JP6489465B2 - Polyurea composite abrasive and method for producing the same - Google Patents

Description

  The present invention relates to a polyurea composite abrasive suitable for use in polishing of metals, stainless steel, titanium alloys, glass, minerals, stones, ceramics, plastics, and the like, more specifically, a computer hard disk substrate and a semiconductor device. Polyurea composite polishing suitable for precision polishing of wafers (silicon, sapphire, silicon carbide, ticker gallium, etc.), aluminum substrates, printed boards, laminates, lenses, precision machine parts surfaces, optical fiber end faces and sheet metal painted surfaces The present invention relates to a material and a manufacturing method thereof.

Glass that is useful in the optical field, brittle materials such as silicon, sapphire, and silicon carbide that are useful in the semiconductor field require mirror finishing, and generally use a polishing pad and a slurry containing fine abrasive grains in combination. Polishing with loose abrasive has been applied. However, this method has poor productivity, requires high costs for waste liquid treatment, is economically disadvantageous, and requires a new technology to replace it.
Therefore, a technique that is actively studied is a method of polishing with a polishing material that holds fine abrasive grains uniformly at a high concentration and with an appropriate bonding force. According to this method, the abrasive grains initially scratched as fixed abrasive grains fall off during the polishing process, and this is used for rolling operation as free abrasive grains, so that excellent productivity and polishing effect can be obtained. The
As a binder for this abrasive, phenol resin has been mainly studied. However, although high-efficiency processing is possible, there is a drawback that scratches are easily generated and damage is large. This is due to the non-uniform dispersion of the fine abrasive grains and the characteristics of the phenol resin itself as a binder (high hardness and brittleness). That is, when a phenol resin is used as the binder, the abrasive grains easily fall off from the abrasive as an aggregate, which is considered to cause scratches.
In addition to phenolic resins, abrasives that use urethane or rubber as a binder, and abrasives that use polyurea as a binder have been studied (for example, Patent Documents 1 to 3).

JP-A-11-291175 Japanese Patent No. 3921056 Japanese Patent No. 4357173

Patent Document 3 describes a grinding material containing fine abrasive grains having a grain size of # 3000 mesh or less as abrasive grains at a high concentration, but the abrasive grain concentration is still 57% by mass (35% by volume). (Example 6 of Patent Document 3). When the abrasive concentration in the abrasive described in Patent Document 3 is further increased, the mixture of abrasive grains and polyurea resin does not exhibit fluidity and cannot be injected into the mold. Even if a large amount of foaming agent is added, the thixotropy is abnormally high due to the fine abrasive system, resulting in a colloidal form and still difficult to inject into the mold. When the mixture that does not exhibit fluidity is filled into a mold using a spatula or the like and molded and cured, the resulting molded product has many cracks and does not have a function as an abrasive. .
The present invention is a polyurea composite abrasive comprising a polyurea resin as a binder and holding a high concentration of fine abrasive grains, and exhibits good scratch abradability when used for polishing, and is polished. It is an object of the present invention to provide an abrasive exhibiting good rolling abrasiveness by dropping fine abrasive grains therein. Another object of the present invention is to provide a method for producing the polyurea composite abrasive.

The present inventor has intensively studied to achieve the above problems. As a result, a polyamine compound and a polyisocyanate compound are mixed and reacted in an organic solvent at a specific ratio, and before the reaction liquid is gelled (that is, the liquid state in which the reaction liquid exhibits fluidity (preferably the reaction liquid). The fine abrasive grains are added at a high concentration with a viscosity of 3000 to 5000 mPa · S), and the mixture is stirred and concentrated while constantly maintaining uniformity (preferably a solid content of 40). -92 mass% concentrate) is obtained, this mold is filled into a mold and pressure-molded, and further polymerized under pressure, and then subjected to heat treatment to complete the polymerization reaction. It has been found that a polishing material having a high compressive modulus can be obtained by holding the abrasive grains at a high concentration and evenly (by completely curing), and when this polishing material is used for polishing, a good scratch polishing property is obtained. Show and polish It has been found that fine abrasive grains fall off at an appropriate speed and show good rolling abrasiveness.
The present invention has been completed based on these findings.

The above-described problems of the present invention have been solved by the following means.
[1]
A polyurea composite abrasive comprising a composite of abrasive grains and a polyurea resin, the polyurea composite abrasive comprising a polyurea resin solution that retains fluidity before gelation, and an abrasive having a particle size finer than # 2000 mesh And a mixture obtained by concentrating the mixture to obtain a concentrate in which the organic solvent in the polyurea resin solution remains, and obtaining the concentrate by pressure molding,
The polyurea composite abrasive particle size fine abrasive than # 2000 mesh containing 50 to 95 vol%, and, density is 0.45~2.0g / cm ^3, polyurea composite abrasive .
[2]
In the polyurea resin, a polyisocyanate compound and a polyamine compound are mixed in an organic solvent at a ratio shown below to cause a polymerization reaction, and the abrasive is mixed before the reaction solution is gelled. The polyurea composite abrasive according to [1], which is polymerized.
[Isocyanate group equivalent of polyisocyanate compound] / [amino group equivalent of polyamine compound] = 0.90 to 2.00
[3]
The polyurea composite abrasive according to [ 2], wherein the polyamine compound is any of the following (a) to (f).
(A) aromatic polyamine oligomer (b) aromatic diamine compound (c) aromatic polyamine oligomer and aromatic diamine compound (d) aliphatic polyamine oligomer and aromatic diamine compound (e) aliphatic polyamine oligomer, aromatic polyamine oligomer And aromatic diamine compound (f) aliphatic polyamine oligomer and aromatic polyamine oligomer [4]
The polyurea composite abrasive according to [3], wherein the aromatic polyamine oligomer includes a polyamine oligomer represented by the following formula (I).

(In the formula, R represents a residue of an n-valent polyalkylene polyol, polyalkylene ether polyol or polyalkylene ester polyol having a number average molecular weight of 200 or more, and n represents 2 or 3. (It may contain a saturated bond.)
[5]
The aromatic diamine compound is 4,4′-methylenebis (2-chloroaniline), 4,4′-methylenebis (2,3-dichloroaniline), 4,4′-methylenebis (2,5-dichloroaniline), 4,4′-methylenebis (3-chloro-2,5-diethylaniline), 4,4′-methylenebis (2-methyl-6-ethylaniline), trimethylenebis (4-aminobenzoate), 4-chloro- 3,5-diamino-benzoic acid isobutyl, 3,5-dimethylthio-2,4-toluenediamine, 3,5-dimethylthio-2,6-toluenediamine, 3,5-diethyl-2,6-toluenediamine, 3, 5-diethyl-2,4-toluenediamine, 4,4′-methylenebis (methylanthraanilate), and 1,2-bis (2-aminophenylthio) ethane It is selected from the group consisting of at least one aromatic diamine compound, [3] or polyurea composite abrasive according to any one of [4].
[6]
The polyurea composite abrasive according to any one of [3] to [5], wherein the aliphatic polyamine oligomer includes a polyamine oligomer represented by any one of the following formulas (II) to (IV).

_{H 2 N-CH (CH 3} ) -CH 2 -R 2 -NH 2 (II)

In formula (II), R ² represents — [O—CH ₂ —CH (CH ₃ )] _p — or — [O—CH (CH ₃ ) —CH ₂ ] _q — [O—CH ₂ —CH]. _{2] r - [O-CH} 2 -CH (CH 3)] s - is a divalent group represented by. Each of p to s indicating the number of repeating units is 1 or more, and q + s is 2 or more.
_{H 2 N- [O-CH (} CH 3) -CH 2 ] _{t - [O-CH 2 -CH} 2 -CH 2 -CH 2] u - _{[O-CH 2 -CH (CH 3} ) ] _v -NH ₂ (III)

In the formula (III), t to v indicating the number of repeating units are all 1 or more, and t + v is 6 or more.

式（IV）中、Ｒ^ａは水素原子又はエチル基である。繰り返し単位の数を示すｗはそれぞれ独立に１以上であり、且つ３つのｗの合計が５以上である。Ｒ^ａが水素原子の場合ｘは０であり、Ｒ^ａがエチル基の場合ｘは１である。
〔７〕
研磨又はみがきに用いる、〔１〕〜〔６〕のいずれか１項に記載のポリ尿素複合研磨材。
〔８〕
圧縮弾性率が２０〜１３０ｋｇｆ／ｍｍ^２である、〔１〕〜〔７〕のいずれか１項に記載のポリ尿素複合研磨材。
〔９〕
砥粒とポリ尿素樹脂を複合したポリ尿素複合研磨材の製造方法であって、該製造方法は、
ポリアミン化合物を含有する有機溶媒中にポリイソシアネート化合物を混合して反応させて、ポリ尿素樹脂を２〜２０質量％含有し、ゲル化前で流動性を保持した溶液を得る工程；
前記ポリ尿素樹脂溶液と、粒度が＃２０００メッシュより微細な砥粒とを混合し、該混合液を濃縮して前記有機溶媒が残存する濃縮物を得る工程；
前記濃縮物を加圧成形し、加圧下でさらに重合させる工程；及び
成形物を熱処理してポリ尿素樹脂を硬化させる工程
を含み、前記ポリ尿素複合研磨材は、粒度が＃２０００メッシュより微細な砥粒を５０〜９５体積％含有し、且つ、密度が０．４５〜２．０ｇ／ｃｍ ^３ である、ポリ尿素複合研磨材の製造方法。

In the formula (IV), R ^a is a hydrogen atom or an ethyl group. Each w indicating the number of repeating units is independently 1 or more, and the total of the three ws is 5 or more. When R ^a is a hydrogen atom, x is 0, and when R ^a is an ethyl group, x is 1.
[7]
The polyurea composite abrasive according to any one of [1] to [6], which is used for polishing or polishing.
[8]
The polyurea composite abrasive according to any one of [1] to [7], wherein the compression elastic modulus is 20 to 130 kgf / mm ² .
[9]
A method for producing a polyurea composite abrasive comprising a composite of abrasive grains and polyurea resin, the production method comprising:
A step of mixing and reacting a polyisocyanate compound in an organic solvent containing a polyamine compound to obtain a solution containing 2 to 20% by mass of a polyurea resin and retaining fluidity before gelation;
Mixing the polyurea resin solution and abrasive grains having a particle size finer than # 2000 mesh, and concentrating the mixed solution to obtain a concentrate in which the organic solvent remains;
Said concentrate to pressure molding, further polymerized to step under pressure; look including the step of curing and polyurea resin by heat-treating the molded product, the polyurea composite abrasive particle size finer than # 2000 mesh The manufacturing method of the polyurea composite abrasive | polishing material which contains 50-95 volume% of an abrasive grain, and a density is 0.45-2.0 g / cm < ³ > .

  The polyurea composite abrasive of the present invention is a composite of a large amount of fine abrasive grains and a binder polyurea resin. When polishing is performed using the abrasive, the composite of abrasive grains and polyurea resin is formed. Good scratch polishing performance is exhibited by the action, and since fine abrasive grains fall off at an appropriate rate during polishing, polishing is also good.

It is the top view (1a) and side view (1b, the figure which looked at the top view 1a from the A side) for demonstrating the structure of the abrasion testing machine used in the Example.

The polyurea composite abrasive of the present invention (hereinafter also referred to as the abrasive of the present invention) will be described below.
The abrasive of the present invention contains a polyurea resin as a binder. The abrasive of the present invention contains 50 to 95% by volume of fine abrasive grains having a particle size smaller than # 2000, and the density of the abrasive is 0.45 to 2.0 g / cm ³ . The abrasive of the present invention is usually in a form in which polyurea resin and abrasive grains are homogeneously mixed.

The polyurea resin that is a binder in the abrasive of the present invention is a polymer obtained by reacting a polyisocyanate compound having two or more isocyanate groups with a polyamine compound having two or more amino groups.
Arbitrary polyisocyanate can be used as a polyisocyanate compound used as a raw material of a binder. For example, toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), MDI polymer, polyphenylene polyisocyanate (crude MDI), carbodiimide modified MDI, carbodiimide modified MDI polymer, cyclohexane diisocyanate (CHDI), isophorone diisocyanate (IPDI), naphthalene diisocyanate (NDI) ), 3,3′-dimethyl-4,4′-diphenylene diisocyanate (TODI), phenylene diisocyanate, and paraphenylene diisocyanate (PPDI) can be used. Further, a hexamethylene diisocyanate dimer (uretidione conjugate), a trimer (isocyanurate conjugate) or a mixture thereof may be used in combination. In addition, a prepolymer obtained by reacting a part of polyisocyanate with polyether, polyester or polybutadiene polyol can be used in combination.

In the polishing material of the present invention, the polyamine compound used as a raw material for the binder is not particularly limited as long as it reacts with the polyisocyanate compound and polymerizes to form a polyurea resin, but the following (a) to ( It is preferable to use any of f).
(A) aromatic polyamine oligomer (b) aromatic diamine compound (c) aromatic polyamine oligomer and aromatic diamine compound (d) aliphatic polyamine oligomer and aromatic diamine compound (e) aliphatic polyamine oligomer, aromatic polyamine oligomer And aromatic diamine compound (f) aliphatic polyamine oligomer and aromatic polyamine oligomer

  In said (b)-(e), there is no restriction | limiting in particular in the ratio of an aromatic diamine compound. As the proportion of the aromatic diamine compound increases, the hardness, tear strength, adhesive strength, and softening point of the resulting polyurea resin increase. As a result, the polishing power of the abrasive is increased, the surface becomes rough and the durability increases. Conversely, when the proportion of the aromatic diamine compound decreases, the resulting polyurea resin hardness, tear strength, and adhesive strength decrease. As a result, the polishing power of the abrasive is reduced, the surface roughness is reduced, and the detachability of the abrasive grains from the abrasive is improved. That is, the ratio of the aromatic diamine compound is appropriately adjusted according to the intended function of the abrasive.

In the above (c), (e) and (f), the ratio of the aromatic polyamine oligomer is not particularly limited. When the ratio of the aromatic polyamine oligomer is increased, the hardness of the resulting polyurea resin is lowered, and the elongation and rubber elasticity are increased. Therefore, although the polishing power of the obtained abrasive is reduced, the surface roughness obtained is small and a mirror surface is easily obtained. On the contrary, when the ratio of the aromatic polyamine oligomer is decreased, the obtained polyurea resin has high hardness, elongation is decreased, rubber elasticity is decreased, and a tendency to resin is increased. As a result, the polishability of the abrasive is increased and the surface roughness is increased. In addition, the abrasive removability is lowered and the durability is improved.
That is, the ratio of the aromatic polyamine oligomer is appropriately adjusted according to the intended function of the abrasive.
In the above (d), (e) and (f), the ratio of the aliphatic polyamine oligomer is not particularly limited. When the proportion of the aliphatic polyamine oligomer is increased, the deureability of the polyurea resin that can be accelerated is improved. Accordingly, it is possible to prevent the abrasive from being damaged when it is demolded. Moreover, the detachability of the abrasive grains from the abrasive can be improved. On the contrary, when the ratio of the aliphatic polyamine oligomer is decreased, the detachability of the abrasive grains is lowered and the durability can be enhanced.
That is, the ratio of the aliphatic polyamine oligomer is appropriately adjusted according to the intended function of the abrasive.

  The aromatic polyamine oligomer preferably contains one or more compounds represented by the following formula (I). The ratio of the compound represented by the following formula (I) in the aromatic polyamine oligomer is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, further preferably 80 to 100% by mass, and 90 to 100% by mass. % Is more preferable. The aromatic polyamine oligomer that can be used in the present invention is more preferably a compound represented by the following formula (I).

In the formula (I), R is a residue of an n-valent polyalkylene polyol, polyalkylene ether polyol or polyalkylene ester polyol having a number average molecular weight of 200 or more (that is, a polyalkylene polyol having a number average molecular weight of 200 or more, a number average molecular weight). It has a structure in which n hydroxyl groups or hydrogen atoms are removed from a polyalkylene ether polyol of 200 or more or a polyalkylene ester polyol having a number average molecular weight of 200 or more, and a site from which the hydroxyl group or hydrogen atom is removed is defined as a linking site. N-valent group). n represents 2 or 3, and is preferably 2. However, the polyalkylene may contain an unsaturated bond. Moreover, it is preferable that each said polyol is diol.
200-2000 are preferable, as for the number average molecular weight of said polyalkylene polyol, polyalkylene ether polyol, or polyalkylene ester polyol, 600-2000 are more preferable, and 1000-2000 are more preferable.
In the present specification, the number average molecular weight can be measured by quantitative determination of the hydroxyl group of the molecular end group or by gel permeation chromatography (GPC).

The aromatic polyamine oligomer represented by the above formula (I) is generally obtained by reacting a polyalkylene polyol, polyalkylene ether polyol or polyalkylene ester polyol having a number average molecular weight of 200 or more with paranitrobenzoic acid chloride, and then reacting the nitro group. It can be synthesized by reduction. Alternatively, it can be obtained by reacting a polyalkylene polyol, polyalkylene ether polyol or polyalkylene ester polyol having a number average molecular weight of 200 or more with an aminobenzoic acid alkyl ester.
Examples of the polyalkylene polyol, polyalkylene ether polyol, or polyalkylene ester polyol having a number average molecular weight of 200 or more used in the above reaction include polytetramethylene ether glycol, polypropylene ether glycol, and a glycol of a copolymer of propylene oxide and ethylene oxide. Polyether polyols; Polyester polyols such as polyethylene adipate polyols, polybutylene adipate polyols, ε-caprolactone, lactone polyester polyols derived from γ-butyrolactone, adipate polyols obtained by the reaction of 3-methylpentanediol and adipic acid; Examples include polyalkylene polyols such as polybutadiene-based polyols.

The terminal group of the aromatic polyamine oligomer is generally an amino group, but in some cases, a part of the end of the oligomer used may remain as a hydroxyl group, or the end group of the oligomer used It can be used even if some of both ends remain as hydroxyl groups. In some cases, an amide group may be contained in a part of the main chain.
The aromatic polyamine oligomer is available as a commercial product. As the above-mentioned polyol, for example, aromatic polyamine oligomer using polytetramethylene ether glycol (PTMEG) as a raw material, Versaring P-250 (polyol molecular weight 250), Versalink P-650 (available from Air Products and Chemicals) Polyol molecular weight 650), Versalink P-1000 (polyol molecular weight 1000), Versalink P-2000 (polyol molecular weight 2000) (both are trade names), and Elastomer 1000 ( In addition to porea S-100A) (polyol molecular weight 1000), a poree SL-100A (polyol molecular weight 1000) modified with a low melting point (both are trade names), an elastomer made from polyester polyol as a polyol. Over 1000ES (polyol molecular weight 1000) (both, trade name) and the like. These aromatic polyamine oligomers can be used singly or in combination of two or more.

The aromatic diamine compound that can be used as a raw material for the binder is not particularly limited.
4,4′-methylenebis (2-chloroaniline),
4,4′-methylenebis (2,3-dichloroaniline),
4,4′-methylenebis (2,5-dichloroaniline),
4,4′-methylenebis (3-chloro-2,5-diethyleneaniline),
4,4′-methylenebis (methylanthraanilate),
Trimethylene bis (4-aminobenzoate),
4,4'-methylenebis (2-methyl-6-ethylaniline)
4-chloro-3,5-diamino-benzoic acid isobutyl ester,
3,5-dimethylthio-2,4-toluenediamine,
3,5-dimethylthio-2,6-toluenediamine,
3,5-diethyl-2,4-toluenediamine,
3,5-diethyl-2,6-toluenediamine,
1,2-bis (2-aminophenylthio) ethane 4,4′-ethylenebis (2,6-dimethylaniline),
4,4′-ethylenebis (2,6-diethylaniline),
4,4′-ethylenebis (2,6-diisopropylaniline),
4,4′-ethylenebis (2-methyl-6-isopropylaniline),
4,4′-ethylenebis (2-ethyl-6-isopropylaniline),
4,4′-ethylenebis (2-methyl-6-tbutylaniline)
Can be mentioned. The aromatic diamine compound used as the raw material for the binder preferably contains one or more of the exemplified aromatic diamine compounds. 50-100 mass% is preferable, as for the ratio of the 1 type (s) or 2 or more types of the said exemplified aromatic diamine compound to the said aromatic diamine compound used as a raw material of a binder, 70-100 mass% is more preferable, 80- 100 mass% is more preferable and 90-100 mass% is further more preferable. It is more preferable that all of the aromatic diamine compounds used as the raw material for the binder are one or more of the exemplified aromatic diamine compounds.

  Although there is no restriction | limiting in particular in the said aliphatic polyamine oligomer used as a raw material of a binder, It is preferable to contain the 1 type (s) or 2 or more types of the compound represented by the formula in any one of following formula (II)-(IV). The ratio of the total amount of the compound represented by any one of the following formulas (II) to (IV) in the aliphatic polyamine oligomer used as the raw material for the binder is preferably 50 to 100% by mass, and 70 to 100% by mass. More preferably, 80-100 mass% is further more preferable, and 90-100 mass% is further more preferable. Moreover, it is more preferable that all of the aliphatic polyamine compounds used as raw materials for the binder are compounds represented by any one of the following formulas (II) to (IV).

_{H 2 N-CH (CH 3} ) -CH 2 -R 2 -NH 2 (II)

In formula (II), R ² represents — [O—CH ₂ —CH (CH ₃ )] _p — or — [O—CH (CH ₃ ) —CH ₂ ] _q — [O—CH ₂ —CH]. _{2] r - [O-CH} 2 -CH (CH 3)] s - is a divalent group represented by. Each of p to s indicating the number of repeating units is 1 or more. p is preferably 1 to 68, and more preferably 5 to 33. q + s is 2 or more, and preferably 3.6 to 6.0. r is preferably 9 to 38.7, more preferably 12 to 38.7.

_{H 2 N- [O-CH (} CH 3) -CH 2 ] _{t - [O-CH 2 -CH} 2 -CH 2 -CH 2] u - _{[O-CH 2 -CH (CH 3} ) ] _v -NH ₂ (III)

In formula (III), tv indicating the number of repeating units is 1 or more. u is preferably 9-17, and more preferably 11-17. t + v is 6 or more, and preferably 6 to 24.

In the formula (IV), R ^a represents a hydrogen atom or an ethyl group. Each w indicating the number of repeating units is independently 1 or more, and the total of the three ws is 5 or more. 5-85 is preferable and, as for the sum total of three w, 5-50 are more preferable.
x is 0 or 1. If Ra is a hydrogen atom x is 0 when R ^a is an ethyl group and x is 1.

  The number average molecular weight of the aliphatic polyamine oligomer that can be used in the present invention is preferably 200 to 5000, more preferably 400 to 5000, and still more preferably 2000 to 5000.

The aliphatic polyamine oligomers represented by the above formulas (II) and (III) can be obtained by ring-opening polymerization of propylene oxide to polyethylene glycol, trimethylolpropane, and glycerin, and ammonolysis of the terminal group.
The aliphatic polyamine oligomers represented by the above formulas (II) and (III) can also be obtained commercially. Examples of the compound of the formula (II) include Jeffamine D400 (number average molecular weight 400), Jeffamine D2000 (number average molecular weight 2000), Jeffamine ED-900 (number average molecular weight 900) commercially available from Sun Techno Chemical Co., Ltd. ), Jeffamine ED2003 (number average molecular weight 2000) can be used. Examples of the compound represented by the formula (III) include Jeffamine T-403 (number average molecular weight 440), Jeffamine T-3000 (number average molecular weight 3000), and Jeffamine T-, which are commercially available from Sun Techno Chemical Co., Ltd. 5000 (number average molecular weight 5000) can be used.

  In the abrasive of the present invention, the polyurea resin of the binder is prepared by mixing the polyisocyanate compound and the polyamine compound in an organic solvent in the following ratio, and preferably reacting at room temperature (usually 20 to 30 ° C.). Before the reaction liquid is gelled, it is preferable that the above-mentioned abrasive grains are mixed and further polymerized in the presence of the abrasive grains, preferably in a state where the viscosity of the reaction liquid is 3000 to 5000 mPa · s. By doing so, the polyurea resin and the abrasive grains can be sufficiently mixed, and the combined effect of the polyurea resin and the abrasive grains is effectively expressed. The viscosity is measured using a B-type viscometer at a temperature of 25 ° C.

[Isocyanate group equivalent of polyisocyanate compound] / [amino group equivalent of polyamine compound] = 0.90 to 2.00

If the above [isocyanate group equivalent of polyisocyanate compound] / [amino group equivalent of polyamine compound] = equivalent ratio [NCO / NH ₂ ] (hereinafter referred to as isocyanate index (NCOindex)) is too small, the softening point of polyurea resin This is undesirable because it causes a decrease in heat resistance. On the other hand, if the isocyanate index is too large, the rubber elasticity of the polyurea resin becomes dull, which is not preferable because it is too hard and too brittle. A more preferable range of the isocyanate index is 0.95 to 1.50, 1.05 to 1.30 is more preferable, and 1.05 to 1.20 is more preferable.

In the production of the abrasive of the present invention, a curing catalyst may be added. Examples of curing catalysts include amine-based triethylenediamine and those dissolved in a glycol solvent, such as DABCO-1027, DABCO-1028, DABCO-33LV (all trade names) manufactured by Sankyo Air Products Co., Ltd. N, N, N ′, N′-tetramethyl-1,6-hexanediamine, N, N-dimethylcyclohexylamine, (N, N-dimethylaminoethyl) ether, etc., and salts of organic acids (acetic acid Potassium salts, potassium oxalate salts, and the like) and organometallic catalysts (dibutyltin dilaurate, stannous octate, and the like), but are not limited thereto.
These may be used alone or in combination of two or more. The amount used is suitably within 5% by mass with respect to the polyamine compound.

  As abrasive grains used in the abrasive of the present invention, alumina such as white alundum (WA) and alundum (A), silicon carbide such as green carborundum (GC) and carborundum (C), diamond (nickel coated diamond) Including), cubic boron nitride (CBN), ferric oxide, manganese oxide, chromium oxide, silicon dioxide (quartz fused silica, colloidal silica, fumed silica), cerium oxide, zirconium oxide, calcium carbonate, barium carbonate, oxidation Magnesium, mica and the like can be used alone or in combination of two or more.

Abrasive grains having a grain size finer than # 2000 mesh size are used for the abrasive of the present invention. If the particle size is finer than # 2000 mesh size, the particle size is not limited. For example, the grain size of the abrasive grains may be finer than # 3000, finer than # 4000, or finer than # 5000. From the viewpoint of availability, it is practical to use abrasive grains whose grain size is larger than # 200000 mesh.
The “mesh” means the number of cells per inch (25.4 mm). For example, # 2000 mesh is a mesh having 2000 cells per inch.

The content (abrasive grain concentration) of abrasive grains in the abrasive of the present invention is 50 to 95 volume%. When the content of abrasive grains in the abrasive is less than 50% by volume, the binding force of the polyurea binder becomes too strong, and the drop-off property of the abrasive grains decreases, which is not preferable. On the other hand, when the content of the abrasive grains in the abrasive exceeds 95% by volume, the binding strength of polyurea is lowered, which is not preferable. The content of abrasive grains in the abrasive is preferably 60% by volume or more. The content of abrasive grains in the abrasive is also preferably 65% by volume or more, preferably 70% by volume or more, and preferably 80% by volume or more. The content (volume%) of the abrasive grains represents the blending quantity (volume) of the abrasive grains in% of the total blending quantity (volume) of the raw materials excluding the solvent. In addition, when an abrasive grain is a hollow body, the volume of an abrasive grain is a volume including a hollow part.
When abrasive grains that are not hollow bodies are used as the abrasive grains, from the same viewpoint as described above, the content of abrasive grains in the abrasive of the present invention is preferably 70% by mass or more, and 80% by mass or more. It is more preferable that it is more than 90 mass%, and it is further more preferable that it is 92 mass% or more. The content of abrasive grains in the abrasive of the present invention is preferably 98% by mass or less, more preferably 97% by mass or less, and further preferably 96% by mass or less. The content (mass%) of the abrasive grains represents the blending quantity (mass) of the abrasive grains in% of the total blending quantity (mass) of the raw materials excluding the solvent.

The density of the abrasive of the present invention is 0.45 to 2.0 g / cm ³ , more preferably 1.0 to 2.0 g / cm ³ , and still more preferably 1.2 to 2.0 g / cm ^3. It is. By setting the abrasive grain density within the above range, moderate abrasive grain detachability is exhibited.
That is, the abrasive of the present invention is formed by forming a composite of abrasive grains finer than # 2000 mesh and a polyurea resin as a binder with an appropriate bonding force, and when polishing is performed using the abrasive, Good scratch polishing performance is exhibited by the combined action of the grains and the polyurea resin, and fine abrasive grains fall off at an appropriate rate during polishing and polishing, so that good rolling abrasiveness is also exhibited.

The abrasive of the present invention may contain titanium oxide, bengara, iron oxide, graphite, hindered amine, hindered phenol, or thiazole compound as a filler.
Moreover, you may contain polyester fiber, polyamide fiber, glass fiber, wool, cotton, silk etc. as a fiber type material (fibrous filler). When the abrasive of the present invention contains a fibrous filler, the content (% by mass) of the fibrous filler in the abrasive is preferably 1 to 15% by mass, and preferably 3 to 13% by mass. More preferably, it is more preferably 5 to 12% by mass. The content (mass%) of the fibrous filler in the abrasive is the percentage (mass) of the fibrous filler in the total blending quantity (mass) of the raw material excluding the solvent.
Moreover, you may contain foam | bubble bodies, such as a polymer hollow microsphere composite (particle diameter 10-14 micrometers), for example, Matsumoto microsphere-MFL series, an inorganic type hollow microsphere (silica type).

The abrasive of the present invention preferably has a compression modulus of 20 to 130 kgf / mm ² . Preferably the compressive elastic modulus is 25 kgf / mm ² or more, more preferably 30 kgf / mm ² or more. It is preferable that the compressive modulus is less than 100 kgf / mm ^2, preferably less than 98kgf / mm ^2, more preferably less than 96kgf / mm ^2. By setting the compression elastic modulus within the above range, it is difficult to apply the end portion, and a more durable abrasive can be obtained.

  Then, the manufacturing method of the abrasive | polishing material of this invention is demonstrated.

The method for producing an abrasive of the present invention includes the following steps:
A step of mixing and reacting a polyisocyanate compound in an organic solvent containing a polyamine compound to obtain a solution containing 2 to 20% by mass of a polyurea resin and retaining fluidity before gelation;
Mixing the polyurea resin solution and abrasive grains having a particle size finer than # 2000 mesh, and concentrating the mixed solution to obtain a concentrate in which the organic solvent remains;
A step of pressure-molding the concentrate and further polymerizing under pressure; and a step of heat-treating the molding to cure the polyurea resin.

The organic solvent that can be used in the production method of the present invention can dissolve (i) both low-molecular and high-molecular polyureas, (ii) can impart wettability to abrasive grains, It is preferable that iii) high volatility and (iv) adhesiveness is maintained even during pressure molding.
Examples of the solvent that satisfies the above requirements include methylene dichloride, HFC-365mfc (CF ₃ CH ₂ CF ₂ CH ₃ ), N-pentane, cyclopentane, n-hexane, n-heptane, cyclohexane, toluene, xylene, N.I. N-dimethylformamide, N.I. N-dimethylacetamide, and N.I. The 1 type (s) or 2 or more types chosen from N-dimethylsulfoxide is mentioned.

The amount of the organic solvent used is preferably an amount sufficient to dissolve the polyamine compound or polyurea resin and disperse the abrasive grains after adding fine abrasive grains. For example, when the amount of abrasive grains to be blended is 100% by mass, it is preferably 90% by mass or more, and more preferably 90 to 150% by mass.
In order to shorten the work of the concentration step described later, a low boiling point solvent (for example, methylene dichloride, HFC-365mfc (CF ₃ CH ₂ CF ₂ CH ₃ ), N-pentane, cyclopentane, n-hexane, It is preferable to use one or two or more solvents selected from n-heptane, cyclohexane, toluene, and xylene), but the high-boiling solvent (for example, NN) is used with respect to 100% by mass of the low-boiling solvent. -One or more solvents selected from dimethylformamide, NN-dimethylacetamide, and NN-dimethylsulfoxide) are added within 20% by mass (preferably 3 to 20% by mass). As a result, the organic solvent can be appropriately left even after the concentration, the tackiness (stickiness) of the concentrate is increased (adhesion is increased), and the moldability is high. The preferred because it is. That is, it is preferable to use an organic solvent obtained by mixing a small amount of a high-boiling solvent with a low-boiling solvent because the above (iii) and (iv) can be achieved at a higher level.

When mixing a polyisocyanate compound in the organic solvent containing said polyamine compound, an isocyanate index becomes like this. Preferably it is 0.90-2.00, More preferably, it is 0.95-1.50, More preferably, it is 1.05-. It is preferable to add a polyisocyanate compound so as to be 1.30, more preferably 1.05 to 1.20. The mixed solution is made homogeneous or stirred, preferably at room temperature (preferably 20 to 30 ° C.) to advance the reaction to some extent to obtain a polyurea resin solution (a solution that retains fluidity, preferably a viscosity of 3000). To ˜5000 mPa · S or less). If the reaction time is too long, the polymerization proceeds too much and the solution gels, making it difficult to uniformly mix the polyurea resin and the abrasive grains. Therefore, the reaction time here is suitably several minutes to several tens of minutes at room temperature.
The concentration of polyurea resin in the solution that retains fluidity before gelation is the ratio of the total amount of polyamine compound and polyisocyanate compound used as raw materials to the total amount of solvent, polyamine compound and polyisocyanate compound used as raw materials It is calculated as (mass%).

When mixing the fine abrasive grains in this solution, the final mixing is performed so that the abrasive grain content in the abrasive is 50 to 95 volume%. The mixing amount of the abrasive grains is preferably set such that the content of the abrasive grains in the abrasive becomes a preferable content of the abrasive grains in the above-described abrasive of the present invention. Subsequently, while stirring at room temperature to 40 ° C. (preferably 20 to 40 ° C.), the mixture is continuously concentrated (or may be concentrated under reduced pressure) to obtain a concentrate. This concentrate is preferably a dango-like high-viscosity material or a powder having a sticky surface. Preferably, the solid content of the concentrate is 40 to 92% by mass, and the solvent remains in an appropriate state. By leaving the solvent at this stage, poor adhesion between the abrasive grains is less likely to occur in subsequent pressure molding, and the moldability is improved.
The time for the concentration is about 10 to 60 minutes, and a shorter one is more preferable. By using a low boiling point solvent in a high ratio as described above, concentration in a shorter time becomes possible. If too much time is spent, the polyurea resin may be gelled before pressure molding.

The concentrate is filled in a mold, press-molded (press-molded), and the polymerization reaction proceeds under pressure as it is. The pressure condition including pressure molding is preferably 50 to 1000 kgf / cm ² . The reaction time under pressure is preferably 2 to 7 hours. Moreover, it is preferable to raise a pressure in steps within the range of the said pressurization conditions. The temperature during pressing and curing is preferably from room temperature to 50 ° C. If the temperature is too high, the solvent may volatilize immediately and a desired molded product may not be obtained.

Thereafter, the mold is removed and subjected to heat treatment. By the heat treatment, the remaining organic solvent is removed, and the polymerization reaction sufficiently proceeds, so that the polyurea resin is completely cured. It is preferable that the temperature of heat processing shall be 50-150 degreeC. The heat treatment time is preferably 2 to 20 hours, and more preferably 5 to 15 hours. Moreover, it is preferable to raise temperature in steps. For example, it can be processed at about 50 ° C. for 1 to 2 hours, then processed at about 80 ° C. for 1 to 2 hours, and then further processed at about 120 ° C. for 4 to 7 hours.
The abrasive of the present invention can be obtained through the above steps.

  In addition, when making the above-mentioned fibrous filler, filler, etc. contain in an abrasive | polishing material, it is preferable to mix | blend at the time of mixing of an abrasive grain.

  In addition, when the abrasive obtained above is cracked or brittle in strength, a polyisocyanate compound corresponding to 1/3 to 1/2 of the polyurea resin required for blending design and A mixture of polyamine compounds (mixed solution mixed in an organic solvent) is reacted for 5 to 30 minutes in the same manner as described above. The resulting polyurea resin solution is mixed with abrasive grains and concentrated to a powder, and a constant temperature bath. Heat treatment (for example, heat treatment at about 50 ° C. for about 2 hours and then at about 120 ° C. for about 5 hours), so that polyurea is primarily coated on the abrasive grains, and this is used as the abrasive raw material for the remaining 2 / A polishing material may be obtained by the same method as described above using a 3-1 / 2 polyurea resin.

EXAMPLES Next, although an Example demonstrates this invention further, this invention is not limited at all by these Examples.
In addition, the following raw materials were used for the main component of polyisocyanate and the curing agent component of aromatic diamines.

[Polyisocyanate compound]
Liq MDI (liquid MDI) [Mitsubishi Chemical Corporation] NCO content 29.0 wt%
・ CMDI (Mitsui Chemicals) NCO content 31.5wt%

[Polyamine compound]
Elastomer 1000 (aromatic polyamine oligomer): poly (tetramethylene oxide) -di-P-aminobenzoate [manufactured by Ihara Chemical Industry] amine value 89.8 KOH mg / g
MOCA (aromatic diamine compound): 4.4'-methylenebis (2-chloroaniline)
[Ihara Chemical Industry Co., Ltd.] Amine value 420 KOH mg / g
・ Jeffamine D-2000 (aliphatic polyamine oligomer)
[Manufactured by Sun Techno Chemical Co., Ltd.] Amine value 56.1 KOH mg / g
CUA-4 (aromatic diamine compound): trimethylene bis (4-aminobenzoate)
[Ihara Chemical Industry Co., Ltd.] Amine value 356.9 KOH mg / g
Heart cure 10 (aromatic diamine compound): a mixture of 3.5-diethyl-2.4-toluenediamine and 3.5-diethyl-2.6-toluenediamine [manufactured by Ihara Chemical Industry Co., Ltd.] amine value 629 KOHmg / g

[Organic solvent]
MC: Methylene chloride (Asahi Glass Co., Ltd.)
DMF: N, N-dimethylformamide (Wako Pure Chemical Industries, Ltd.)

[Abrasive grain]
・ Green Carborundum (Nanko Ceramics)
GC # 2000, GC # 3000, GC # 8000
・ White Alundum WA # 3000

[Preparation of polyurea resin solution]
(Polyamine solution A)
1.35 g of MOCA was added to 3.65 g of Elastomer 1000, heated to 120 ° C., MOCA was completely dissolved with stirring, and cooled to room temperature to obtain polyamine solution A.
(Polyamine solution B)
0.5 g of MOCA was added to 4.50 g of Elastomer 1000, and the mixture was humidified to 120 ° C., MOCA was completely dissolved with stirring, and cooled to room temperature to obtain polyamine solution B.
(Polyamine solution C)
Elastomer 1000 was designated as polyamine solution C.
(Polyamine solution D)
1.35 g of CUA-4 was added to 3.65 g of Elastomer 1000, completely dissolved at 130 ° C., cooled to room temperature, and polyamine solution D was obtained.

[Examples 1 to 11]
In accordance with the formulation shown in the table below (unit of blending amount in the table: mass (g)), first, a predetermined amount of MC and DMF was taken as a predetermined amount of the polyamine solution and stirred to obtain a uniform solution. To this, a predetermined amount of CMDI was taken and stirred to obtain a homogeneous solution. In order to advance the reaction in advance, the container was covered and allowed to stand at room temperature (20-25 ° C.) for 10 minutes. Remove the lid, mix a predetermined amount of abrasive grains with a polyurea resin solution that maintains fluidity before gelation (viscosity 3000 to 5000 mPa · s), and concentrate (or stir) at room temperature for 10 minutes while stirring. The solution was concentrated under reduced pressure) to obtain a powder with a little stickiness (organic solvent remained) on the surface of the abrasive grains.
This powder (concentrate) is filled in a mold (mold) for molding an abrasive with a shaft having an outer diameter of 26 mmφ and a depth (thickness) of 15 mm and an outer diameter of 6 mmφ, and is sandwiched between press machines, 100 kg / cm ² was pressurized. Leave in this state for 10 minutes, then pressurize to 200 kg / cm ² and leave for another 10 minutes. Finally pressurize to 500 kg / cm ² and press for 3 to 5 hours, then release the pressure and remove from the mold. Typed. The polymerization reaction also proceeds during the above process. The obtained molded product was transferred to a thermostatic bath, heat-treated at 50 ° C. for 1.5 hours, then at 80 ° C. for 1.5 hours, and further at 120 ° C. for 6 hours, and then cooled to room temperature. Got.

  Set the test piece dressed with the workpiece aluminum plate and diamond grinding wheel in the polishing test machine shown in Fig. 1, apply the load, stop the operation in 2.5 minutes after starting the operation, and reduce the weight of the test piece in the meantime The amount was determined. Thereafter, the test piece was set again, and the weight loss after 2.5 to 5 minutes was determined. Thereafter, the polished surface properties on the workpiece were observed.

<Polishing conditions>
・ Work: Aluminum plate 130 × 130 × 1mm
・ Load: 1kg
・ Turntable rotation speed 100rpm
-Position of the test piece on the workpiece Torsion angle 17.5 °
Radius 43mm
・ Dust collection speed 3m ³ / min.
・ Test piece φ26 × 15mm Shaft diameter φ6mm

-Surface roughness measurement-
Measurement was performed according to JIS B 0601-1982 using a Talysurf type 6 manufactured by Taylor Hobson.

−Compressive modulus−
Compression test method of thermosetting resin It measured according to JIS K-6911 (1995).
Measurement conditions: load self scale 4000 kgf.
Crosshead speed 2 mm / min.
Chart speed 50 mm / min.
Test piece: cylinder of φ26.8 mm × thickness 17 mm

[Comparative example]
After adding 9.2 g of MC to 17 g of GC # 3000 abrasive grains and adding 2.92 g of polyamine A solution to the stirred mixture, 1.33 g of CMDI was added and mixed uniformly. I tried to fill this into a mold with an outer diameter of 26 mmφ and a depth of 15 mm, and a shaft with an outer diameter of 6 mmφ, but the mixture has high thixotropic properties and cannot be filled easily. I stir up. After press molding, it was cured at room temperature for 60 minutes and removed from the mold, but the molded product was frequently cracked and could not be used as a test piece.

According to the results of Table 1, in Examples 1 to 4 employing the production method of the present invention, it is easy to obtain an abrasive that uniformly contains fine abrasive grains at a concentration of 68 to 94% by volume (85 to 97.5% by mass). Could get to. In Examples 1 to 4, fine abrasive grains dropped off at a substantially constant speed, and Nashiji pattern polishing traces indicating that the dropped abrasive grains were subjected to rolling wear were confirmed on the aluminum plate used as a workpiece.
On the other hand, in the comparative example, the abrasive grains were mixed before the polyamine compound and the polyisocyanate compound were reacted. In this method, an abrasive having a grain concentration of 60.4% by volume (80% by mass) was prepared using fine abrasive grains having a grain size GC # 3000. However, cracks occurred frequently, and an abrasive that could be polished was not obtained. .

In Examples 5 to 7 in Table 2, all had a fine abrasive grain concentration of 85 to 86% by volume, and the abrasive grains had detachability (consumable) at a constant speed. Further, it was found that the surface roughness Ra and Rz of the polished surface became smaller and the gloss increased as the hardness of the binder (A = D>B> C when compared with the resin alone) became softer (Rdq The smaller the value, the more glossy it is.)
Further, in Examples 8 and 9, the difference due to the difference in the abrasive grain size was observed. However, even when the abrasive grain size became finer, the falling off of the abrasive grain was recognized, and the polished surface of the workpiece at that time As the abrasive grains became finer, Ra and Rz became smaller, and Rdq also became smaller and gloss was increased.
In Example 10, the aromatic amine of the polyurea raw material was changed from MOCA to CUA-4, and in Example 11, the type of fine abrasive grains was changed from GC to WA. As a result.

[Examples 12 and 13]
In accordance with the formulation shown in the table below (unit of blending amount in the table: mass (g)), a solvent is added to the finely pulverized aromatic diamine compound and mixed until the aromatic diamine compound is completely dissolved. Obtained. Then, the polyisocyanate compound was mixed according to the mixing | blending of the following table | surface, the abrasive material with a shaft for a test was obtained like Example 1-11, and the performance was evaluated.

[Examples 14 and 15]
According to the composition shown in the table below (unit of blending quantity in the table: mass (g)), Jeffamine D-2000, the aromatic diamine compound and the solvent were mixed to obtain a uniform solution. Then, the polyisocyanate compound was mixed according to the mixing | blending of the following table | surface, the abrasive material with a shaft for a test was obtained like Example 1-11, and the performance was evaluated.

[Example 16]
According to the composition shown in the table below (unit of blending quantity in the table: mass (g)), Jeffamine D-2000, aromatic diamine compound, elastomer 1000 and solvent were mixed to obtain a uniform solution. Then, the polyisocyanate compound was mixed according to the mixing | blending of the following table | surface, the abrasive material with a shaft for a test was obtained like Example 1-11, and the performance was evaluated.

[Example 17]
Heart Cure 10, Jeffamine D-2000, and the solvent were mixed according to the formulation shown in the table below (unit of blending amount in the table: mass (g)). Thereafter, a polyisocyanate compound was mixed according to the formulation shown in the table below, and the reaction was allowed to proceed for 1 minute while stirring. A predetermined amount of abrasive grains is mixed with a polyurea resin solution in a state in which fluidity is maintained before gelation (viscosity 3000 to 5000 mPa · s), and an abrasive with a test shaft is prepared in the same manner as in Examples 1 to 11. And its performance was evaluated.

  The results are shown in Table 3 below.

  In Examples 12 and 13, an aromatic diamine compound that is solid at room temperature is used alone as a polyamine compound, but a good abrasive can be obtained by dissolving in a solvent and reacting with a polyisocyanate. I understood. Experimental Examples 14 to 17 are examples in which an aliphatic polyamine oligomer is used in combination as a polyamine compound, and an abrasive with good performance was obtained in all cases.

[Examples 18 to 21]
Abrasive material with a test shaft was prepared in the same manner as in Examples 1 to 11 with the formulation shown in Table 4 (unit of blending amount in the table: mass (g)), and its properties were examined.

  In Examples 19 to 21, the abrasive grains are blended at a high concentration and further a fibrous filler is blended, but the compression modulus is increased as compared with Example 18 in which the fibrous filler is not blended. I was able to. This result shows that the physical properties of the abrasive can be further stabilized (brittleness can be further improved) by blending the fibrous filler.

DESCRIPTION OF SYMBOLS 1 Turntable 2 Turntable rotation direction 3 Test piece 4 Test piece rotation direction 5 Test piece twist angle 6 Test piece position (radius)
7 Dust collector nozzle 8 Dust collection direction 9 Polishing trace 10 Load 11 Workpiece

Claims (9)

A polyurea composite abrasive comprising a composite of abrasive grains and a polyurea resin, the polyurea composite abrasive comprising a polyurea resin solution that retains fluidity before gelation, and an abrasive having a particle size finer than # 2000 mesh And a mixture obtained by concentrating the mixture to obtain a concentrate in which the organic solvent in the polyurea resin solution remains, and obtaining the concentrate by pressure molding,
The polyurea composite abrasive particle size fine abrasive than # 2000 mesh containing 50 to 95 vol%, and, density is 0.45~2.0g / cm ^3, polyurea composite abrasive . In the polyurea resin, a polyisocyanate compound and a polyamine compound are mixed in an organic solvent at a ratio shown below to cause a polymerization reaction, and the abrasive is mixed before the reaction solution is gelled. The polyurea composite abrasive according to claim 1, which is polymerized.
[Isocyanate group equivalent of polyisocyanate compound] / [amino group equivalent of polyamine compound] = 0.90 to 2.00 The polyurea composite abrasive according to claim 2 , wherein the polyamine compound is any one of the following (a) to (f).
(A) aromatic polyamine oligomer (b) aromatic diamine compound (c) aromatic polyamine oligomer and aromatic diamine compound (d) aliphatic polyamine oligomer and aromatic diamine compound (e) aliphatic polyamine oligomer, aromatic polyamine oligomer And aromatic diamine compound (f) aliphatic polyamine oligomer and aromatic polyamine oligomer The polyurea composite abrasive | polishing material of Claim 3 in which the said aromatic polyamine oligomer contains the polyamine oligomer represented by following formula (I).

(In the formula, R represents a residue of an n-valent polyalkylene polyol, polyalkylene ether polyol or polyalkylene ester polyol having a number average molecular weight of 200 or more, and n represents 2 or 3. (It may contain a saturated bond.)   The aromatic diamine compound is 4,4′-methylenebis (2-chloroaniline), 4,4′-methylenebis (2,3-dichloroaniline), 4,4′-methylenebis (2,5-dichloroaniline), 4,4′-methylenebis (3-chloro-2,5-diethylaniline), 4,4′-methylenebis (2-methyl-6-ethylaniline), trimethylenebis (4-aminobenzoate), 4-chloro- 3,5-diamino-benzoic acid isobutyl, 3,5-dimethylthio-2,4-toluenediamine, 3,5-dimethylthio-2,6-toluenediamine, 3,5-diethyl-2,6-toluenediamine, 3, 5-diethyl-2,4-toluenediamine, 4,4′-methylenebis (methylanthraanilate), and 1,2-bis (2-aminophenylthio) ) At least one aromatic diamine compound selected from the group consisting of ethane, polyurea composite abrasive according to any one of claims 3 or 4. The polyurea composite abrasive according to any one of claims 3 to 5, wherein the aliphatic polyamine oligomer includes a polyamine oligomer represented by any one of the following formulas (II) to (IV).

_{H 2 N-CH (CH 3} ) -CH 2 -R 2 -NH 2 (II)

In formula (II), R ² represents — [O—CH ₂ —CH (CH ₃ )] _p — or — [O—CH (CH ₃ ) —CH ₂ ] _q — [O—CH ₂ —CH]. _{2] r - [O-CH} 2 -CH (CH 3)] s - is a divalent group represented by. Each of p to s indicating the number of repeating units is 1 or more, and q + s is 2 or more.

_{H 2 N- [O-CH (} CH 3) -CH 2 ] _{t - [O-CH 2 -CH} 2 -CH 2 -CH 2] u - _{[O-CH 2 -CH (CH 3} ) ] _v -NH ₂ (III)

In the formula (III), t to v indicating the number of repeating units are all 1 or more, and t + v is 6 or more.

In the formula (IV), R ^a is a hydrogen atom or an ethyl group. Each w indicating the number of repeating units is independently 1 or more, and the total of the three ws is 5 or more. When R ^a is a hydrogen atom, x is 0, and when R ^a is an ethyl group, x is 1.   The polyurea composite abrasive | polishing material of any one of Claims 1-6 used for grinding | polishing or polishing. The polyurea composite abrasive | polishing material of any one of Claims 1-7 whose compression elastic modulus is 20-130 kgf / mm < ² >. A method for producing a polyurea composite abrasive comprising a composite of abrasive grains and polyurea resin, the production method comprising:
A step of mixing and reacting a polyisocyanate compound in an organic solvent containing a polyamine compound to obtain a solution containing 2 to 20% by mass of a polyurea resin and retaining fluidity before gelation;
Mixing the polyurea resin solution and abrasive grains having a particle size finer than # 2000 mesh, and concentrating the mixed solution to obtain a concentrate in which the organic solvent remains;
Said concentrate to pressure molding, further polymerized to step under pressure; look including the step of curing and polyurea resin by heat-treating the molded product, the polyurea composite abrasive particle size finer than # 2000 mesh The manufacturing method of the polyurea composite abrasive | polishing material which contains 50-95 volume% of an abrasive grain, and a density is 0.45-2.0 g / cm < ³ > .

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