyurethane compound which is 300,000.

In the non-alkylphenol-type nonionic surfactant (a-1) represented by the general formula (1) of the present invention, Z is a residue of an alcohol having a p value (p is a number of 1 to 6).

The above-mentioned p-valent alcohols include C1-C6 alcohols having 1-6 carbon atoms, preferably aliphatic or alicyclic alcohols. Specifically, methanol, ethanol, n- and i-propanol,
monohydric alcohols such as n-, i-, sec- and t-butanol, hexanol, cyclohexanol; dihydric alcohols such as ethylene glycol; trihydric alcohols such as glycerin, trimethylolpropane; pentaerythritol, diglycerin, sorbitol, Examples thereof include 4- to 6-valent alcohols such as xylitol, mannitol, and glucose. Among these alcohols, preferred are divalent to tetravalent alcohols having 2 to 5 carbon atoms.

In the non-alkylphenol-type nonionic surfactant (a-1) represented by the general formula (1) of the present invention, (AO) n adds an alkylene oxide having 3 to 4 carbon atoms (hereinafter abbreviated as AO). Represents a polyoxyalkylene group formed as a result. As AO, propylene oxide (hereinafter abbreviated as PO), 1,2-, 2,3-,
1,3- and 1,4-butylene oxide, and a combination of two or more of these (block and / or random addition) are used. Preferred is PO. (EO) m represents a (poly) oxyethylene group formed by adding EO. The addition of AO and EO to alcohols can be carried out in a usual manner, and can be carried out in the absence of a catalyst or in the presence of a catalyst (alkali catalyst, amine catalyst, acidic catalyst) in one or multiple stages under normal pressure or pressure. Done in

[0011] In the general formula (1), n represents the number of oxyalkylene groups having 3 to 4 carbon atoms, that is, the number of moles of AO added. It is a positive integer of 10 to 50. When the content is within the above range, it is easily soluble in water and foaming does not become too large, so that the surface of the object to be polished is less likely to be scratched. M in the general formula (1) is the number of oxyethylene groups, that is, EO
Represents the number of moles of addition, usually the sum of p m is an average of 1 to
It is an integer of 300, preferably 10 to 100, 0 or 1 or more. When the content is within the above range, it is easily soluble in water and foaming does not become too large, so that the surface of the object to be polished is less likely to be scratched. m / n is 1/10 to 6/1, particularly 3/10 to 5/1 from the viewpoint of solubility in water and low foaming property.
Is preferred.

In the general formula (1), ｛(AO) n / (E
O) m} represents random addition and / or block addition of AO and EO. The form of addition is random addition, block addition (for example, AO-EO, EO-AO, AO-
(Sequential addition of EO-AO, AO-EO-AO-EO, etc.)
Or a mixture of both (for example, EO addition after random addition). Of these, block addition is preferred, and further, AO is first added to alcohols and then EO is added to the terminal, that is, R ¹
Those having an oxyethylene group at the terminal bonded to are preferred.

In the non-alkylphenol type nonionic surfactant represented by the general formula (1) of the present invention, R ¹ is an alkyl or alkenyl group having 1 to 18 carbon atoms, an acyl group having 2 to 24 carbon atoms or a hydrogen atom. . When p is 2 or more, a plurality of R ¹ may be the same or different.
Examples of the alkyl group having 1 to 18 carbon atoms include linear and / or branched alkyl chains such as ethyl, methyl, propyl,
Decyl, stearyl group and the like. 1 to 1 carbon atoms
Examples of the alkenyl group 8 include an oleyl group. As a method for producing a compound having an alkyl group having 1 to 18 carbon atoms, after adding AO and EO to an alcohol, an alkyl halide having 1 to 18 carbon atoms such as alkyl chloride and alkyl bromide can be reacted. . Examples of the acyl group having 2 to 24 carbon atoms include aliphatic acyl such as acetyl, butyl, stearoyl and oleoyl; and aromatic acyl (aroyl) such as benzoyl, toluoyl and naphthoyl. Among these acyl groups, preferred are aliphatic acyl groups, and particularly preferred are acetyl and oleoyl. As a method for producing a compound having an acyl group having 2 to 24 carbon atoms, after adding AO and EO to alcohols, acetic acid, propionic acid, butyric acid, stearic acid, benzoic acid, naphthoic acid having 2 to 24 carbon atoms are added. It can be obtained by dehydration esterification with a carboxylic acid such as an acid. It can also be obtained by using an ester-forming derivative of the above carboxylic acid (acid anhydride, acid chloride, lower alkyl ester).

The number average molecular weight of the non-alkylphenol-type nonionic surfactant (a-1) represented by the general formula (1) of the present invention is not particularly limited as long as it satisfies the general formula (1), but is preferred. Is 2,000 to 20,000, more preferably 3,000 to 10,000. [The molecular weight is measured by gel permeation chromatography (GPC). The same applies to the following. ]

Examples of the polyoxyalkylene polyol from which the polyurethane compound (a-2) of the present invention is derived include a compound having a structure in which AO is added to a polyhydric alcohol, and a mixture of two or more of these. Examples of the polyhydric alcohol (a1) include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, bis (hydroxymethyl) cyclohexane, bis Dihydric alcohols such as (hydroxyethyl) benzene; glycerin, trimethylolpropane, pentaerythritol, diglycerin,
α-Methylglucoside, sorbitol, xylit, mannitol, dipentaerythritol, glucose, fructose, tri- to polyhydric alcohols such as sucrose, and the like. As AO (alkylene group having 2 to 18 carbon atoms) to be added to the polyhydric alcohol, EO, PO, 1,
2-, 2,3- or 1,3-butylene oxide,
Tetrahydrofuran (THF), styrene oxide,
Α-olefin oxides having 6 to 18 carbon atoms, epichlorohydrin and the like. AO may be used alone or in combination of two or more types. In the latter case, a block addition (chip type, balanced type, active secondary type, etc.) or a random addition or a mixed system of both (a chip added after random addition: molecule) Having 0 to 50% by weight (preferably 5 to 40% by weight) of ethylene oxide chains arbitrarily distributed therein;
0 to 30% by weight (preferably 5 to 25% by weight) of an EO chain chipped at the molecular end]. From the viewpoint of reactivity with the polyisocyanate, a polyoxyalkylene polyol having EO added to a terminal portion (chip type, random chip type, balanced type) is preferable. Of these, particularly preferred are those obtained by adding EO to polyethylene glycol and polypropylene glycol. The average oxyethylene unit content in the polyoxyalkylene polyol is preferably at least 50% by weight, particularly preferably at least 85% by weight.

The number average molecular weight of the polyoxyalkylene polyol is usually from 2,000 to 25,000, preferably from 3,000 to 20,000. Number average molecular weight is 2,
If it is 000 or more, the polyurethane compound becomes easily soluble in water, and if it is 25,000 or less, the reactivity with the polyisocyanate is good, and it is easy to obtain a polymer compound having the intended performance. . Further, a low molecular polyol may be used in combination as long as the water solubility or water dispersibility is not impaired. Examples of the low molecular polyol used in the present invention include polyhydric alcohols having 2 to 8 valences and alkylene oxides of the polyhydric alcohols (ethylene oxide, propylene oxide, 1,2-, 1,3-, 2,
3- or 1,4-butylene oxide, α-olefin oxide, styrene oxide, epichlorohydrin, etc.) adducts (molecular weight less than 500) and the like. Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, neopentyl glycol, 1,4- Dihydric alcohols such as bis (hydroxymethyl) cyclohexane, 1,4-bis (hydroxyethyl) benzene, 2,2-bis (4,4'-hydroxycyclohexyl) propane; trihydric alcohols such as glycerin and trimethylolpropane; Pentaerythritol, diglycerin, α-methylglucoside, sorbitol, xylitol, mannitol,
Dipentaerythritol, glucose, fructose,
Examples thereof include 4- to 8-valent alcohols such as sucrose.

As the organic polyisocyanate for deriving the polyurethane compound (a-2) of the present invention, those which have been conventionally used for producing polyurethane can be used. Such polyisocyanates include aromatic polyisocyanates having 6 to 20 carbon atoms (excluding carbon in the NCO group, the same applies hereinafter), aliphatic polyisocyanates having 2 to 18 carbon atoms, and alicyclic rings having 4 to 15 carbon atoms. Formula polyisocyanates, araliphatic polyisocyanates having 8 to 15 carbon atoms and modified products of these polyisocyanates (urethane group, carbodiimide group, allophanate group, urea group, buret group, uretdione group, uretoimine group, isocyanurate group, Oxazolidone group-containing modified products) and mixtures of two or more thereof.

Specific examples of the aromatic polyisocyanate include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, ,
4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl -4,4'-diisocyanatodiphenylmethane, crude MDI [crude diaminophenylmethane [condensation product of formaldehyde and aromatic amine (aniline) or a mixture thereof; diaminodiphenylmethane and a small amount (for example, 5 to 20% by weight)]
A mixture with a triamine or higher polyamine]: polyallyl polyisocyanate (PAPI)],
1,5-naphthylene diisocyanate, 4,4 ', 4 "
-Triphenylmethane triisocyanate, m- and p-isocyanatophenylsulfonyl isocyanate.

Specific examples of the aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (H
DI), dodecamethylene diisocyanate, 1,6,1
1-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate And aliphatic polyisocyanates such as 2-isocyanatoethyl-2,6-diisocyanatohexanoate.

Specific examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate,
Methylcyclohexylene diisocyanate (hydrogenated TD
I), bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- and / or 2,6-norbornane diisocyanate.

Specific examples of the araliphatic polyisocyanate include m- and / or p-xylylene diisocyanate, α, α, α ′, α′-tetramethyl xylylene diisocyanate.

The modified polyisocyanate may be modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MD).
I), urethane-modified TDI, biuret-modified HDI, isocyanurate-modified HDI, isocyanurate-modified IP
Modified product of polyisocyanate such as DI and a mixture of two or more of these [for example, combined use of modified MDI and urethane-modified TDI (isocyanate-containing prepolymer)]
Is included. As the polyol used in the production of the urethane-modified polyisocyanate [free isocyanate-containing prepolymer obtained by reacting an excess of polyisocyanate (TDI, MDI, etc.) with a polyol], a polyol having an equivalent weight of 30 to 200, such as ethylene glycol, Glycols such as propylene glycol, diethylene glycol and dipropylene glycol; triols such as trimethylolpropane and glycerin; highly functional polyols such as pentaerythritol and sorbitol; and alkylene oxide (ethylene oxide and / or propylene oxide) adducts thereof. . Of these, preferred are those having 2 to 3 functional groups.
belongs to. The free isocyanate group content of the modified polyisocyanate and prepolymer is usually from 8 to 33.
%, Preferably 10 to 30%, particularly preferably 12 to
29%. Among these, preferred are diisocyanates and crude MDI, and particularly preferred are MDI, HDI, IPDI, and HDI.

The urethane group (-N) in (a-2) of the present invention
The concentration of HCOO-) is preferably between 0.1 and 5% by weight. When the urethane group concentration is 0.1% or more, the dispersion stability function of the abrasive grains is good, and when the urethane group concentration is 5% by weight or less, (a-
2) Good water solubility. The weight average molecular weight of (a-2) is usually from 10,000 to 300,000, preferably 3
It is between 000 and 200,000. Molecular weight distribution (GP
(The numerical value obtained by dividing the weight average molecular weight measured using C by the number average molecular weight) is preferably 1.2 to 6.0, and more preferably 1.3 to 4.0. When the weight average molecular weight of (a-2) is 10,000 or more, the dispersion stability of the abrasive grains is good, and when the weight average molecular weight is 300,000 or less, the viscosity of the abrasive slurry is in an appropriate range, and the workability is low. It will be good. When deriving (a-2) of the present invention, the molar ratio (OH) / (NCO) of the hydroxyl group (OH) in the polyoxyalkylene polyol and the functional group of the isocyanate group (NCO) in the organic polyisocyanate is: Preferably 8/10 to 10 /
8

The production method (a-2) of the present invention is not particularly limited, and it can be obtained by reacting a polyoxyalkylene polyol and an organic polyisocyanate by a usual method for producing a urethane polymer. The reaction temperature is usually 3
The temperature is 0 to 200 ° C, preferably 50 to 180 ° C. The reaction time is usually 0.1 to 8 hours. After the completion of the reaction, a known reaction terminator such as ethylenediamine may be used.
This reaction is usually performed in a solventless system, but may be performed in an organic solvent inert to isocyanate. Examples of the solvent include acetone, tetrahydrofuran, dimethylformamide, dimethylsulfoxide, toluene, dioxane and the like. When these solvents are used, the solvent is usually distilled off after the reaction to obtain (a-2).

The non-alkylphenol type polyether of the present invention
When (a-1) and (a-2) are used in combination in the tellurium compound (A), the weight ratio of (a-1) and (a-2) is wide, for example, (a-1) / (a- 2) = 90 / 10-0 /
Can vary over 100.

As the component (A) of the present invention, from the viewpoint of the stability of the dispersant, a polyoxyethylene monoalkyl ether or a polyoxyethylene monoalkenyl ether having an alkyl group having 6 to 24 carbon atoms (a-3) It is preferable to include (A-3) usually has 6 to 24 carbon atoms.
Obtained by adding ethylene oxide (hereinafter abbreviated as EO) to the aliphatic alcohol. 6-24 carbon atoms
The aliphatic alcohol may be a natural alcohol or a synthetic alcohol (Ziegler alcohol, oxo alcohol, etc.). Specific examples include octyl alcohol,
Nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol,
Saturated aliphatic alcohols such as myristyl alcohol, cetyl alcohol, stearyl alcohol and nonadecyl alcohol; octenyl alcohol, decenyl alcohol, dodecenyl alcohol, tridecenyl alcohol,
Unsaturated fatty alcohols such as pentadecenyl alcohol, oleyl alcohol, gadoleyl alcohol, and linoleyl alcohol; ethylcyclohexyl alcohol;
Propylcyclohexyl alcohol, octylcyclohexyl alcohol, nonylcyclohexyl alcohol,
Cyclic aliphatic alcohols such as adamantyl alcohol; These aliphatic alcohols are primary or secondary.
Grade is preferred, and primary is particularly preferred. Further, the alkyl group portion may be linear or branched, and preferably has 8 to 18 carbon atoms. The HLB of (a-3) of the present invention is usually 1
It is 0-15, preferably 11-15. As the HLB defined in the present invention, an HLB defined by Griffin, which is obtained by multiplying a value obtained by dividing a molecular weight of a hydrophilic group portion by a molecular weight of a surfactant by 20, is used. As a specific example of (a-3), an EO 3-mol adduct of octyl alcohol (HLB10.
1), EO 7 mol adduct of lauryl alcohol (HLB)
12.5), EO 9 mol adduct of myristyl alcohol (HLB13.0), EO12 of myristyl alcohol
Molar adduct (HLB 14.2) EO 9 molar adduct of palmityl alcohol (HLB 12.4). Preference is given to a 7 mole adduct of EO of lauryl alcohol and a 9 mole adduct of EO of myristyl alcohol.

The number average molecular weight of (a-3) of the present invention is usually from 200 to 1500, preferably from 300 to 1,000.

In the present invention, (a-1) and / or (a-
The weight ratio of 2) to (a-3) is preferably 1/5 to 5 /
1, and more preferably 1/3 to 4/1. When the weight ratio is larger than 1/5, the polishing rate is sufficiently high, and when the weight ratio is smaller than 5/1, there is no possibility that the dispersant separates over time.

The inorganic rust preventive (B) in the present invention is not particularly restricted but includes, for example, silicates such as sodium silicate and calcium silicate, sodium phosphate,
Phosphates such as potassium phosphate and sodium polyphosphate; and nitrites such as sodium nitrite. Specifically, the corrosion inhibitors described in [Encyclopedia of Rust Prevention] (published on June 30, 1981, published by the Industrial Research Institute Publishing Division) can be used. Of these, preferred are silicates,
Phosphates are more preferable, and sodium silicate, sodium phosphate and sodium polyphosphate are more preferable.

The proportion of (B) in the abrasive dispersant (I) for polishing of the present invention is not particularly limited, but is preferably 10 to 100 parts by weight, preferably 30 to 80 parts by weight, per 100 parts by weight of (A). Parts by weight. (A) and (B) may use two or more of the above-mentioned compounds in combination.

The organic rust inhibitor (C) can be added to (I) of the present invention, if necessary. (C)
Although not particularly limited, for example, an aliphatic or alicyclic amine having 2 to 16 carbon atoms (alkylamine such as octylamine; oleylamine and the like; cycloalkylamine such as cyclohexylamine); and its EO (1 to 2 mol)
Adducts; alkanolamines (monoethanolamine, diethanolamine, monopropanolamine, etc.); their EO (1-2 mol) adducts; aliphatic carboxylic acids (oleic acid, stearic acid, etc.) and alkali metals or alkaline earth metals And sulfonates (such as petroleum sulfonate); and phosphates (such as lauryl phosphate). Specifically, rust inhibitors described in [Petroleum Product Additives] (published by Koshobo on August 10, 1974) can be used. These may be used in combination of two or more. When (C) is used, the weight ratio (B) / (C) of (B) and (C) is not particularly limited, but is preferably 100/0 to 10/90. When (C) is used, the total amount of (B) and (C) is not particularly limited, but is preferably 10 to 100 parts by weight, preferably 30 to 100 parts by weight based on 100 parts by weight of (A). 80 parts by weight.

In the present invention, for the purpose of adjusting the viscosity, monohydric water-soluble alcohols such as methanol, ethanol and propanol; ethylene glycol, propylene glycol, butylene glycol, glycerin, polyethylene glycol (degree of polymerization 2) To 50) may be blended in an amount that does not adversely affect the performance (for example, 40 parts by weight or less based on 100 parts by weight of the total of (A) and (B)). . These may be used in combination of two or more.

The (I) of the present invention includes (a-
Nonionic surfactants and cationic surfactants other than 1) and (a-3) may be blended. Further, known additives such as a chelating agent, a pH adjuster, a preservative, and an antifoaming agent, and water can be further blended. Specifically, the nonionic surfactants other than (a-1) and (a-3) of the present invention include 1: 1 type coconut oil fatty acid diethanolamide, lauryl dimethylamine oxide, glycerin monostearate, and sorbitan monolaurate. And the like. Examples of the cationic surfactant include stearyltrimethylammonium chloride, distearyldimethylammonium chloride, and lanolin fatty acid aminopropylethyldimethylammonium ethyl sulfate. As a chelating agent, sodium polyacrylate, sodium ethylenediaminetetraacetate, sodium succinate, 1-hydroxyethane-
And sodium 1,1-diphosphonate. p
Examples of the H adjuster include acids such as acetic acid, boric acid, citric acid, oxalic acid, phosphoric acid, and hydrochloric acid; and alkalis such as sodium hydroxide and potassium hydroxide. The amount of these additives can be variously changed depending on the purpose, but usually 0.01%.
-40% by weight, preferably 0.01-20% by weight. Although the amount of water in (I) of the present invention can be arbitrarily changed, it is usually 10 to 80% by weight.

In the present invention (I), even when (A), (B), water and other additives are mixed in advance, (A), (B), water and Other additives may be mixed.

The polishing slurry according to the second invention of the present invention is a polishing slurry comprising the polishing abrasive dispersant (I) of the first invention, abrasive grains (D) and water. The polishing slurry preferably contains the abrasive (D) in an amount of 10 to 30% by weight, particularly preferably 15 to 25%, and the (A) and (B) preferably in an amount of 0.1 to 10% by weight, particularly preferably 0 to 10% by weight. It is constituted as an aqueous dispersion containing 0.2 to 2% by weight.

The abrasive grains (D) in the present invention are not particularly limited. For example, alumina, zircon sand, silicon carbide and the like can be dried using a dry or wet mill or the like to have an average particle diameter of 0.1 to 0.1.
What was ground to 50 micrometers is mentioned. Slurry in the present invention, silicon wafer, glass, aluminum,
It is useful for polishing ceramics, synthetic quartz, quartz, sapphire and the like.

[0037]

EXAMPLES The present invention will be further described with reference to examples below, but the present invention is not limited to these examples. In the following, parts and% indicate parts by weight or% by weight, respectively.

Examples 1 to 3 and Comparative Example 1 were blended in the proportions shown in Table 1. Table 1 shows the surface tension at 25 ° C. and the dispersion stability of the abrasive grains of a 100-fold water diluent of each dispersant. The measurement was performed by the following method. Surface tension: Make a 100 times water dilution of each dispersant,
The surface tension at 25 ° C. was measured with an automatic surface tensiometer manufactured by Kyowa Interface Chemical Co., Ltd. Dispersion stability: A slurry was prepared by mixing silicon carbide abrasive grains (C # 400, manufactured by Fujimi Incorporated) with an average particle diameter of 10 μm in a water diluent 100 times the amount of each dispersant so as to be 20% by weight. 100ml slurry at ℃
Take it in a measuring cylinder with a stopcock, shake it up and down 30 times, mix well, and let it stand still.
The time required to descend the sample was measured and similarly divided by the settling time measured for the slurry prepared without using a dispersant to obtain dispersion stability as compared with the case of using water alone.

[0039]

[Table 1] Numbers in the table represent parts by weight

A-11: First, PO38 was added to ethylene glycol.
A-12: methyl etherified product of a-11 a-21: polyethylene glycol (number average molecular weight 800
0) Polyurethane compound obtained by reacting 100 parts with 5.4 parts of HDI at 170 ° C. for 5 hours a-31: lauryl alcohol with 7 moles of EO added (HLB12.5) a-32: myristyl alcohol with 9 moles of EO (HLB13.0) c: Nonylphenol to which 9 mol of EO is added (HLB12.9) b: Sodium silicate (inorganic rust inhibitor)

The dispersant shown in Table 2 was 1.0% by weight, and the abrasive (FO1200 manufactured by Fujimi Incorporated) was 1% by weight.
8% by weight of water was added and mixed.
And the polishing slurry of Comparative Example 2 was obtained.

Using the polishing slurries of Examples 4 to 6 and Comparative Example 2, 20 silicon wafers having a diameter of 3 inches and a thickness of 600 μm were polished for 15 minutes with a precision flat lapping machine 9BF4M5G (manufactured by Hamai Sangyo Co., Ltd.). Are shown in Table 2. Evaluation and judgment were performed by the following methods. Processing speed: Measure the thickness of silicon wafer before and after polishing,
The amount of reduction in thickness per minute was calculated. Scratches: Twenty polished silicon wafers were visually observed, and the total number of scratches was counted.

[0043]

[Table 2]

1.0% by weight of the dispersant of Examples 1 and 2, and abrasive grains (GC40 manufactured by Fujimi Incorporated)
Water was added and mixed so that 0) was 20% by weight, and the polishing slurries of Examples 7 and 8 and the dispersant of Comparative Example 1 were 1.0% by weight, and abrasive grains (Fujimi Incorporated) (GC400) was added and mixed to give 20% by weight to obtain a polishing slurry of Comparative Example 3.

Using the polishing slurries of Examples 7 and 8 and Comparative Example 3, 20 glass disks having a diameter of 3 inches and a thickness of 1000 μm were precision precision lapping machines 9BF4M5
Table 3 shows the results of polishing for 7 minutes with G (manufactured by Hamai Sangyo Co., Ltd.).
Shown in Evaluation and judgment were performed by the following methods. Processing speed: Measure the thickness of the glass disk before and after polishing,
The amount of reduction in thickness per minute was calculated. Scratches: Twenty polished glass disks were visually observed, and the total number of scratches was counted.

[0046]

[Table 3]

From these results, it can be seen that when polishing is performed using the slurry containing the abrasive dispersant for polishing of the present invention, the occurrence of scratches is small and the processing speed is excellent.

[0048]

The polishing slurry containing the abrasive dispersant for polishing of the present invention has a higher processing speed than the polishing slurry containing ethylene oxide of alkylphenols such as nonylphenol and octylphenol which has been conventionally used. It is excellent and can be polished without causing scratches on the surface. Furthermore, the abrasive grain dispersant for polishing of the present invention essentially does not contain an ethylene oxide adduct of an alkylphenol such as nonylphenol and octylphenol, so that there is no concern about an environmental hormone-like effect. It is useful for polishing aluminum, ceramic, synthetic quartz, quartz, sapphire and the like.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (Reference) C08K 3/32 C08K 3/32 3/34 3/34 5/05 5/05 C08L 71/00 C08L 71/00 Y 71 / 02 71/02 75/08 75/08 H01L 21/304 622 H01L 21/304 622D 622A F-term (reference) 3C058 AA07 CA06 CB02 CB03 CB06 DA02 DA17 4D077 AA01 AB20 AC05 BA01 BA02 BA04 BA07 BA15 DD05X DD05Y DD32X DD32Y DD33 DD DD35X DD35Y DD46X DD46Y DE02X DE02Y DE07X DE07Y DE08X DE08Y 4J002 CH02W CH03W CK04W CK04X DE148 DH047 DH057 DJ007 DJ008 EC036 EC066 FD310 GT00

Claims (11)

[Claims] 1. A non-alkylphenol type polyether compound (A) and an inorganic rust preventive (B), and the surface tension of a 100-fold water diluent at 25 ° C. is 20 to 40 dyne.
/ G, wherein the dispersion stability of the abrasive grains is 1.3 times or more that of water alone. 2. The abrasive dispersant (I) according to claim 1, wherein (A) contains the following (a-1) and / or (a-2). (A-1): a non-alkylphenol-type nonionic surfactant comprising one or a mixture of two or more compounds represented by the following general formula (1) Z-[｛(AO) n / (EO) m｝ R ¹ P (1) (wherein, R ¹ is an alkyl or alkenyl group having 1 to 18 carbon atoms, an acyl group having 2 to 24 carbon atoms, or a hydrogen atom;
Z is a residue of a p-valent alcohol having 1 to 6 carbon atoms; A is an alkylene group having 3 to 4 carbon atoms; E is an ethylene group;
An integer of 6; the sum of p n is a positive integer with an average of 10 to 200; the sum of p m is 0 with an average of 1 to 300
Or an integer of 1 or more; {(AO) n / (EO) m} indicates that the addition form is a block form or a random form. (A-2): derived from a polyoxyalkylene polyol having a number average molecular weight of 2,000 to 25,000 and an organic polyisocyanate, and having a weight average molecular weight of 10,000 to
A water-soluble or water-dispersible polyurethane compound having a molecular weight of 300,000. 3. The method according to claim 1, wherein (A) further comprises an alkyl group having 6 to 6 carbon atoms.
24 polyoxyethylene monoalkyl ethers or polyoxyethylene monoalkenyl ethers (a-
The abrasive grain dispersant (I) for polishing according to claim 2, further comprising (3). 4. In (a-1), ｛(AO) n / (E
O) The abrasive dispersant for polishing according to claim 2, wherein m｝ is a block-like addition, and the terminal bonded to R ¹ is an oxyethylene group. 5. In (a-1), m / n is 1/10 to 10
The abrasive grain dispersant for polishing according to claim 2 or 3, which is 6/1. 6. The abrasive dispersant for polishing according to claim 2, wherein the HLB of (a-3) is from 10 to 15. 7. The polishing composition according to claim 1, wherein (B) is at least one inorganic rust inhibitor selected from the group consisting of sodium silicate, sodium phosphate and sodium polyphosphate. Abrasive dispersant. 8. A polishing method for polishing a silicon wafer.
The abrasive grain dispersant for polishing according to any one of the above. 9. The abrasive grain dispersant for polishing according to claim 1, which is for polishing glass. 10. A weight ratio (A) / (B) of (A) and (B).
Is 1/1 to 10/1, the abrasive dispersant for polishing according to any one of claims 1 to 9. 11. A polishing slurry comprising the abrasive dispersant (I) for polishing according to any one of claims 1 to 10, an abrasive (D) and water.