JP5528648B1 - Polishing aid and abrasive composition containing the polishing aid - Google Patents

Abstract

An object of the present invention is to provide a polishing aid that improves the polishing efficiency of an abrasive (particularly abrasive grains) while suppressing polishing scratches to the extent that it can withstand practical use. Moreover, it aims at providing the abrasive | polishing agent composition containing the said grinding aid and abrasive | polishing agent.
According to the present invention, a polishing aid containing a cyclodextrin treated with a silane coupling agent is provided. Also provided is a polishing aid containing cyclodextrin treated with a silane coupling agent and resin particles having a plurality of depressions on the surface. Furthermore, an abrasive composition containing the polishing aid and an abrasive is provided.

Description

  The present invention relates to a polishing aid and an abrasive composition containing the polishing aid. Specifically, the present invention relates to a polishing aid containing a cyclodextrin treated with a silane coupling agent. In addition to the cyclodextrin, the present invention also relates to a polishing aid containing resin particles having a plurality of depressions on the surface. And this invention also relates to the abrasive | polishing agent composition containing the said grinding aid and abrasive | polishing agent.

  In recent years, an abrasive slurry in which cerium oxide is dispersed in water has been used to obtain a highly accurate polished surface of a glass material. This is because the polishing power is high and the polishing rate is high compared to silica, alumina and the like, and the hardness is low compared to silica and alumina, so that the polished surface is hardly scratched.

  Transition metal oxides such as cerium oxide are used as polishing agents for semiconductor substrates, thin film magnetic head substrates, optical components such as optical fibers, laser mirrors, lenses, and magnetic desk substrates. In general, abrasive grains such as cerium oxide tend to be scratched on the polished surface when the particle diameter exceeds 10 μm, and the polishing rate becomes slow when the particles become fine. Further, when the particles become fine, there is a problem that aggregation occurs and polishing scratches are generated. In addition, transition metal oxides are rare, and in recent years, the price of transition metal oxides has risen in recent years, making it difficult to obtain and has become a major problem.

  In order to prevent such aggregation of transition metal oxides such as cerium oxide and to improve dispersibility and generation of polishing scratches, for example, a dispersant body composed of a compound having a glucose skeleton and abrasive grains (cerium oxide) ) Is known to be used as an abrasive for semiconductor processing (Patent Document 1). Furthermore, a polishing pad composition containing abrasive grains (cerium oxide) and a water-soluble substance (cyclodextrin) in a water-insoluble substance is known (Patent Document 2). Further, in order to create a situation where the abrasive particles are strongly held by the polishing pad during polishing, an abrasive composition containing abrasive grains (cerium oxide) surface-treated with water and a coupling agent is known (Patent Literature). 3).

JP 2002-110596 A JP 2001-214154 A JP 2000-53946 A

  However, in the combination of a water-soluble substance such as cyclodextrin as a dispersant of Patent Document 1 and abrasive grains such as cerium oxide, there is still a point to be improved in the dispersibility of the abrasive grains. It is still insufficient to prevent the occurrence. Further, Patent Document 2 describes that when the abrasive slurry is caused to flow down between the polishing pad and the surface to be polished, the proportion that works effectively for polishing is less than 1%. It is described that the polishing rate can be increased by using a polishing pad comprising a polishing pad composition containing abrasive grains such as cerium oxide and a water-soluble substance such as cyclodextrin. Also, in Patent Document 3, the abrasive grains are surface-treated with water and a coupling agent in order to increase the affinity of the polishing pad with the organic compound, whereby the abrasive grains are strongly held on the polishing pad, and the surface to be polished It is described that it is possible to realize both the surface accuracy and the polishing rate at a high level. However, Patent Documents 1 to 3 do not mention a reduction in the amount of abrasive grains. In recent years, it has become difficult to obtain transition metal oxides and the price has been rising, and in situations where it is required to reduce the amount of transition metal oxide used as abrasive grains, There is a demand for an abrasive composition that can suppress polishing scratches while increasing polishing efficiency.

  Accordingly, the present invention provides a polishing aid that improves polishing efficiency of a polishing agent (especially abrasive grains) while suppressing polishing scratches to the extent that it can withstand practical use, and a polishing agent composition containing the polishing aid and the polishing agent. The purpose is to provide goods.

  The present inventors have found that polishing efficiency is improved when cyclodextrin treated with a silane coupling agent is used in combination with abrasive grains. Furthermore, it has been found that the use of cyclodextrins treated with a silane coupling agent and resin particles having a plurality of depressions on the surface in combination with abrasive grains for polishing further improves the polishing efficiency. And based on these knowledge, it came to complete this invention, repeating improvement further.

That is, the present invention includes, for example, the subject matters described in the following sections.
Item 1.
A polishing aid containing cyclodextrin treated with a silane coupling agent.
Item 2.
Item 2. The polishing aid according to Item 1, wherein the cyclodextrin is at least one selected from the group consisting of α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin. Item 3.
Item 1 or 2, wherein the silane coupling agent is at least one selected from the group consisting of an aminosilane coupling agent, a vinyl silane coupling agent, a methacrylic silane coupling agent, an isocyanate silane coupling agent, and an epoxy silane coupling agent. 2. The polishing aid according to 2.
Item 4.
Item 4. The polishing aid according to any one of Items 1 to 3, further comprising resin particles having a plurality of depressions on the surface.
Item 5.
Item 5. The polishing aid according to Item 4, wherein the resin particles having a plurality of depressions on the surface are particles comprising a resin having a crosslinked structure.
Item 6.
Item 6. The polishing aid according to Item 5, wherein the crosslinked structure is a crosslinked structure by a siloxane bond.
Item 7.
Resin particles having a plurality of depressions on the surface are particles in which a monomer having a polymerization group and a crosslinking group is polymerized, and are particles comprising a resin having a crosslinked structure crosslinked by a crosslinking group derived from the monomer. Item 7. A polishing aid according to any one of Items 4 to 6.
Item 8.
The monomer-derived crosslinking group is represented by formula (1);

(Wherein R ^{1 to} R ³ each independently represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 5 carbon atoms, or an alkoxyl group having 1 to 5 carbon atoms). Item 8. The polishing aid according to Item 7, which is a group.
Item 9.
The monomer having a polymerization group and a crosslinking group is selected from 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, and 3- Item 9. The polishing aid according to Item 7 or 8, which is at least one selected from the group consisting of (meth) acryloxypropyltriethoxysilane.
Item 10-1.
Resin particles having a plurality of depressions on the surface are seed-polymerized with a seed polymerization monomer in the presence of seed particles containing a monomer having a crosslinking group, and then at least a part of the crosslinking group is crosslinked. Item 10. The polishing aid according to any one of Items 4 to 9, which is obtained by
Item 10-2.
Item 10. The polishing aid according to any one of Items 4 to 10, wherein the resin particles having a plurality of depressions on the surface are composed of a resin having a crosslinked structure and a seed polymer.
Item 10-3.
Item 10. The polishing aid according to Item 10-2, wherein the resin particles having a plurality of depressions on the surface are composed of a resin having a crosslinked structure and a seed polymer, and the seed polymer forms a depression.
Item 10-4.
The seed polymer is obtained by seed polymerization of at least one seed polymerization monomer selected from the group consisting of (meth) acrylic acid alkyl ester having 1 to 8 carbon atoms, aromatic vinyl, and olefin. Item 10-2 or 10-3.
Item 11.
A polishing agent composition comprising the polishing aid according to any one of Items 1 to 10-4 and an abrasive.
Item 12.
Item 12. The abrasive composition according to Item 11, wherein the abrasive is abrasive grains.
Item 13.
Item 13. The abrasive composition according to item 11 or 12, wherein the abrasive is a transition metal oxide.
Item 14.
14. The abrasive composition according to item 13, wherein the transition metal oxide is at least one selected from the group consisting of cerium oxide, zirconium oxide, and titanium oxide.
Item 15.
Item 15. The abrasive composition according to any one of Items 11 to 14, which is an abrasive slurry.

  By using the polishing aid of the present invention in combination with an abrasive (in other words, by using an abrasive composition containing the polishing aid of the present invention and an abrasive), the polishing scratches can be put to practical use. The substrate to be polished and the like can be efficiently polished while suppressing. Therefore, it is possible to significantly reduce abrasives of transition metal oxides such as cerium oxide, which have been increasing in price in recent years. Examples of the polishing target include a semiconductor substrate, a thin film magnetic head substrate, an optical component such as an optical fiber, a laser mirror, and a lens, an aluminosilicate glass substrate, a glass surface such as a magnetic desk substrate, and the like.

The electron micrograph of the resin particle which can be used for the grinding | polishing adjuvant of this invention and which has a some dent on the surface is shown. The resin is prepared in Preparation Example 1 of the present specification.

  Hereinafter, the present invention will be described in more detail. In the present specification, “comprising” includes the meanings of “consisting of” and “essentially consisting of”.

  The cyclodextrin used in the present invention is a cyclic oligosaccharide composed of D-glucopyranose units. Although not particularly limited, α-cyclodextrin (hexamer), β-cyclodextrin (7-mer), γ-cyclodextrin (octamer) and the like can be preferably used. In particular, α-cyclodextrin is water. Since it is easy to soften, it is preferable because it easily enters between abrasive grains. Further, cyclodextrin (which may be any number, preferably hexamer, heptamer and octamer) may be chemically modified. For example, it can be methylated cyclodextrin, hydroxypropylated cyclodextrin, monochlorotriazinylated cyclodextrin and the like. Such cyclodextrins can be used singly or in combination of two or more.

Moreover, when using cyclodextrin, a powdery thing can be used, for example. In this case, although not particularly limited, preferably has a water content of 5 wt% or less, more preferably of 3 wt% or less, more preferably those which are 0.01 to 3 wt%. This is because, when the moisture content is smaller, the silane coupling agent is less likely to undergo dehydration decomposition when the silane coupling treatment is performed (the coupling treatment is less likely to be hindered). The water content here is an amount obtained from the amount of mass reduction after the cyclodextrin powder is dried at 110 ° C. for 3 hours.

  The cyclodextrin used in the present invention preferably has an average particle size of about 2 to 30 μm, more preferably about 5 to 15 μm. When the average particle size is less than 2 μm, the polishing efficiency may be slightly lowered, and when it exceeds 30 μm, polishing scratches are likely to occur. The average particle size of the cyclodextrin refers to the particle size at an integrated value of 50% in the particle size distribution measured by a laser diffraction scattering method using a hydrocarbon solvent (n-heptane) as a solvent.

  Examples of silane coupling agents for treating cyclodextrin include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2- Aminosilane coupling agents such as aminoethyl) -3-aminopropylmethyldimethoxysilane, 3- (N-phenyl) aminopropyltrimethoxysilane; vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, Vinyl silane coupling agents such as vinyl methyl methoxy silane; Methacryl silane coupling agents such as 3-methacryloxy propyl triethoxy silane, 3-methacryloxy propyl trimethoxy silane; 3-mercaptopropyl trimethoxy silane Mercapto or sulfur silane coupling agents such as 3-mercaptopropyltriethoxysilane, 3-octanoylthio-1-propyltriethoxysilane; 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, etc. Isocyanate silane coupling agent; epoxy silane coupling agent such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane; n- There are silane monomers such as octyltriethoxysilane, methyltriethoxysilane, and methyltrimethoxysilane, but the aminosilane coupling agents such as 3-aminopropyltriethoxysilane and vinylsilane Vinyltriethoxysilane coupling agent, a methacrylic silane coupling agent, isocyanate silane coupling agent, an epoxy silane coupling agent is preferred. Moreover, a silane coupling agent can also be used individually by 1 type or in combination of 2 or more types. Furthermore, you may use it in combination with a titanate coupling agent, a zirconate coupling agent, an aluminum coupling agent, a phosphate coupling agent, or the like.

  In producing a cyclodextrin treated with a silane coupling agent, the amount of the silane coupling agent used is preferably 0.01 to 20 parts by mass, and 0.05 to 5 parts by mass with respect to 100 parts by mass of cyclodextrin. More preferred. That is, the cyclodextrin treated with the silane coupling agent is preferably obtained by reacting (coupling treatment) the silane coupling agent with the cyclodextrin in this proportion. When the amount is 0.01 parts by mass or more, better dispersibility can be obtained. In addition, when the amount is 20 parts by mass or less, the possibility that the water repellency becomes strong and the abrasive grains are not easily blended can be further reduced.

  It is preferable that the water | moisture content (110 degreeC dry reference | standard) of the cyclodextrin processed with the silane coupling agent is 5 mass% or less, and it is more preferable that it is 0.01-3 mass%. When the water content exceeds 5% by mass, the cyclodextrin treated with the silane coupling agent is attracted to the hydrophilic glass surface during polishing, which may hinder polishing and reduce polishing efficiency. In addition, a 110 degreeC drying reference | standard shows drying at 110 degreeC for 3 hours.

  The cyclodextrin treated with the silane coupling agent is prepared by, for example, drying and pulverizing cyclodextrin at a temperature of 80 to 150 ° C., adjusting the particle size and moisture of the cyclodextrin, For example, 0.01 to 20 parts by mass can be added to 100 parts by mass of cyclodextrin. The temperature for the coupling treatment is preferably 50 to 150 ° C, more preferably 60 to 105 ° C. When the treatment temperature of cyclodextrin and silane coupling agent is lower than 50 ° C, unreacted silane coupling agent remains and may react with water and hydrolyze, so that a silane coupling treatment cyclodextrin is obtained. It may be difficult to get it. When it is higher than 150 ° C., cyclodextrin is likely to be decomposed.

  The resin particles used as necessary in the present invention have a plurality of depressions on the surface. “Plurality” means two or more per particle, usually about 10 to 1000. The polishing rate can be improved by using particles having more depressions on the particle surface. In one embodiment, the resin particles having a plurality of depressions on the surface can be said to have, for example, a golf ball-like structure.

  The average particle diameter of the resin particles having a plurality of depressions on the surface is preferably 3 to 20 μm, and more preferably 5 to 10 μm. When the average particle size is 3 μm or more, the polishing rate can be further improved when used as a polishing aid. If it is 20 μm or less, the possibility of occurrence of polishing scratches is further reduced. The average particle size of the resin particles refers to the particle size at an integrated value of 50% in the particle size distribution measured by a laser diffraction scattering method using water as a solvent.

  In addition, the plurality of indentations of the resin particles usually have substantially circular openings. On the particle surface, there are mixed indentations having substantially the same or different diameters of the openings. The average diameter of the opening of the recess is preferably about 0.01 to 3 μm, and more preferably about 0.03 to 0.9 μm.

  The dent does not penetrate through the resin particles, but means a dent on the surface of the resin particles. The depth of the recess is not particularly limited, but is preferably about twice or less the diameter of the opening of the recess, and more preferably about 1 or less.

  In addition, the diameter and depth of the opening part of a hollow are measured by observing a resin particle with an electron microscope. The average diameter is obtained by averaging the diameters of 20 randomly selected indentations.

  The resin particles having a plurality of depressions on the surface used in the present invention preferably comprise a resin having a crosslinked structure. In particular, the crosslinked structure is preferably a structure (crosslinked structure) in which a polymer obtained by polymerizing a monomer that is a raw material of the resin is crosslinked by a crosslinkable reactive group (crosslinked group) derived from the monomer. That is, in this case, the monomer that is a raw material of the resin particles has a polymerization group and a crosslinking group, and the resin has a structure in which the monomer is polymerized by the polymerization group and is crosslinked by the crosslinking group. Have. For example, in one embodiment of the production, the monomer is polymerized by the polymerization group to form a polymer, and then the polymer is crosslinked by the crosslinking group to obtain a resin having a crosslinked structure. In addition to the monomer having a polymerization group and a crosslinking group, other monomers can also be used as a raw material for the resin particles. The other monomer is preferably a monomer having a polymerization group but no crosslinking group, and the polymerization group of the other monomer is the same as the polymerization group of the monomer having a polymerization group and a crosslinking group. Is more preferable.

  The crosslinking structure is not particularly limited. For example, “carboxyl group” and “glycidyl group, hydroxyl group, amino group, oxazoline, oxetane, carbonate, hydroxyalkylamide, aluminum halide, azetidinium, isocyanate, halohydrin, alkoxysilane, etc. Cross-linking structure with “Alcohol (hydroxyl group)” and “Glycidyl group or isocyanate”; Self-crosslinking structure of glycidyl group; Siloxane-bonded cross-linking structure between silyl groups, etc. It can be said that the group mentioned here for explaining the crosslinked structure is a preferable crosslinking group possessed by the monomer that is a raw material of the resin particles. That is, the monomer is preferably exemplified by those having a carboxyl group, a glycidyl group, a hydroxyl group, an amino group, an alkoxysilane group, a silyl group, and the like, and among them, those having a silyl group are preferred. In addition, it is preferable to use the monomer used as a raw material of the resin particle in combination of at least one type or two or more types of monomers capable of forming a crosslinked structure. As the said combination, the combination of each group mentioned above as an illustration about a crosslinked structure is illustrated. In particular, the combination is preferably a combination of “carboxyl group” and “glycidyl group, hydroxyl group, or amino group”, or a combination of “silyl groups”.

  A monomer having a glycidyl group or a silyl group (these groups can form a self-crosslinked structure), or a monomer having a plurality of types of groups capable of forming a crosslinked structure is different from other types of monomers. Even if not used in combination, a crosslinked structure can be formed with only one of the monomers, so that only one of the monomers may be used.

  In particular, as resin particles having a plurality of depressions on the surface, a structure in which a polymer containing a monomer having a silyl group is bonded to each other by a siloxane bond (Si—O—Si bond) between the silyl groups (crosslinked structure). It is preferable that the resin particles have.

  Further, the polymerization group possessed by the monomer that is the raw material of the resin particles is not limited as long as it is a group that can be polymerized by polymerization to form a monomer, but a vinyl group, a styryl group, a (meth) acryloxy group, an amino group. Preferred examples include groups. [In this specification, “acryloxy” and “methacryloxy” are collectively referred to as “(meth) acryloxy”. The same applies below. ]

 As described above, the resin particles can be produced, for example, by polymerizing the monomer with the polymerized group to form a polymer, and then crosslinking the polymer with the crosslinking group. In this case, the depression on the particle surface can be formed, for example, by carrying out seed polymerization in the presence of the monomer for seed polymerization after the monomer is polymerized into a polymer. And after a dent is formed in the particle | grain surface, bridge | crosslinking is performed. That is, in this production process, particles obtained when the monomer is polymerized by the polymerization group to become a polymer are seed particles, and a depression is formed on the surface of the seed particles, followed by crosslinking. Therefore, in this case, it can be said that the resin particles are composed of a resin having a crosslinked structure and a seed polymer.

  More specifically, the resin particle precursor having a plurality of depressions on the surface is obtained by, for example, seed-polymerizing a seed polymerization monomer in the presence of the seed particles to have a resin particle precursor having a plurality of depressions on the surface of the seed particles. After obtaining the above, the precursor can be obtained by crosslinking with a crosslinking group. In this case, the polymer obtained by seed polymerization of the monomer for seed polymerization is generated in such a manner that the surface of the seed particle is pushed in, so that a depression is formed on the surface of the seed particle. Therefore, in this case, the resin particles having a plurality of depressions on the surface used in the present invention are composed of a resin having a crosslinked structure and a seed polymer, and the seed polymer forms a depression. it can. Although not intended to be limited in interpretation, the polymer of the monomer for seed polymerization is produced in such a way as to push the surface of the seed particle, for example, the solvent contained in the polymer evaporates, so that the polymer itself It is presumed that a dent is formed on the particle surface due to the depression.

  In addition, as a monomer for seed polymerization, for example, (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, etc. 8 alkyl esters; aromatic vinyls such as styrene, α-methylstyrene, vinyltoluene, and dimethylstyrene; olefins such as ethylene and propylene. The monomer for seed polymerization may be used independently and may use 2 or more types together.

  The siloxane bond cross-linking structure between silyl groups will be described in more detail with respect to the present invention.

  In order for the seed particle component of the resin particle having a plurality of indentations to have a siloxane bond cross-linked structure, the seed particle is preferably a polymer particle having a monomer having a silyl group as a constituent component. In particular, particles obtained by polymerization containing a monomer having a silyl group are preferred, and particles obtained by polymerizing a monomer having a silyl group are more preferred.

  As a monomer which has a silyl group, the compound which has a silyl group represented by Formula (1) is mentioned, for example.

In formula (1), R ^{1 to} R ³ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 5 carbon atoms (1, 2, 3, 4 or 5), or 1 to 1 carbon atoms. 5 (1, 2, 3, 4 or 5) alkoxyl group is shown.

  As a C1-C5 alkyl group, a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group etc. are mentioned, for example.

  As a C1-C5 alkoxyl group, a methoxy group, an ethoxy group, a propoxy group, n-butoxy group, t-butoxy group, n-pentyloxy group etc. are mentioned, for example.

Although there is no particular limitation as long as the effects of the present invention are obtained, among R ^{1 to} R ³ , one or more are preferably alkoxyl groups, and more preferably two or three are alkoxyl groups.

  Specific examples of the monomer having a silyl group used in the present invention include, for example, vinyl compounds such as vinyltrimethoxysilane and vinyltriethoxysilane; 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycol. Epoxy compounds such as sidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane; styryl compounds such as p-styryltrimethoxysilane; 3- (meth) acryloxy (Meth) acryloxy compounds such as propylmethyldimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyltriethoxysilane; N -2- (Amino Til) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltri Amino compounds such as methoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane; 3-ureido Ureido compounds such as propyltriethoxysilane; chloropropyl compounds such as 3-chloropropyltrimethoxysilane; mercapto compounds such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; bis (triethoxysilylpropyl) te Sulfide compound of sulfides; 3- isocyanate propyl isocyanate compounds such as triethoxy silane, and the like. Among these, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acrylic silane, from the viewpoint of the reactivity of the monomer having a silyl group in the production of seed particles and the solubility in the reaction solvent. (Meth) acryloxy compounds such as loxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, and 3- (meth) acryloxypropyltriethoxysilane are preferably used. These monomers having a silyl group may be used alone or in combination of two or more.

  When polymer particles having a silyl group-containing monomer as a constituent component are used as seed particles, resin particles having a plurality of depressions on the surface are seed-polymerized with seed polymerization monomers in the presence of the seed particles. After obtaining a resin particle precursor having a plurality of indentations on the surface of the particle, it can be obtained by a method of crosslinking the silyl group by a siloxane bond by a chemical reaction.

  There are no particular limitations on the method for producing seed particles that use the silyl group-containing monomer as a constituent monomer component used in the present invention, and examples thereof include conventionally known polymerization methods such as emulsion polymerization and dispersion polymerization.

  In this specification, the dispersion polymerization method will be described in more detail as an example of the embodiment. In this method, the monomer having a silyl group and, if necessary, other monomers are subjected to a polymerization reaction in a reaction solvent containing a dispersant using a polymerization initiator.

  Other monomers include, for example, methyl (meth) acrylate [In this specification, “acryl” and “methacryl” are collectively referred to as “(meth) acryl”. The same shall apply hereinafter), ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (Meth) acrylic acid esters such as dodecyl (meth) acrylate and stearyl (meth) acrylate; vinyl esters such as vinyl acetate and vinyl propionate; aromatic vinyls such as styrene, α-methylstyrene, vinyltoluene and dimethylstyrene And olefins such as ethylene and propylene. Among these, methyl (meth) acrylate, butyl (meth) acrylate, and styrene are preferably used from the viewpoint of increasing the polishing rate of the resin particles having a plurality of depressions on the surface to be obtained. These other monomers may be used alone or in combination of two or more.

  The amount of the other monomer used is preferably 100 to 900 parts by mass, and more preferably 150 to 900 parts by mass with respect to 100 parts by mass of the monomer having a silyl group. When the usage-amount of another monomer is 100 mass parts or more, the seed particle obtained is more difficult to aggregate and is preferable. Moreover, if the usage-amount of another monomer is 900 mass parts or less, the grinding | polishing speed | rate of the resin particle which has a several hollow on the surface obtained can be improved more.

  Examples of the polymerization initiator include azo compounds such as 2,2′-azobis (2-methylpropionitrile) and 1,1′-azobis (cyclohexane 1-carbonitrile); dibenzoyldioxidane, 2,4- Dichlorobenzoyl peroxide, t-butylperoxypivalate, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, succinic acid peroxide, acetyl peroxide, t -Butylperoxy-2-ethylhexanoate, m-toluoyl peroxide, benzoyl peroxide, t-butylperoxymaleic acid, t-butylperoxylaurate, t-butylperoxy-3,5 5-trimethylhexano , Cyclohexanone peroxide, t-butylperoxyisopropyl carbonate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,2-bis (t-butylperoxy) octane, t-butyl Peroxyacetate, 2,2-bis (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-bis (t-butylperoxy) valerate, di-t-butyl-di Examples include peroxides such as peroxyisophthalate, methyl ethyl ketone peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and t-butylcumyl peroxide. Among these, 2,2′-azobis (2-methylpropionitrile), 1,1′-azobis (cyclohexane 1-carbonitrile) and dibenzoyldioxidane are preferably used from the viewpoint of easy control of the polymerization reaction. From the viewpoint of material safety, 2,2′-azobis (2-methylpropionitrile) and 1,1′-azobis (cyclohexane 1-carbonitrile) are more preferably used. These polymerization initiators may be used alone or in combination of two or more.

  The amount of the polymerization initiator used is preferably 0.5 to 5 parts by mass and more preferably 0.8 to 4 parts by mass with respect to 100 parts by mass of all monomers used for the production of seed particles. . If the amount of the polymerization initiator used is 0.5 parts by mass or more, the polymerization reaction can proceed smoothly (that is, it does not require much time), and if the amount of the polymerization initiator used is 5 parts by mass or less. For example, the risk of a rapid polymerization reaction is reduced, and the monomer used for the production of seed particles is less likely to be decomposed.

  Examples of the dispersant include xanthan gum, guar gum, carboxymethylcellulose, polyvinylpyrrolidone, carboxyvinyl polymer, polyacrylic acid, polyvinyl alcohol, polyethylene glycol, polyethylene oxide, starch derivatives, polysaccharides and the like. Among these, polyvinylpyrrolidone and polyacrylic acid are preferably used from the viewpoints of solubility in the reaction solvent, stability of the polymerization reaction, and control of the particle size of the seed particles. These dispersing agents may be used independently and may use 2 or more types together.

  The amount of the dispersant used is preferably 30 to 100 parts by mass and more preferably 50 to 80 parts by mass with respect to 100 parts by mass of all monomers used for the production of seed particles. When the amount of the dispersant used is 30 parts by mass or more, the aggregation of the obtained seed particles can be further reduced. Moreover, when the usage-amount of a dispersing agent is 100 mass parts or less, a dispersing agent is easy to melt | dissolve in a reaction solvent more.

  Examples of the reaction solvent include acetone, acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, 1-butanol, 2-propanol, 1-propanol, ethanol, methanol, water, and the like. Among these, methanol and ethanol are preferably used from the viewpoint of the solubility of the monomer used for producing the seed particles and the stability of the polymerization reaction. These reaction solvents may be used alone or in combination of two or more.

  The amount of the reaction solvent used is preferably 200 to 1500 parts by mass, and more preferably 500 to 1000 parts by mass with respect to 100 parts by mass of all monomers used for the production of seed particles. If the usage-amount of a reaction solvent is 200 mass parts or more, the monomer used for manufacture of a seed particle will melt | dissolve more easily. Moreover, when the usage-amount of a reaction solvent is 1500 mass parts or less, a possibility that reaction rate may become slow is reduced.

  The reaction temperature in the polymerization reaction is preferably 20 to 100 ° C., more preferably 40 to 80 ° C. from the viewpoint of not only increasing the polymerization reaction rate but also allowing the polymerization reaction to proceed smoothly. The reaction time is usually 12 to 48 hours.

  Thus, dispersion polymerization is performed to obtain seed particles having a monomer having a silyl group as a constituent monomer component.

  In the present invention, for example, seed polymerization of a seed polymerization monomer in the presence of seed particles containing a monomer having a silyl group as a constituent monomer component can form a plurality of depressions on the surface of the seed particles. . The seed polymerization method is not particularly limited, and examples thereof include seed polymerization methods such as a seed emulsion polymerization method and a seed dispersion polymerization method.

  In this specification, the seed dispersion polymerization method will be described in more detail as an example of the embodiment. In the method, the seed polymerization monomer is added in a solvent (S1) in which seed particles (hereinafter, may be simply referred to as “seed particles”) having the silyl group-containing monomer as a constituent monomer component are dispersed. A plurality of depressions can be formed on the surface by seed dispersion polymerization in the presence of the solvent (S2) and drying. In this case, the monomer for seed polymerization that becomes a factor for forming the depression is soluble in the solvent (S1), and the polymer generated from the monomer for seed polymerization is more resistant to the seed particles than the solvent (S1). It is preferred that the affinity is high or equivalent.

  As the solvent (S1), for example, a methanol / water mixed solvent is particularly preferably used (the solvent (S1) will be described in detail later). The polymerization reaction is preferably performed by adding the solvent (S2), the polymerization initiator, and the dispersant to the solvent (S1). That is, the polymerization reaction is preferably performed in the presence of a solvent (S2), a polymerization initiator, and a dispersant. The solvent (S2) is a poor solvent or non-solvent for the seed particles, but is a good solvent for the monomer for seed polymerization and is an organic solvent that is insoluble or partially dissolved in the solvent (S1).

  Examples of the solvent (S1) include acetone, acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, 1-butanol, 2-propanol, 1-propanol, ethanol, methanol, water, and the like. Among these, methanol, ethanol, and water are preferably used from the viewpoints of solubility of the monomer for seed polymerization and stability of the polymerization reaction. These solvent (S1) may be used independently and may use 2 or more types together. In particular, a mixed solvent of methanol and water (methanol / water mixed solvent) is preferably used.

  The amount of the solvent (S1) used is preferably 500 to 2500 parts by mass and more preferably 1000 to 2000 parts by mass with respect to 100 parts by mass of the seed particles used. If the amount of use of the solvent (S1) is 500 parts by mass or more, the monomer for seed polymerization is more easily dissolved. If the amount of use of the solvent (S1) is 2500 parts by mass or less, the polymerization reaction is smooth. Can progress to.

  As the monomer for seed polymerization, as described above, for example, carbon number of (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, etc. 1-8 alkyl esters; aromatic vinyls such as styrene, α-methylstyrene, vinyltoluene, and dimethylstyrene; and olefins such as ethylene and propylene. Among these, butyl (meth) acrylate, ethyl (meth) acrylate, and styrene are particularly preferably used from the viewpoints of solubility in the solvent (S1) and stability of the polymerization reaction. These seed polymerization monomers may be used alone or in combination of two or more.

  The amount of the seed polymerization monomer used is preferably 20 to 100 parts by mass, and more preferably 30 to 80 parts by mass with respect to 100 parts by mass of the seed particles used. If the use amount of the monomer for seed polymerization is 20 parts by mass or more, a dent is more easily formed on the surface of the seed particle. Moreover, if it is 100 mass parts or less, a hollow can be formed more reliably.

  The organic solvent (S2) is a poor solvent or non-solvent for the seed particles, but is a good solvent for the monomer for seed polymerization and an organic solvent that is insoluble or partially soluble in the solvent (S1). For example, decahydronaphthalene, cyclohexane, n-dodecane, limonene and the like can be mentioned. Among these, n-dodecane and cyclohexane are preferably used from the viewpoint of forming a dent on the surface of the seed particle during seed dispersion polymerization. These organic solvents (S2) may be used independently and may use 2 or more types together. The polymer generated on the surface of the seed particles is a polymer generated by polymerization of the monomer for seed polymerization, and a portion where the polymer is generated becomes a dent on the particle surface. That is, the polymer is produced in such a way as to push the particle surface, and then the solvent (S2) contained in the polymer is removed to obtain a resin particle precursor having a depression on the surface.

  The amount of the organic solvent (S2) used is preferably 50 to 2000 parts by mass and more preferably 100 to 1500 parts by mass with respect to 100 parts by mass of the seed polymerization monomer. If the organic solvent (S2) is used in an amount of 50 parts by mass or more, the surface of the seed particles is more easily formed, and if the organic solvent (S2) is used in an amount of 2000 parts by mass or less, the seed particles are used. The risk of flocculation is further reduced.

  Examples of the polymerization initiator include azo compounds such as 2,2′-azobis (2-methylpropionitrile) and 1,1′-azobis (cyclohexane 1-carbonitrile); dibenzoyldioxidane, 2,4- Dichlorobenzoyl peroxide, t-butylperoxypivalate, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, succinic acid peroxide, acetyl peroxide, t -Butylperoxy-2-ethylhexanoate, m-toluoyl peroxide, benzoyl peroxide, t-butylperoxymaleic acid, t-butylperoxylaurate, t-butylperoxy-3,5 5-trimethylhexano , Cyclohexanone peroxide, t-butylperoxyisopropyl carbonate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,2-bis (t-butylperoxy) octane, t-butyl Peroxyacetate, 2,2-bis (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-bis (t-butylperoxy) valerate, di-t-butyl-di Examples include peroxides such as peroxyisophthalate, methyl ethyl ketone peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and t-butylcumyl peroxide. Among these, 2,2′-azobis (2-methylpropionitrile), 1,1′-azobis (cyclohexane 1-carbonitrile) and dibenzoyldioxidane are preferably used from the viewpoint of easy control of the polymerization reaction. From the viewpoint of material safety, 2,2′-azobis (2-methylpropionitrile) and 1,1′-azobis (cyclohexane 1-carbonitrile) are more preferably used. These polymerization initiators may be used alone or in combination of two or more.

  The amount of the polymerization initiator used is preferably 2 to 10 parts by mass and more preferably 5 to 8 parts by mass with respect to 100 parts by mass of the seed particles used. If the amount of the polymerization initiator used is 2 parts by mass or more, the polymerization reaction can be performed smoothly (that is, it does not require much time), and if the amount of the polymerization initiator used is 10 parts by mass or less, rapid polymerization is performed. The risk of reaction occurring is further reduced.

  Examples of the dispersant include xanthan gum, guar gum, carboxymethylcellulose, polyvinylpyrrolidone, carboxyvinyl polymer, polyacrylic acid, polyvinyl alcohol, polyethylene glycol, polyethylene oxide, starch derivatives, polysaccharides and the like. Among these, polyvinylpyrrolidone and polyacrylic acid are preferably used from the viewpoints of solubility in the reaction solvent and stability of the polymerization reaction. These dispersing agents may be used independently and may use 2 or more types together.

  The amount of the dispersant used is preferably 30 to 100 parts by mass, and more preferably 40 to 90 parts by mass with respect to 100 parts by mass of the seed particles to be used. When the amount of the dispersant used is 30 parts by mass or more, the aggregation of the obtained seed particles can be further reduced. Moreover, when the usage-amount of a dispersing agent is 100 mass parts or less, a dispersing agent is easy to melt | dissolve in a reaction solvent more.

  The reaction temperature during the seed dispersion polymerization reaction is preferably 20 to 100 ° C., more preferably 40 to 80 ° C., from the viewpoint of not only forming a dent on the surface of the seed particles but also promoting the polymerization reaction smoothly. The reaction time is usually 12 to 24 hours.

  Thus, seed dispersion polymerization is performed. For example, after washing with a solvent such as methanol, the residual solvent in the particles is removed by drying to obtain a resin particle precursor having a plurality of depressions on the surface.

  In the present invention, for example, the resin particles having a plurality of depressions on the surface having a crosslinked structure by crosslinking silyl groups contained in the resin particle precursor having a plurality of depressions on the surface by siloxane bonding. Can be obtained.

  The method for bonding the silyl group to the siloxane is not particularly limited. For example, the silyl group can be bonded to the siloxane group by dispersing in a water-containing medium in the presence of an acid catalyst.

  Examples of the acid catalyst include p-toluenesulfonic acid, acetic acid, formic acid, citric acid, and oxalic acid. Among these, paratoluenesulfonic acid and acetic acid are preferably used from the viewpoint of solubility in a water-containing medium and uniform siloxane bonding. These may be used alone or in combination of two or more.

  The amount of the acid catalyst used is preferably 20 to 100 parts by mass, and 40 to 80 parts by mass with respect to 100 parts by mass of the resin particle precursor having a plurality of depressions on the surface, from the viewpoint of smoothly promoting the siloxane bonding reaction. More preferably, it is a part.

  The water-containing medium may be mixed with an alcohol such as methanol, ethanol or isopropanol; or a hydrophilic organic solvent such as acetonitrile.

  The amount of water in the water-containing medium is preferably 50 to 3000 parts by mass with respect to 100 parts by mass of the resin particle precursor having a plurality of indentations on the surface, from the viewpoint of smoothly promoting the siloxane bonding reaction. More preferably, it is -2000 mass parts.

  Thus, a siloxane bond reaction is performed, and resin particles having a crosslinked structure and having a plurality of depressions on the surface are obtained. The resin particles can be preferably used for the polishing aid of the present invention.

  In addition, a commercial item can also be used as a resin particle which has a several hollow on the surface obtained in this way. For example, multi-dimple beads (manufactured by Sumitomo Seika Co., Ltd.) can be used particularly preferably.

  Cyclodextrin treated with a silane coupling agent (silane coupling-treated cyclodextrin) can be used as a polishing aid, but it is preferably used as a polishing aid in combination with resin particles having a plurality of depressions on the surface. it can.

  When resin particles having a plurality of depressions on the surface are used in combination with a silane coupling-treated cyclodextrin, the amount of the resin particles used is 2 to 50 parts by mass with respect to 100 parts by mass of the silane coupling-treated cyclodextrin. Preferably, 5-30 mass parts is more preferable, and 10-25 mass parts is still more preferable.

  If the amount of resin particles having a plurality of depressions on the surface is 2 parts by mass or more, the polishing rate can be further improved, and if it is 50 parts by mass or less, it is more economical in view of the amount of the particles to be used. (Preferably cost performance) polishing rate can be obtained.

  The polishing aid of the present invention improves the polishing efficiency of the polishing agent when used in combination with the polishing agent. Therefore, the present invention also includes a polishing composition containing the above polishing aid and abrasive. As the abrasive, it is preferable to use abrasive grains. Examples of the material of the abrasive grains used in the present invention include transition metal oxides, iron oxides, aluminum oxides, silicon oxides, silica sols, titanium oxides, silicon carbides, diamonds and the like. A transition metal oxide is particularly preferable. As the transition metal, cerium oxide, zirconium oxide and the like are preferable, and cerium oxide is particularly preferable.

  The average particle size of these abrasive grains is preferably 10 μm or less, and more preferably 5 μm to 8 μm. When it is 10 μm or less, the possibility of scratches due to polishing is reduced. In addition, the average particle diameter of an abrasive grain means the particle diameter in the integrated value 50% in the particle size distribution measured by the laser diffraction scattering method using water as a solvent.

  The amount of abrasive grains used is preferably such that the mixing mass ratio of the abrasive grains and the polishing aid is 80:20 to 20:80, and 50:50 to 20:80 from the viewpoint that the amount of abrasive grains used can be reduced. Is more preferable.

  Although there is no particular limitation, the abrasive composition of the present invention is preferably in the form of a slurry (in this specification, the slurry-like abrasive composition is also referred to as an abrasive slurry in particular). In order to produce an abrasive slurry using the polishing aid of the present invention, for example, a method of uniformly mixing an abrasive, a polishing aid and water can be mentioned.

  The mass ratio of the polishing aid composition in the abrasive slurry is preferably from 0.01 to 10 mass%, more preferably from 0.05 to 5 mass%, still more preferably from 0.1 to 1 mass%.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention in detail, this invention is not limited to these Examples at all.

<Preparation of silane coupling-treated cyclodextrin>
100 kg of α-cyclodextrin (manufactured by Cyclochem Co., Ltd.) was pulverized with a pin mill pulverizer, and further adjusted with a sieve to a particle size of 5 to 25 μm, and dried with an air dryer at 100 to 120 ° C. for 3 hours. The treated α-cyclodextrin is placed in a Henschel mixer, and 50 g of 3-aminopropyltriethoxysilane is added as a silane coupling agent at room temperature, and the mixture is stirred at 60 ° C. for 30 minutes to obtain a silane coupling treatment α- Cyclodextrin was obtained.

<Preparation of resin particles having a plurality of depressions on the surface>
[Preparation Example 1]
[Manufacture of seed particles having a monomer having a silyl group as a constituent monomer component]
In a 500 mL reaction vessel equipped with a stirrer and a condenser, 178 g of methanol, 22 g of styrene, 5.6 g of 3-methacryloxypropyltrimethoxysilane, 18 g of polyvinylpyrrolidone (K-30), 2,2′-azobis (2- 0.6 g of methylpropionitrile) was charged, and the polymerization reaction was carried out for 24 hours at a stirring speed of 300 rpm and 60 ° C.

  After the polymerization, filtration was performed to obtain 20.2 g of seed particles having a monomer having a silyl group as a constituent monomer component.

[Production of resin particle precursor having a large number of depressions on the surface]
In a 500 mL reaction vessel equipped with a stirrer and a condenser, 48.67 g of methanol and 21.89 g of water were charged, and 4.19 g of seed particles containing a monomer having a silyl group as a constituent monomer component were dispersed. 2.7 g of polyvinylpyrrolidone (K-30), 2.625 g of 70% by weight aqueous methanol solution containing 8% by weight of polyvinylpyrrolidone (K-90), 0.1398 g of 2,2′-azobis (2-methylpropionitrile), An additional 0.0021 g of 1,1′-azobis (cyclohexane 1-carbonitrile) was added.

  Under a nitrogen gas atmosphere, a mixed solvent of 2.1 g of n-butyl acrylate and 7.54 g of n-dodecane was continuously added over 5 hours at a stirring speed of 300 rpm and 60 ° C., and further reacted at the same temperature for 5 hours. .

  After polymerization, it was filtered, washed with methanol, and then dried under reduced pressure at 25 ° C. to obtain 5.56 g of a resin particle precursor having a large number of depressions on the surface.

[Production of resin particles having a large number of depressions on the surface]
In a 200 mL reaction vessel equipped with a stirrer and a condenser tube, 14.35 g of methanol and 26.98 g of water were charged, and 2.50 g of a resin particle precursor having a number of depressions on the surface was dispersed. Furthermore, 1.518 g of paratoluenesulfonic acid monohydrate was added, and the mixture was reacted for 3 hours at a rotation speed of 200 rpm and 60 ° C. in a nitrogen gas atmosphere.

  After the reaction, it was filtered to obtain 2.50 g of resin particles having a large number of depressions on the surface. The electron micrograph of the resin particle which has many dents on the obtained surface is shown in FIG.

[Preparation Example 2]
Other than changing 5.6 g of 3-methacryloxypropyltrimethoxysilane to 5.2 g of 3-methacryloxypropylmethyldimethoxysilane in [Production of seed particles using monomer having silyl group as constituent monomer component] in Preparation Example 1 In the same manner as in Preparation Example 1, 2.50 g of resin particles having many indentations on the surface were obtained.

[Preparation Example 3]
Other than changing 5.6 g of 3-methacryloxypropyltrimethoxysilane to 6.5 g of 3-methacryloxypropyltriethoxysilane in [Production of seed particles using monomer having silyl group as constituent monomer component] in Preparation Example 1 In the same manner as in Preparation Example 1, 2.50 g of resin particles having many indentations on the surface were obtained.

[Preparation Example 4]
Other than changing 5.6 g of 3-methacryloxypropyltrimethoxysilane to 5.3 g of 3-acryloxypropyltrimethoxysilane in [Production of seed particles using monomer having silyl group as constituent monomer component] in Preparation Example 1 In the same manner as in Preparation Example 1, 2.50 g of resin particles having many indentations on the surface were obtained.

Example 1
To 45 g of the silane coupling-treated α-cyclodextrin obtained as described above, 5 g of resin particles having a plurality of depressions were added to the surface obtained in Preparation Example 1 and mixed uniformly to obtain a polishing aid. .

To a polishing machine UTS-III (manufactured by Nagata Seisakusho), 50 g of cerium oxide abrasive (general product; ceria) as abrasive grains, 50 g of the above-obtained polishing aid and 10 L of water were added and mixed uniformly to form a slurry. An abrasive (abrasive slurry) was obtained.
Using the obtained abrasive slurry, a polishing test was conducted by the following method to evaluate the polishing performance.

  The φ35 convex / concave grinding lens of optical glass types SF2 and SFL57 (manufactured by Shot) is pre-ground with a mixture of diamond powder and brass fine powder. Using the circulating polishing liquid, the glass surface was slid for 30 minutes with a polyurethane polishing pad for polishing work. “Φ” represents the filter diameter (millimeter) of the lens.

The degree of polishing per unit polishing time (reduced weight mg ÷ polishing surface area cm ² × 100) was calculated. As can be seen from the calculation formula, the greater the degree of polishing, the higher the polishing efficiency. Further, the presence or absence of polishing scratches after polishing was measured (visually). The results are shown in Table 1. In each table, “cyclodextrin” may be abbreviated as “CD”.

Example 2
Using β-cyclodextrin (manufactured by Cyclochem Co., Ltd.) instead of α-cyclodextrin, silane coupling-treated β-cyclodextrin was obtained in the same manner as in the above <Preparation of silane coupling-treated cyclodextrin>. Using the obtained silane coupling-treated β-cyclodextrin instead of the silane coupling-treated α-cyclodextrin, an abrasive slurry was obtained in the same manner as in Example 1, and the polishing performance was evaluated. The results are shown in Table 1.

Comparative Example 1
Without using a polishing aid, 10 g of water was added to 100 g of cerium oxide abrasive (general product; ceria) as abrasive grains and mixed uniformly to obtain an abrasive slurry. The polishing performance was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Example 3
In Example 1, instead of the optical lens glass types SF2 and SFL57 (manufactured by SCHOTT), a φ35 convex / concave grinding lens of optical lens glass type BK7 (manufactured by Nagata Manufacturing Co., Ltd.) was used. And evaluated. The results are shown in Table 2.

Example 4
In Example 1, the amount of silane coupling-treated α-cyclodextrin was changed from 45 g to 40 g, and the amount of resin particles having a plurality of depressions on the surface was changed from 5 g to 10 g. Evaluation was performed in the same manner as in Example 1 except that a φ35 convex / concave grinding lens of optical glass type BK7 (manufactured by Nagata Seisakusho Co., Ltd.) was used instead of the optical lens. The results are shown in Table 2.

Example 5
In Example 2, the amount of silane coupling-treated β-cyclodextrin was changed from 45 g to 40 g, and the amount of resin particles having a plurality of depressions on the surface was changed from 5 g to 10 g. Evaluation was made in the same manner as in Example 2 except that a φ35 convex / concave grinding lens of optical glass type BK7 (manufactured by Nagata Seisakusho Co., Ltd.) was used instead. The results are shown in Table 2.

Example 6
A silane coupling-treated γ-cyclodextrin was obtained in the same manner as in the above <Preparation of silane coupling-treated cyclodextrin> using γ-cyclodextrin (manufactured by Cyclochem) instead of α-cyclodextrin. The obtained silane coupling-treated γ-cyclodextrin is used instead of the silane coupling-treated α-cyclodextrin, and instead of the optical lens glass types SF2 and SFL57 (manufactured by Schott), optical lens glass type BK7 (manufactured by Nagata Manufacturing Co., Ltd.) The evaluation was made in the same manner as in Example 1 except that a φ35 convex / concave grinding lens was used. The results are shown in Table 2.

Example 7
In Example 6, evaluation was performed in the same manner as in Example 6 except that the amount of silane coupling-treated γ-cyclodextrin was changed from 45 g to 40 g, and the amount of resin particles having a plurality of depressions on the surface was changed from 5 g to 10 g. . The results are shown in Table 2.

Comparative Example 2
In Comparative Example 1, instead of optical lens glass types SF2 and SFL57 (manufactured by Schott), optical lens glass type BK7 (manufactured by Nagata Mfg. Co., Ltd.), φ35 convex / concave grinding lens was used. And evaluated. The results are shown in Table 2.

Example 8
In Example 3, evaluation was performed in the same manner as in Example 3 except that the amount of silane coupling-treated α-cyclodextrin used was changed to 45 g and resin particles having a plurality of depressions on the surface were not used. The results are shown in Table 3.

Example 9
In Example 5, evaluation was carried out in the same manner as in Example 5 except that 40 g of the silane coupling-treated β-cyclodextrin was changed to 50 g, and resin particles having a plurality of depressions on the surface were not used. The results are shown in Table 3.

Comparative Example 3
In Example 8, it evaluated similarly to Example 8 except having used (alpha) -cyclodextrin which has not implemented the silane coupling process instead of the silane coupling process (alpha) -cyclodextrin. The results are shown in Table 3.

Comparative Example 4
In Example 9, it evaluated similarly to Example 9 except having used (beta) -cyclodextrin which is not implementing the silane coupling process instead of the silane coupling process (beta) cyclodextrin. The results are shown in Table 3.

Example 10
Example 8 is the same as Example 8 except that 50 g of zirconium oxide (ZrO ₂ ) was used in place of 50 g of cerium oxide abrasive (general product; ceria) as abrasive grains, and the polishing time was changed from 30 minutes to 60 minutes. Evaluation was performed in the same manner. The results are shown in Table 4.

Example 11
In Example 3, instead of 50 g of cerium oxide abrasive (general product; ceria) as abrasive grains, 50 g of zirconium oxide (ZrO ₂ ) was used, and the polishing time was changed from 30 minutes to 60 minutes. Evaluation was performed in the same manner. The results are shown in Table 4.

Example 12
In Example 4, instead of 50 g of cerium oxide abrasive (general product; ceria) as abrasive grains, 50 g of zirconium oxide (ZrO ₂ ) was used, and the polishing time was changed from 30 minutes to 60 minutes. Evaluation was performed in the same manner. The results are shown in Table 4.

Example 13
In Example 3, in place of 50 g of cerium oxide abrasive (general product; ceria) as abrasive grains, 50 g of titanium oxide (TiO ₂ ) was used, and the polishing time was changed from 30 minutes to 120 minutes. Evaluation was performed in the same manner. The results are shown in Table 4.

Example 14
In Example 4, instead of 50 g of cerium oxide abrasive (general product; ceria) as abrasive grains, 50 g of titanium oxide (TiO ₂ ) was used, and the polishing time was changed from 30 minutes to 120 minutes. Evaluation was performed in the same manner. The results are shown in Table 4.

Comparative Example 5
Comparative Example 2 was the same as Comparative Example 2 except that 100 g of zirconium oxide (ZrO ₂ ) was used instead of 100 g of cerium oxide abrasive (general product; ceria) as the abrasive grains, and the polishing time was changed from 30 minutes to 60 minutes. Evaluation was performed in the same manner. The results are shown in Table 4.

Comparative Example 6
In Comparative Example 2, Example 4 was used except that 100 g of titanium oxide (TiO ₂ ) was used in place of 100 g of cerium oxide abrasive (general product; ceria) as abrasive grains, and the polishing time was changed from 30 minutes to 120 minutes. Evaluation was performed in the same manner. The results are shown in Table 4.

  In Examples 10 to 14 and Comparative Examples 5 to 6, the polishing time was changed from the other examples because an appropriate polishing time corresponding to each abrasive grain was adopted along with the change of the abrasive grains. It is.

Claims (15)

A polishing aid containing cyclodextrin treated with a silane coupling agent. The polishing aid according to claim 1, wherein the cyclodextrin is at least one selected from the group consisting of α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin. The said silane coupling agent is at least 1 sort (s) chosen from the group which consists of an aminosilane coupling agent, a vinyl silane coupling agent, a methacryl silane coupling agent, an isocyanate silane coupling agent, and an epoxy silane coupling agent. Or the polishing aid according to 2. Furthermore, the grinding | polishing adjuvant in any one of Claims 1-3 containing the resin particle which has a some hollow on the surface. The polishing aid according to claim 4, wherein the resin particles having a plurality of depressions on the surface are particles comprising a resin having a crosslinked structure. The polishing aid according to claim 5, wherein the crosslinked structure is a crosslinked structure by a siloxane bond. Resin particles having a plurality of depressions on the surface are particles in which a monomer having a polymerization group and a crosslinking group is polymerized, and are particles comprising a resin having a crosslinked structure crosslinked by a crosslinking group derived from the monomer. The polishing aid according to any one of claims 4 to 6. The monomer-derived crosslinking group is represented by formula (1);

(Wherein R ^{1 to} R ³ each independently represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 5 carbon atoms, or an alkoxyl group having 1 to 5 carbon atoms). The polishing aid according to claim 7, which is a base. The monomer having a polymerization group and a crosslinking group is selected from 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, and 3- The polishing aid according to claim 7 or 8, which is at least one selected from the group consisting of (meth) acryloxypropyltriethoxysilane. Resin particles having a plurality of depressions on the surface are seed-polymerized with a seed polymerization monomer in the presence of seed particles containing a monomer having a crosslinking group, and then at least a part of the crosslinking group is crosslinked. The polishing aid according to any one of claims 4 to 9, which is obtained by An abrasive composition comprising the polishing aid according to any one of claims 1 to 10 and an abrasive. The abrasive | polishing agent composition of Claim 11 whose abrasive | polishing agent is an abrasive grain. The abrasive composition according to claim 11 or 12, wherein the abrasive is a transition metal oxide. The abrasive composition according to claim 13, wherein the transition metal oxide is at least one selected from the group consisting of cerium oxide, zirconium oxide, and titanium oxide. The abrasive | polishing agent composition in any one of Claims 11-14 which is an abrasive | polishing agent slurry.

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