Organic-inorganic composite fine particle dispersion liquid, method for producing the same, and abrasive grain dispersion liquid

Abstract

To provide organic / inorganic composite fine particle dispersion having excellent polishing characteristics.SOLUTION: Organic / inorganic composite fine particle dispersion has the following requirements [1], [2] and [3], and is obtained by dispersing organic / inorganic composite fine particles having an average particle diameter (D1) measured by a dynamic light scattering method of 20 nm or more and 600 nm or less in a solvent. [1] The organic / inorganic composite fine particles have base particles which are composed of an inorganic component containing no organic component, and an organic / inorganic composite layer containing an inorganic component and an organic component on the surface of the base particles. [2] The organic / inorganic composite fine particles have a COD value per inorganic component of 100 ppm or more and 10% or less. [3] A thickness of the organic / inorganic composite layer is 1 nm or more and 500 nm or less.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an organic-inorganic composite fine particle dispersion suitable as an abrasive grain dispersion for polishing, a method for producing the same, and an abrasive grain dispersion. Further, the present invention relates to an organic-inorganic composite fine particle dispersion containing particle-linked type organic-inorganic composite fine particles, a method for producing the same, and an abrasive grain dispersion.

Background Art

[0002] For example, among silica sols in which silica fine particles are dispersed in a solvent, as silica sols in which the shape of the silica fine particles is other than spherical, those having a chain shape, a bead shape, or an oblong shape are known. In addition, a particle-linked type silica sol in which particle-linked type silica fine particles are dispersed in a solvent is also known, and these are used, for example, as various abrasives.

[0003] Patent Document 1 discloses an invention of a particle-linked type alumina-silica composite sol in which particle-linked type alumina-silica composite fine particles having a structure in which two or more alumina-silica composite primary particles having an average particle diameter measured by an image analysis method in the range of 5 to 300 nm are bonded are dispersed in a dispersion medium, and a method for producing the same. In Patent Document 1, these particle-linked type alumina-silica composite fine particles are characterized in that, as alumina-silica composite primary particles, they include spherical particles having a plurality of wart-like protrusions on the surface. This invention has a specific structure different from that of ordinary particle-linked type organic-inorganic composite fine particles or non-spherical alumina-silica composite fine particles. Therefore, for example, it is useful as an abrasive and an abrasive composition, and is particularly excellent in the effect of high polishing speed. However, aluminum becomes a contaminant depending on the type of polishing substrate, which is not preferable.

[0004] Patent Document 2 discloses an invention of a particle-linked type silica sol in which particle-linked type organic-inorganic composite fine particles containing a structure in which two or more silica primary particles having an average particle diameter measured by an image analysis method in the range of 5 to 300 nm are bonded are dispersed in a dispersion medium, and a method for producing the same. In Patent Document 2, this particle-linked type organic-inorganic composite fine particle is characterized in that, as the silica primary particle, it contains spherical particles having a plurality of wart-like protrusions on the surface. Since this invention has a specific structure different from ordinary particle-linked type organic-inorganic composite fine particles or non-spherical organic-inorganic composite fine particles, for example, it is useful as an abrasive and an abrasive composition, and is particularly excellent in the effect of high polishing speed. However, since it includes a tetrapod type as a bonding mode and further includes wart-like protrusions, stress concentration on the local polishing substrate is likely to occur, and polishing scratches such as scratches are likely to occur.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] An object of the present invention is to provide an organic-inorganic composite fine particle dispersion having excellent polishing characteristics, a method for producing the same, and an abrasive grain dispersion. Furthermore, an object is to provide an organic-inorganic composite fine particle dispersion containing particle-linked type organic-inorganic composite fine particles, a method for producing the same, and an abrasive grain dispersion.

Means for Solving the Problems

[0007] According to one aspect of the present invention, there is provided an organic-inorganic composite particle dispersion in which organic-inorganic composite particles having the following requirements [1], [2] and [3] and having an average particle diameter (D1) measured by the dynamic light scattering method of 20 nm or more and 600 nm or less are dispersed in a solvent. [1] The organic-inorganic composite particles have a mother particle composed of an inorganic component containing no organic component, and an organic-inorganic composite layer containing an inorganic component and an organic component on the surface of the mother particle. [2] The organic-inorganic composite particles have a COD value per inorganic component of 100 ppm or more and 10% or less. [3] The thickness of the organic-inorganic composite layer is 1 nm or more and 500 nm or less.

[0008] According to one aspect of the present invention, there is provided an abrasive grain dispersion liquid containing the organic-inorganic composite particle dispersion liquid according to one aspect of the present invention.

[0009] According to one aspect of the present invention, there is provided a method for producing the organic-inorganic composite particle dispersion liquid according to one aspect of the present invention, including the following step 1. Step 1: A cationic organic polymer component is added to a silica particle dispersion liquid having a SiO2 concentration of 0.1% by mass or more and 30% by mass or less within the following ratio (WA / WS1), and then heated to 40°C or more and 98°C or less and held for 0.5 hours or more to obtain a particle-linked organic-inorganic composite particle dispersion liquid. 0.002 ≦ WA / WS1 ≦ 0.3 (Here, WS1 is the mass of silica in the silica particle dispersion liquid, and WA is the mass of the cationic organic polymer component.)

Effects of the Invention

[0010] According to the present invention, it is possible to provide an organic-inorganic composite particle dispersion liquid having excellent polishing characteristics and a method for producing the same, and an abrasive grain dispersion liquid. Furthermore, it is possible to provide an organic-inorganic composite particle dispersion liquid containing particle-linked organic-inorganic composite particles and a method for producing the same, and an abrasive grain dispersion liquid.

Brief Description of the Drawings

[0011]

Figure 1

Figure 2

Mode for Carrying Out the Invention

[0012] [Organic-Inorganic Composite Fine Particle Dispersion Liquid] The organic-inorganic composite fine particle dispersion liquid of the present invention satisfies the following requirements [1], [2], and [3], and is characterized in that organic-inorganic composite fine particles having an average particle diameter (D1) measured by the dynamic light scattering method of 20 nm or more and 600 nm or less are dispersed in a solvent. [1] The organic-inorganic composite fine particles have a mother particle composed of an inorganic component containing no organic component, and an organic-inorganic composite layer containing an inorganic component and an organic component on the surface of the mother particle. [2] The organic-inorganic composite fine particles have a COD value per inorganic component of 100 ppm or more and 10% or less. [3] The thickness of the organic-inorganic composite layer is 1 nm or more and 500 nm or less.

[0013] (Dynamic Light Scattering Method / Particle Diameter / Particle Shape) The shape of the organic-inorganic composite fine particles of the present invention is not particularly limited. However, when the organic-inorganic composite fine particles are applied to polishing applications, a non-spherical or particle-linked type is preferably suitable in order to obtain a practical polishing rate. The size of the organic-inorganic composite fine particles needs to be in the range where the average particle diameter (D1) measured by the dynamic light scattering method is 20 nm or more and 600 nm or less. When the organic-inorganic composite fine particle dispersion liquid is applied to polishing applications, if the average particle diameter (D1) is less than 20 nm, a practical polishing rate may not be obtained. Also, when the average particle diameter (D1) exceeds 600 nm, scratches (linear marks) are likely to occur on the polishing substrate. The range of the average particle diameter (D1) is preferably 30 nm or more and 400 nm or less, more preferably 50 nm or more and 300 nm or less.

[0014] (Mother particle / Organic-inorganic composite layer / COD value) The organic-inorganic composite fine particles of the present invention need to satisfy the following requirement [1]. Requirement [1]: Having mother particles composed of inorganic components containing no organic components, and an organic-inorganic composite layer containing inorganic components and organic components on the surface of the mother particles. That is, the structure of the organic-inorganic composite fine particles of the present invention includes at least mother particles and a coating layer covering the mother particles. The mother particles are composed of inorganic components containing no organic components. Further, the coating layer contains inorganic components and organic components. In the present invention, this coating layer is also referred to as an "organic-inorganic composite layer". Note that the organic-inorganic composite fine particles may include mother particles MOT, an organic-inorganic composite layer CMP covering the mother particles, and an outermost layer OUT covering the organic-inorganic composite layer CMP, as shown in FIG. 1(A).

[0015] The organic-inorganic composite fine particles of the present invention need to satisfy the following requirement [2]. Requirement [2]: The COD value per inorganic component is 100 ppm or more and 10% or less. Note that the organic-inorganic composite layer is a composite system of inorganic components and organic components. The presence of the organic components can be confirmed by measuring the COD (chemical oxygen demand) when the organic-inorganic composite fine particles are dissolved. It is more preferable that the organic-inorganic composite fine particles have a COD value per inorganic component of 300 ppm or more and 5% or less. Note that the COD measurement value can be measured by the method described in the examples below. In addition, it is preferable that the organic component in the organic-inorganic composite layer has a concentration gradient from the center of the particle toward the outside. That is, the mother particle including the center of the particle does not contain the organic component, but the organic-inorganic composite layer outside the mother particle contains the organic component. The concentration of the organic component in the organic-inorganic composite layer gradually decreases toward the outside. Further, the layer outside the organic-inorganic composite layer, that is, the outermost layer does not contain the organic component. In this way, when the concentration of the organic component varies from the center of the particle toward the outside, it is said that there is a concentration gradient. In addition, the presence or absence of the organic component and the concentration gradient can be confirmed by measuring the COD value from the center of the particle toward the outside (see Figure 2). Since the organic component contained inside such particles is softer than the inorganic component, when used as abrasive grains for polishing, it tends to be easily elastically deformed. When the abrasive grains are elastically deformed, the contact area with the substrate increases, which is preferable because the polishing rate is improved. However, if there is a region where the concentration of the organic component is locally high inside the particle, there is a concern that the strength of the particle is insufficient and the particle collapses during polishing, resulting in a decrease in the polishing rate. Therefore, it is estimated that by having the organic component unevenly distributed in the polishing particles, that is, by providing a concentration gradient of the organic component, the strength of the particles is maintained while showing a high polishing rate without the particles collapsing.

[0016] Examples of the inorganic component of the mother particle include silica, alumina, a composite system of silica and alumina (so-called silica-alumina), titania, zirconia, and ceria, as well as these composite oxides. Among these, silica or a silica-alumina composite system is preferable. Examples of the inorganic component of the organic-inorganic composite layer include silica, alumina, a composite system of silica and alumina (so-called silica-alumina), titania, zirconia, and ceria, and composite oxides thereof. Among these, silica or a silica-alumina composite system is preferable. Similarly, the organic component of the organic-inorganic composite layer is not limited as long as it is an organic compound (including organic polymer compounds). Usually, it is an organic compound (including organic polymer compounds) used in the synthesis stage of the organic-inorganic composite fine particles or a decomposition product thereof. Specific decomposition products include compounds having an imino group or an amino group, carboxylic acids, aldehydes, nitriles, ketones, alcohols, ethers, alkenes, alkynes, esters, amides, or compounds having a cyano group, amino acid-based compounds, and salts thereof. Specific organic compounds include compounds such as poly(diethylaminoethyl methacrylate) (PDEAEM), poly(dimethyldiallylammonium chloride) (PDMDAAC), and polyalkyleneimine, and compounds having the aforementioned functional groups in these compounds. The average particle diameter of the mother particles is usually in the range of 5 nm or more and 500 nm or less.

[0017] The organic-inorganic composite fine particles of the present invention need to satisfy the following requirement [3]. Requirement [3] The thickness of the organic-inorganic composite layer is 1 nm or more and 500 nm or less. When the organic-inorganic composite fine particle dispersion of the present invention is applied to polishing applications, if the thickness of the organic-inorganic composite layer is within the above range, the abrasive grains also originate from the organic-inorganic composite layer and are easily elastically deformed during polishing, so polishing scratches are less likely to occur, and furthermore, the flatness of the polished substrate is improved, which is useful. When the thickness of the organic-inorganic composite layer is less than 1 nm, since the organic-inorganic composite layer is thin, it becomes difficult for the abrasive grains to be elastically deformed, and thus the polishing rate and flatness tend to be difficult to improve.

[0018] The thickness of the organic-inorganic composite layer is preferably 3 nm or more and 300 nm or less. The thickness of the organic-inorganic composite layer can be measured using the method described below.

[0019] (Shape of the organic-inorganic composite fine particles) The shape of the organic-inorganic composite fine particles of the present invention is not particularly limited as described above, and may be any of independent spherical particles, independent non-spherical particles, and particle-linked type particles formed by linking independent spherical particles or non-spherical particles. Here, the spherical particles mean those having a minor axis / major axis ratio in the range of 0.8 or more and 1 or less. When the organic-inorganic composite fine particles are applied to polishing applications, particle-linked type particles are preferable in order to obtain a practical polishing rate. On the other hand, spherical particles are preferable when it is desired to reduce scratches after polishing or improve flatness.

[0020] (Organic-inorganic composite fine particle dispersion liquid containing particle-linked type organic-inorganic composite fine particles) In the present invention, it is preferable that the organic-inorganic composite fine particles are the above-mentioned organic-inorganic composite fine particle dispersion liquid containing particle-linked type organic-inorganic composite fine particles. The particle-linked type organic-inorganic composite fine particles have a structure in which single-particle organic-inorganic composite fine particles are linked. Here, the shape of the single-particle organic-inorganic composite fine particles may be spherical or non-spherical.

[0021] The organic-inorganic composite fine particle dispersion liquid of the present invention satisfies the following requirements [1A], [2], and [3], and is characterized in that particle-linked type organic-inorganic composite fine particles having an average particle diameter (D1) measured by the dynamic light scattering method of 20 nm or more and 600 nm or less are dispersed in a solvent. [1A] The particle-linked type organic-inorganic composite fine particles are formed by linking primary organic-inorganic composite fine particles having a mother particle composed of an inorganic component containing no organic component and an organic-inorganic composite layer containing an inorganic component and an organic component on the surface of the mother particle, or the mother particles composed of an inorganic component containing no organic component are linked, and the surface of the linked mother particles has an organic-inorganic composite layer containing an inorganic component and an organic component. [2] The particle-linked type organic-inorganic composite fine particles have a COD value per inorganic component of 100 ppm or more and 10% or less. [3] The thickness of the organic-inorganic composite layer is 1 nm or more and 500 nm or less.

[0022] The particulate-linked organic-inorganic composite microparticles of the present invention are required to satisfy the following requirement [1A]. Requirement [1A]: Either primary organic-inorganic composite microparticles formed by linking mother particles composed of inorganic components not containing an organic component and an organic-inorganic composite layer containing an inorganic component and an organic component on the surface of the mother particles, or mother particles formed by linking mother particles composed of inorganic components not containing an organic component, and having an organic-inorganic composite layer containing an inorganic component and an organic component on the surface of the linked mother particles. That is, the particulate-linked organic-inorganic composite microparticles have a structure in which single-particle organic-inorganic composite microparticles (hereinafter also referred to as "single-particle organic-inorganic composite microparticles") are linked. Further, the particulate-linked organic-inorganic composite microparticles may have an organic-inorganic composite layer containing an inorganic component and an organic component on the surface of mother particles having a structure in which primary particles composed of inorganic components not containing an organic component are linked. In the present specification, the term "organic-inorganic composite microparticles" is a concept including both "single-particle organic-inorganic composite microparticles" and "particulate-linked organic-inorganic composite microparticles".

[0023] The size of the particulate-linked organic-inorganic composite microparticles, requirements [2] and [3], and the mother particles are as described above.

[0024] As described above, "linked organic-inorganic composite microparticles" means that adjacent organic-inorganic composite microparticles are fixed to each other by a bond formed between adjacent organic-inorganic composite microparticles. Here, the type of bond is not particularly limited, and examples thereof include chemical bonds such as siloxane bonds formed by a condensation reaction between surface silanol groups of adjacent primary composite microparticles. Hereinafter, the dispersion of the particulate-linked organic-inorganic composite microparticles is also referred to as "dispersion of particulate-linked organic-inorganic composite microparticles" or "dispersion of linked particles". The primary particles constituting the particulate-linked organic-inorganic composite microparticles, that is, the "primary organic-inorganic composite microparticles" are also referred to as "primary composite microparticles". Further, the particulate-linked organic-inorganic composite microparticles having a structure in which the above-mentioned primary composite microparticles are linked are also referred to as "linked particles". Particles-connected type organic-inorganic composite microparticles having a three-dimensional branched structure formed by connecting the primary composite microparticles of the present invention are also referred to as "three-dimensional connected particles".

[0025] Furthermore, particles-connected type organic-inorganic composite microparticles (connected particles) having a structure formed by connecting primary composite microparticles other than the particles-connected type organic-inorganic composite microparticles (three-dimensional connected particles) having a three-dimensional branched structure formed by connecting the primary composite microparticles of the present invention are also referred to as "planar connected particles". Connected particles have a structure in which a large number of primary composite microparticles are bonded. In the connected particles, the smallest structural unit containing one primary composite microparticle may be referred to as a "unit structure" for the sake of convenience in the present application. Here, the "unit structure" includes one primary composite microparticle and a part of the neck portion formed between the primary composite microparticle and the adjacent primary composite microparticle. The particles-connected type organic-inorganic composite microparticles in the present invention can also be referred to as particles-connected type organic-inorganic composite microparticles having a structure in which the above unit structures are connected. The same applies to the three-dimensional connected particles and the planar connected particles. As described later, the organic-inorganic composite microparticle dispersion or the organic-inorganic composite microparticles, which are one of the main raw materials for producing the particles-connected type organic-inorganic composite microparticle dispersion, may be referred to as the "organic-inorganic composite microparticle dispersion used as a raw material" and the "organic-inorganic composite microparticles used as a raw material", respectively. In addition, primary composite microparticles other than the connected particles are also referred to as "single particles".

[0026] The organic-inorganic composite microparticles contained in the particles-connected type organic-inorganic composite microparticle dispersion of the present invention refer to all the organic-inorganic composite microparticles (connected particles and single particles) contained in the particles-connected type organic-inorganic composite microparticle dispersion. In the present invention, the characteristics of the particles may be specified using a transmission microscope photograph or a scanning microscope photograph. In this case, a transmission microscope image can be used in the same manner instead of the photograph. Similarly, a scanning microscope image can be used in the scanning microscope photograph.

[0027] (Particles-connected type organic-inorganic composite microparticles) The particulate-linked organic-inorganic composite microparticles of the present invention are composed of particulate-linked organic-inorganic composite microparticles having a three-dimensional branched structure (three-dimensional linked particles) and particulate-linked organic-inorganic composite microparticles other than the particulate-linked organic-inorganic composite microparticles having a three-dimensional branched structure (planar linked particles).

[0028] Regarding the primary composite microparticles in the "particulate-linked organic-inorganic composite microparticles", it is preferable that the shape thereof is spherical or substantially spherical. Note that a small amount of particles having other shapes (for example, oval, cubic or rod-shaped particles) may be mixed with such spherical particles or the like. The particle diameters of the primary composite microparticles may be uniform or different from each other. Here, the shape of the primary composite microparticles can be confirmed from a transmission electron micrograph (magnification: 200,000 times).

[0029] The average particle diameter (transmission electron micrograph, magnification 200,000 times) of the primary composite microparticles in the linked particles is preferably 20 nm or more and 600 nm or less, more preferably 30 nm or more and 400 nm or less, and still more preferably 50 nm or more and 300 nm or less. In the present application, such average particle diameter is represented by average particle diameter [F]. The measurement method of the average particle diameter [F] is as described below. When the average particle diameter of the primary composite microparticles in the linked particles is less than 5 nm, the linked particles obtained by aggregation of the primary composite microparticles tend to be in a lump shape. Also, in the case of polishing applications, sufficient polishing speed cannot be obtained, presumably because stress concentration on the polishing substrate cannot be obtained, which is not preferable. When the average particle diameter of the primary composite microparticles exceeds 600 nm, for example, in polishing applications, the contact area between the polishing substrate and the linked particles is significantly reduced, which may lead to a decrease in the polishing speed. Also, scratches (linear marks) may easily occur on the polished surface. There is no significant difference between the average particle diameter of the primary composite microparticles in the three-dimensional linked particles, the average particle diameter of the primary composite microparticles in the planar linked particles, and the average particle diameter of the primary composite microparticles in the linked particles.

[0030] [Particulate-linked organic-inorganic composite microparticles having a three-dimensional branched structure (three-dimensional linked particles)] The particulate-linked organic-inorganic composite fine particles having a three-dimensional branched structure according to the present invention are characterized by having a chain-like structure with at least one branch (a) and a three-dimensional structure with respect to this structure. More specifically, as shown in FIG. 1(B), the particulate-linked organic-inorganic composite fine particles have a chain-like structure (Ch) in which primary composite fine particles indicated by white circles are linked in a chain. Further, primary composite fine particles are linked to this chain-like structure (Ch) to have a branch (a). Here, the number of branches (a) may be one or more and is not particularly limited. The chain-like structure (Ch) and the branch (a) exist substantially on the same plane. And, primary composite fine particles indicated by black circles are bonded in a direction intersecting this plane and forming an angle (hereinafter also referred to as the "three-dimensional direction") to form a branch (b) or a terminal (c) so as to have a three-dimensional structure.

[0031] Having a structure with at least one branch (a) and a three-dimensional structure with respect to this structure specifically means at least one of the following structures (1) or (2). (1) A branch (b) extending in the three-dimensional direction with respect to the branch (a) (2) A terminal (c) extending in the three-dimensional direction with respect to the branch (a)

[0032] The above-mentioned chain-like refers to an elongated structure formed by linking primary organic-inorganic composite fine particles, and can also be called a bent or linear shape. Note that a particulate-linked structure in which such chain-like particles are joined at both ends to form a ring, a network structure, a structure in which primary composite fine particles aggregate to form a tetrapod-like shape, and an irregular aggregate of primary composite fine particles (for example, a massive aggregate containing a plurality of primary composite fine particles) are not included in the scope of the above-mentioned chain-like.

[0033] The above-mentioned branch (a) refers to a branched structure formed by the binding of the ends of primary composite fine particles or a conjugate of primary composite fine particles in a direction other than the linear direction in particles excluding the primary composite fine particles at both ends of the three-dimensionally linked particles. (A chain-like portion including the primary composite fine particles to which the branch (a) is bonded in the three-dimensionally linked particles is referred to as the "main chain".) The branch (b) refers to a branched structure formed by the bonding of the ends of primary composite fine particles or a conjugate of primary composite fine particles in a direction other than the linear direction in particles excluding the primary composite fine particles at both ends of the three-dimensional linked particles, and refers to a branch extending in a three-dimensional direction with respect to the extending direction of the branch (a). The three-dimensional direction can be determined from a transmission electron micrograph as described below. The end (c) refers to a bent structure formed by the bonding of the ends of primary composite fine particles or a conjugate of primary composite fine particles in a direction other than the linear direction in particles excluding the primary composite fine particles at both ends of the three-dimensional linked particles, and refers to a bent structure extending in a three-dimensional direction with respect to the extending direction of the branch (a). Here, the three-dimensional direction can be determined from a transmission electron micrograph as described below. The average number of connected primary composite fine particles in the particle-linked organic-inorganic composite fine particles having the three-dimensional branched structure is preferably in the range of 5 or more and 20 or less.

[0034] The particle-linked organic-inorganic composite fine particles having a three-dimensional branched structure in the present invention have a chain-like structure defined in requirement [2] and have at least one branch (a), and have a three-dimensional structure with respect to this structure. Such a three-dimensional structure can be confirmed using an electron micrograph (transmission electron micrograph, TEM micrograph) of a dispersion of particle-linked organic-inorganic composite fine particles.

[0035] The three-dimensional linked particles of the present invention have the branch (a) and the branch (b) or the branch (a) and the end (c) as described above. The extending direction of the branch (a) and the extending direction of the branch (b) are in a three-dimensional structure relationship. Similarly, the extending direction of the branch (a) and the extending direction of the end (c) are also in a three-dimensional structure relationship. Therefore, when the three-dimensional linked particles are applied as abrasive grains on a polishing substrate, stress is likely to concentrate at a plurality of contact points between the polishing machine substrate and the three-dimensional linked particles of the present invention during polishing, so that it can contribute to the enhancement of the polishing rate. Furthermore, the abrasive grains composed of three-dimensional linked particles increase the dynamic contact area with the polishing substrate due to their rotational movement, so this can also contribute to an increase in the polishing rate.

[0036] In the present invention, the confirmation of the particle-linked organic-inorganic composite fine particles having a three-dimensional branched structure is carried out as follows. A transmission electron micrograph (magnification: 200,000 times) of a particle-linked organic-inorganic composite fine particle dispersion liquid (SiO2 concentration: 1% by mass, average particle diameter measured by dynamic light scattering method in the range of 20 nm to 600 nm) containing particle-linked organic-inorganic composite fine particles having a structure in which primary composite fine particles are linked is prepared, and among at least 200 particles of an arbitrary shape in which the particles are linked, the number of particles corresponding to three-dimensionally linked particles is measured, and the number ratio of the three-dimensionally linked particles is calculated. The criteria for determining three-dimensionally linked particles are as follows. That is, for specific particle-linked organic-inorganic composite fine particles, it is confirmed whether the following requirements (1) to (3) are satisfied. (1) The number of linked primary composite fine particles is 5 or more and forms a chain structure (2) Among the particles constituting the main chain, there is at least one branch (branch (a)) bonded to a particle other than the terminal particle. (3) It is possible to confirm a portion with a darker shade overlapping on the specific particle-linked organic-inorganic composite fine particles compared to other primary particles. Particle-linked organic-inorganic composite fine particles that satisfy the above requirements are determined to have a branch (branch (b)) extending in the three-dimensional direction or a terminal (c) extending in the three-dimensional direction with respect to branch (a), and are defined as three-dimensionally linked particles having a three-dimensional structure with respect to branch (a).

[0037] [Organic component] The particle-linked organic-inorganic composite fine particles of the present invention contain an organic component. Here, "contain" refers to the inclusion inside the particle-linked organic-inorganic composite fine particles, but a part of the organic component may be adsorbed on the particle surface. In addition, in the particle-linked organic-inorganic composite fine particle dispersion liquid, a part of the organic component may be eluted in the dispersion liquid.

[0038] The particle-linked organic-inorganic composite fine particles of the present invention preferably enclose an organic component. When an organic component is added to inorganic particles, the organic component usually adsorbs onto the surface of the inorganic particles. When such organic-inorganic composite fine particles with the organic component adsorbed on the particle surface are used as abrasive grains, the organic component may act as a cushion layer between the abrasive substrate and the particles, which may reduce the polishing rate and is not preferable. Also, it is not preferable because the organic component desorbed from the surface of the organic-inorganic composite fine particles may adsorb onto the substrate to be polished and cause contamination. On the other hand, in the particle-linked organic-inorganic composite fine particles of the present invention, since most or all of the organic component is encapsulated, there is an advantage that the above-mentioned reduction in polishing rate and contamination of the substrate do not occur. The organic component is derived from the organic polymer component added as a raw material in the production method of the present invention. The organic polymer component may maintain the properties of the organic polymer in the particle-linked organic-inorganic composite fine particles having a three-dimensional branched structure obtained through the production method of the present invention, or may not maintain the properties of the organic polymer and may be, for example, an organic compound.

[0039] Note that the encapsulation of the organic component inside the particle-linked organic-inorganic composite fine particles can be confirmed, for example, by the following method. That is, it can be confirmed by measuring the COD (chemical oxygen demand) of the dissolution solution when the particle-linked organic-inorganic composite fine particles are dissolved. The COD measurement value can be measured by the method described in the examples below. From the viewpoint that the particle-linked organic-inorganic composite fine particles encapsulate the organic polymer component inside, this COD measurement value is preferably 100 ppm or more and 10% or less with respect to 100 parts by weight of silica.

[0040] The molecular structure of the organic polymer component used in the production method of the present invention is not limited and may be linear, planar branched, or three-dimensional branched. The organic polymer component is cationic and has a cationic functional group, and its structure contains a cationic functional group, but may contain any one or all of an anionic functional group and a nonionic functional group. As described above, having a cationic functional group is preferable because it enables control of the surface charge of the organic-inorganic composite fine particles. The weight average molecular weight of the organic polymer component is preferably 300 or more and 100,000 or less, more preferably 300 or more and 50,000 or less, particularly preferably 300 or more and 5,000 or less, and most preferably 300 or more and 2,000 or less. When the weight average molecular weight of the organic polymer component is below the above range, a large amount of the organic polymer component is required to promote the aggregation of the organic-inorganic composite fine particles, which is not economically preferable. Further, when the weight average molecular weight of the organic polymer component exceeds the above range, the aggregation of the organic-inorganic composite fine particles cannot be controlled, and it tends to be difficult to obtain desired particles.

[0041] The organic polymer component is not particularly limited, and examples thereof include poly(diethylaminoethyl methacrylate) (PDEAEM), poly(dimethyldiallylammonium chloride) (PDMDAAC), and polyalkyleneimine. The polyalkyleneimine used in the present invention means, for example, a polymer obtained by polymerizing alkyleneimines having 2 to 8 carbon atoms such as ethyleneimine, propyleneimine, butyleneimine, dimethylethyleneimine, pentyleneimine, hexyleneimine, heptyleneimine, and octyleneimine, and a polymer chemically modified by reacting these with various compounds.

[0042] [In the particulate-linked organic-inorganic composite fine particles having a three-dimensional branched structure 29 [Si-NMR spectrum] When measuring the 29 Si-NMR spectrum of the particulate-linked organic-inorganic composite fine particles having a three-dimensional branched structure in the present invention, it is preferable to satisfy the following conditions. The ratio of the sum of the peak areas of Q2 and Q3 to the peak area of Q4 [(Q2 + Q3) / Q4)] is preferably in the range of 1.1 or more and 2.0 or less. Although this mechanism is not clear, the inventors presume that in the particle preparation process, the adsorption of the organic component to the silanol group inhibits the polycondensation reaction. As a result, when the value of [(Q2 + Q3) / Q4)] exceeds 1.1. That is, based on the above hypothesis and the fact that the particle-linked organic-inorganic composite fine particles of the present invention contain an organic component, since the value of [(Q2 + Q3) / Q4)] is within this range, it is presumed that polycondensation has not progressed inside the particle-linked organic-inorganic composite fine particles of the present invention as compared with conventionally known organic-inorganic composite fine particles. Since polycondensation has not progressed, it is presumed that the particle density of the particle-linked organic-inorganic composite fine particles of the present invention is relatively sparse. That is, the inventors presume that when used as abrasive grains, the number of particles increases, and more specifically, the contact area between the particle-linked organic-inorganic composite fine particles and the polishing substrate can be increased, and a high polishing rate can be obtained. Furthermore, since the particles contain an organic component inside, the particles become soft and are easily elastically deformed. As a result, the contact area with the substrate increases, so the polishing rate is improved. On the other hand, if it exceeds 2.0, the siloxane bond is insufficient and the strength of the particles is significantly reduced. Therefore, when used as abrasive grains, particle breakage occurs and the polishing performance deteriorates, which is not preferable.

[0043] [Average longest diameter (DLa) in the longitudinal direction of particle-linked organic-inorganic composite fine particles having a three-dimensional branched structure] The particle-linked organic-inorganic composite fine particles (three-dimensionally linked particles) having a three-dimensional branched structure in the present invention preferably satisfy the following requirement [4]. Requirement [4] 20 nm ≤ DLa ≤ 1,000 nm Here, the average longest diameter (DLa) in the longitudinal direction of the particle-linked organic-inorganic composite fine particles having a three-dimensional branched structure is the average value obtained by measuring the longest diameters (DL) of 50 particle-linked organic-inorganic composite fine particles having a three-dimensional branched structure. Specifically, for the particle-connected organic-inorganic composite microparticles having a three-dimensional branched structure, the longest diameter (DL) in the length direction is measured for 50 particles corresponding to the three-dimensional connected particles using a scanning electron microscope (200,000 times magnification) of an organic-inorganic composite microparticle dispersion (SiO2 concentration: 0.05% by mass), and the average value is calculated for each of the longest diameters (DL).

[0044] It is preferable that the average longest diameter (DLa) in the length direction of the three-dimensional connected particles is 20 nm or more and 1,000 nm or less, because an excellent polishing rate can be obtained. If the average longest diameter (DLa) in the length direction of the three-dimensional connected particles is less than 20 nm, a sufficient polishing rate may not be obtained, which is not preferable. Further, if the average longest diameter (DLa) in the length direction of the three-dimensional connected particles exceeds 1,000 nm, scratches are likely to occur on the polished substrate, which is not preferable. The longest diameter (DLa) in the length direction of the three-dimensional connected particles is more preferably 30 nm or more and 600 nm or less, and most preferably 50 nm or more and 600 nm or less.

[0045] [Average diameter (DTa) in the thickness direction of particle-connected organic-inorganic composite microparticles having a three-dimensional branched structure] The particle-connected organic-inorganic composite microparticles (three-dimensional connected particles) having a three-dimensional branched structure in the present invention preferably satisfy the following requirement [5]. Requirement [5] 10 nm ≤ DTa ≤ 800 nm Here, the average diameter DTa in the thickness direction of the particle-connected organic-inorganic composite microparticles (three-dimensional connected particles) having a three-dimensional branched structure refers to the value obtained by further averaging the average value of the maximum values (DTmax) in each particle for 50 three-dimensional connected particles ([the sum of DTmax for 50 three-dimensional connected particles] / 50). The three-dimensional connected particles have, in terms of their outer shape, at least two minimum values (DTmin) and maximum values (DTmax) in the thickness direction respectively. The thickness direction of the particle-connected organic-inorganic composite microparticles having a three-dimensional branched structure refers to the direction orthogonal to the longest diameter (DL) in the length direction. In the particle-connected organic-inorganic composite microparticles having a three-dimensional branched structure, the outer diameter DT in the thickness direction refers to the distance between two intersection points where the outer edge of the particle intersects with a line segment in the thickness direction. The "outer edge of the particle-connected organic-inorganic composite microparticles" refers to the contour of the particle-connected organic-inorganic composite microparticles when the particle-connected organic-inorganic composite microparticles are viewed in plan (photograph projection diagram) using a scanning microscope photograph (such as an SEM photograph). The outer diameter DT in the thickness direction of the particle-connected organic-inorganic composite microparticles having a three-dimensional branched structure is measured using a scanning electron microscope (200,000 times magnification).

[0046] It is preferable that the average diameter (DTa) in the thickness direction of the three-dimensional connected particles is 10 nm or more and 800 nm or less, as this causes no practical inconvenience. If the average diameter (DTa) in the thickness direction of the three-dimensional connected particles is less than 10 nm, it is accompanied by significant thickening of the dispersion liquid, resulting in handling inconvenience, so it is not preferable. Also, if the average diameter (DTa) in the thickness direction of the three-dimensional connected particles exceeds 800 nm, the sedimentation property of the particles increases, resulting in handling inconvenience, so it is not preferable. The average longest diameter (DTa) in the thickness direction of the three-dimensional connected particles is more preferably 20 nm or more and 600 nm or less. Even more preferably, it is 40 nm or more and 600 nm or less, and most preferably, it is 60 nm or more and 600 nm or less.

[0047] It is preferable that the average longest diameter (DLa) in the length direction of the particle-connected organic-inorganic composite microparticles having a three-dimensional branched structure in the present invention is in the range of 20 nm or more and 1000 nm or less, and the average diameter (DTa) in its thickness direction is in the range of 10 nm or more and 800 nm or less.

[0048] [Coefficient of variation (C.V.) of the diameter (DT) in the thickness direction of the particle-connected organic-inorganic composite microparticles having a three-dimensional branched structure] The particle-connected organic-inorganic composite microparticles (three-dimensional connected particles) having a three-dimensional branched structure in the present invention preferably satisfy the following requirement [6]. Requirement [6] 10% ≤ C.V. ≤ 40% The coefficient of variation and the average coefficient of variation (C.V.) of the diameter (DT) in the thickness direction of the particle-linked organic-inorganic composite fine particles having a three-dimensional branched structure are determined as follows. (1) Use the scanning electron microscope photograph used when obtaining the longest diameter DL in the particle-linked organic-inorganic composite fine particles having a three-dimensional branched structure. (2) Bisect the longest diameter DL, obtain two intersection points where the orthogonal line segments intersect the outer edge of the particle, and define the line segment connecting the two intersection points as DT. (3) Perform the measurement of (2) above for 50 arbitrarily selected three-dimensionally linked particles, and take their average value (total of 50 DT's / 50) as the average diameter DTa in the thickness direction. (4) Perform the measurement of (2) above for 50 arbitrarily selected three-dimensionally linked particles, determine the coefficient of variation for each value of DT of the 50 three-dimensionally linked particles, and take the averaged value as the average coefficient of variation (C.V.). It is preferable that the average coefficient of variation (C.V.) is in the range of 10% or more and 40% or less because a good polishing rate can be obtained. If the average coefficient of variation (C.V.) is less than 10%, the formation of branches is insufficient and the desired polishing characteristics cannot be obtained, so it is not preferable. Also, if the average coefficient of variation (C.V.) exceeds 40%, the contact between the particles and the substrate becomes non-uniform, so the desired polishing characteristics cannot be obtained, and the tendency for scratches to occur on the polishing substrate increases, which is not preferable. More preferably, the average coefficient of variation (C.V.) is in the range of 15% or more and 35% or less.

[0049] [Neck portion of the particle-linked organic-inorganic composite fine particles having a three-dimensional branched structure] In the three-dimensionally linked particles of the present invention, depending on the degree of silica reinforcement treatment such as a silicic acid solution after the generation of the three-dimensionally linked particles, there are differences in the neck portions formed between adjacent primary composite fine particles. Draw a straight line C that circumscribes both of the adjacent primary composite fine particles (p1) and primary composite fine particles (p2), obtain a line segment perpendicular to the straight line C from the joint portion of the primary composite fine particles (p1) and (p2), and define that line segment as the neck portion depth (L) [nm]. Define Ls, Lm, and F as follows. F: Average particle diameter of primary composite particles in three-dimensional linked particles (transmission electron microscope) L: Neck depth Ls: Average value of neck depth in the same three-dimensional linked particles Lm: Average value of neck depth in 50 three-dimensional linked particles At this time, Lm preferably satisfies the range represented by the following mathematical formula (2-1). 0 ≦ Lm ≦ F / 3 ··· (2-1) When Lm is within the above range, the neck between primary particles is sufficiently reinforced with silica, and even when receiving the load during polishing, the particle connection structure and three-dimensional structure are retained, so a high contact area between the particles and the polishing substrate can be obtained, and the desired polishing performance can be obtained. On the other hand, when the value of Lm is larger than the value of F / 3, that is, when the average value (Lm) of the neck depth is larger than one-third of the average particle diameter (F) of the primary composite particles, the neck depth between primary particles is not sufficiently reinforced with silica, and the structure of the three-dimensional linked particles may collapse due to the load during polishing, and the polishing rate may decrease. When Lm exceeds F / 2, it cannot be regarded as a particle connection state. Lm more preferably satisfies the range represented by the following mathematical formula (2-2), and even more preferably satisfies the range represented by the following mathematical formula (2-3). 0 < Lm < F / 6 ··· (2-2) 0 < Lm < F / 9 ··· (2-3)

[0050] [Coefficient of variation of the average neck depth (C.V.(Lm)) of particle-linked organic-inorganic composite microparticles having a three-dimensional branched structure] The particle-linked organic-inorganic composite microparticles (three-dimensional linked particles) having a three-dimensional branched structure in the present invention preferably satisfy the following requirements. 0% ≦ C.V.(Lm) ≦ 40% Here, C.V.(Lm) is the coefficient of variation among 50 three-dimensionally linked particles obtained by determining Ls for each particle as described above. It is more preferable that C.V.(Lm) is in the range of 0% or more and 35% or less, and even more preferable that it is in the range of 0% or more and 30% or less. When C.V.(Lm) is within the above range, neck reinforcement is uniform, particle disintegration during polishing can be suppressed, and the polishing rate becomes stable. When C.V.(Lm) exceeds 40%, that is, when the variation in the depth of the neck portion between particles is large, the contact area between each particle and the substrate may also vary, and thus the polishing rate may decrease or defects such as scratches may easily occur.

[0051] [Method for Measuring Neck Portion Depth] At an arbitrary location of the three-dimensionally linked particles, draw a straight line C that circumscribes both of the adjacent primary composite fine particles (p1) and primary composite fine particles (p2), and obtain a line segment perpendicular to the straight line C from the joint portion of the primary composite fine particles (p1) and (p2). Let that line segment be the neck portion depth (L) [nm]. At three arbitrary locations of the same three-dimensionally linked particles, obtain the above neck portion depth (L) [nm], and calculate their average value (Ls) [nm]. Perform this measurement and calculation for 50 three-dimensionally linked particles, and obtain their average value (Lm) [nm].

[0052] [Average Number of Linked Primary Composite Fine Particles in Particle-Linked Organic-Inorganic Composite Fine Particles Having a Three-Dimensional Branch Structure] The average number of linked primary composite fine particles in the three-dimensionally linked particles of the present invention is preferably in the range of 5 or more and 20 or less. If the average number of linked particles is less than 5, it is not preferable because a sufficient dynamic contact area cannot be obtained and thus a desired polishing rate cannot be achieved. Also, if the average number of linked particles exceeds 20, it becomes more in the form of an aggregate rather than a linked type, which may cause defects and is therefore not preferable. The average number of linked primary composite fine particles in the three-dimensionally linked particles of the present invention is more preferably in the range of 5 or more and 15 or less.

[0053] The average number of linked primary composite fine particles in the three-dimensional linked particles of the present invention is measured using a scanning electron micrograph (200,000 times magnification) of a three-dimensional linked particle dispersion liquid. Using a scanning electron micrograph, for each three-dimensional linked particle, the number of linked primary composite fine particles is counted visually. Then, the average value of the number of links of 50 three-dimensional linked particles is defined as the average number of links.

[0054] [Primary composite fine particles in particle-linked organic-inorganic composite fine particles having a three-dimensional branched structure] The average particle size range of the primary composite fine particles in the three-dimensional linked particles is the same as that of the primary composite fine particles in the linked particles. That is, the average particle size of the primary composite fine particles in the three-dimensional linked particles is preferably 5 nm or more and 600 nm or less, more preferably 20 nm or more and 400 nm or less, and even more preferably 60 nm or more and 300 nm or less. When the average particle size is less than 5 nm, the linked particles obtained by aggregation of primary particles tend to be in a lump shape. Also, in the case of polishing applications, it is not preferable because sufficient polishing speed cannot be obtained, presumably due to no stress concentration being obtained. When the average particle size exceeds 600 nm, for example, in polishing applications, the contact area decreases significantly, sometimes leading to a decrease in the polishing speed. Also, when the average particle size exceeds 600 nm, for example, scratches (linear marks) may occur on the polished surface.

[0055] [Particle-linked organic-inorganic composite fine particles (planar linked particles) other than particle-linked organic-inorganic composite fine particles (three-dimensional linked particles) having a three-dimensional branched structure] The planar linked particles of the present invention are particle-linked organic-inorganic composite fine particles (linked particles) other than particle-linked organic-inorganic composite fine particles (three-dimensional linked particles) having a three-dimensional branched structure. Therefore, particles in which two or more primary composite fine particles are linked and which are other than three-dimensional linked particles are included in the planar linked particles. For example, those in which two primary composite fine particles are linked are all included in the planar linked particles because a branched structure cannot be assumed. Further, the planar linked particles are not limited to those linked in a chain like the three-dimensional linked particles. For example, the planar linked particles include those in which some or all of the primary composite fine particles are linked in a ring in the structure of the linked particles.

[0056] [Organic-inorganic composite fine particles (single particles) other than the particle-linked type organic-inorganic composite fine particles (linked particles)] The organic-inorganic composite fine particles (single particles) other than the particle-linked type organic-inorganic composite fine particles (linked particles) of the present invention include those other than those in which two or more primary composite fine particles are linked. The organic-inorganic composite fine particles (single particles) mainly consist of unreacted primary composite fine particles in the primary composite fine particles used as reactants for generating the linked particles.

[0057] [Ratio of Ca, Mg and Al contained in the organic-inorganic composite fine particles of the particle-linked type organic-inorganic composite fine particle dispersion liquid] In the particle-linked type organic-inorganic composite fine particle dispersion liquid of the present invention, the ratios of Ca, Mg, Al and Fe contained in the organic-inorganic composite fine particles are preferably 25 ppm or less, 25 ppm or less, 150 ppm or less and 50 ppm or less, respectively. The content ratio of each element is expressed as the ratio of the mass of each element contained per unit mass of the organic-inorganic composite fine particles. The organic-inorganic composite fine particles of the particle-linked type organic-inorganic composite fine particle dispersion liquid of the present invention are primary composite fine particles or those bonded by silica. Therefore, for example, they do not contain a binder component such as CaO, MgO, Al2O3 or Fe2O3. Thus, when the particle-linked type organic-inorganic composite fine particle dispersion liquid containing the organic-inorganic composite fine particles of the present invention is applied to the polishing of semiconductor devices such as semiconductor substrates or wiring substrates, the problem of metal contamination caused by these binder components is less likely to occur. The Ca content in the organic-inorganic composite fine particles in the particle-linked type organic-inorganic composite fine particle dispersion liquid is more preferably 10 ppm or less, the Mg content is more preferably 10 ppm or less, the Al content is more preferably 100 ppm or less, and the Fe content is more preferably 30 ppm or less.

[0058] The particulate-linked organic-inorganic composite particulate dispersion of the present invention preferably contains 5 to 50% by number of three-dimensionally linked particles as the dispersed substance. The proportion by number of the three-dimensionally linked particles is preferably in the range of 5 to 50% by number. More preferably, it is in the range of 5 to 30% by number, and even more preferably, it is in the range of 5 to 25% by number. Also, the proportion of the planar-linked particles is preferably 50 to 95% by number.

[0059] When the proportion by number of the three-dimensionally linked particles is in the range of 5 to 50% by number, when the particulate-linked organic-inorganic composite particulate dispersion of the present invention is applied to polishing applications, it can effectively contribute to the increase in the polishing rate described above. When the proportion by number of the three-dimensionally linked particles is less than 5% by number, among the abrasive grains, since the proportion of the three-dimensionally linked particles having the three-dimensional structure is low, although the surface roughness of the substrate after polishing becomes low, the polishing rate also decreases. When the proportion by number of the three-dimensionally linked particles exceeds 50% by number, among the abrasive grains, the proportion of the three-dimensionally linked particles having the three-dimensional structure is excessive, and although the polishing rate increases, problems such as the generation of scratches on the polished substrate and the deterioration of the surface roughness are likely to occur. When the proportion by number of the three-dimensionally linked particles is 50% by number or less, single particles existing in excess of 50% and particles with low connectivity and planar-linked particles improve the roughness of the polished substrate, and the three-dimensionally linked particles of 50% or less exhibit a high polishing rate. Therefore, it is possible to balance the polishing rate and the surface roughness.

[0060] The percentage by number of the three-dimensionally linked particles is determined as follows. From a transmission microscope photograph (200,000 times magnification) of a linked particle dispersion liquid (solid content concentration: 0.05% by mass), 200 particles in at least a shape where the particles are linked are arbitrarily selected. Each of the 200 selected particles is classified as either a three-dimensionally linked particle or a planar-linked particle. Then, the value obtained by dividing the number of the three-dimensionally linked particles by 200 is taken as the percentage by number of the three-dimensionally linked particles.

[0061] In the particulate-linked organic-inorganic composite particulate dispersion of the present invention, the volume% of the three-dimensionally linked particles is preferably in the range of 40 to 95% by volume. When the volume ratio of the three-dimensional linked particles is in the range of 40% by volume or more and 95% by volume or less, when the particulate-linked organic-inorganic composite particle dispersion of the present invention is applied to polishing applications, it can effectively contribute to the increase in the polishing rate described above. When the volume ratio of the three-dimensional linked particles is less than 40% by volume, among the abrasive grains, the ratio of the three-dimensional linked particles having the three-dimensional structure is low, and the contribution to the increase in the polishing rate is also small. When the volume ratio of the three-dimensional linked particles exceeds 95% by volume, among the abrasive grains, the ratio of the three-dimensional linked particles having the three-dimensional structure is excessive, and although the polishing rate increases, problems such as the occurrence of scratches on the polishing substrate are likely to occur. The volume ratio of the three-dimensional linked particles is preferably 45% by volume or more and 90% by volume or less, more preferably 50% by volume or more and 86% by volume or less.

[0062] The method for obtaining the volume% (W) of the three-dimensional linked particles is as described below.

[0063] The particulate-linked organic-inorganic composite particle dispersion of the present invention may contain unlinked single particles within a range that does not significantly affect the effects of the invention, in addition to the three-dimensional linked particles and the planar linked particles. For example, when used as an abrasive grain, the ratio of the volume of the single particles to the volume of the particulate-linked organic-inorganic composite particles is desirably 55 (parts by volume) or less with respect to 100 (parts by volume) of the former. (Here, the volume of the particulate-linked organic-inorganic composite particles means the sum of the volume of the three-dimensional linked particles and the volume of the planar linked particles.) If the ratio of the volume of the single particles to the volume of the particulate-linked organic-inorganic composite particles is within the above range, the effects of the present invention will not be impaired. When the volume ratio of the single particles exceeds 55 (parts by volume), the ratio of the three-dimensional linked particles having the three-dimensional structure among the abrasive grains is relatively low. For example, the effect on the increase in the polishing rate is also less likely to occur. Also, the ratio of the number of single particles to the number of particle-linked organic-inorganic composite microparticles is desirably 210 (parts by number) or less with respect to 100 (parts by number) of the former. (Here, the number of particle-linked organic-inorganic composite microparticles means the sum of the number of three-dimensional linked particles and the number of planar linked particles.) If the ratio of the number of single particles to the number of particle-linked organic-inorganic composite microparticles is within the above range, the effects of the present invention will not be impaired. When the number ratio of the single particles exceeds 210 (parts by number), the proportion of the three-dimensional linked particles having the three-dimensional structure among the abrasive grains is relatively low. For example, it becomes difficult to produce an effect on the increase in the polishing rate.

[0064] The solid content concentration of the linked particle dispersion is preferably 2% by mass or more and 50% by mass or less. Within this range, sedimentation of particles over time is less likely to occur, and it can also be applied to storage or transportation. If it exceeds 50% by mass, aggregation of particles and accompanying sedimentation are likely to occur. Particularly when the linked particle dispersion is applied to polishing applications, such particle aggregation or sedimentation impairs the stability of the abrasive grain dispersion and may reduce the polishing rate and polishing efficiency. Also, in the container for storing the abrasive grain dispersion for polishing treatment or in the supply process, the abrasive grain dispersion adhering to the inner wall of the container or the supply device easily dries and becomes an aggregate, and may mix into the abrasive grain dispersion again to cause scratches during the polishing treatment. If it is less than 2% by mass, concentration is required when applying the linked particle dispersion to various applications, which is not practical. The solid content concentration is more preferably 5% by mass or more and 30% by mass or less. Here, the solid content concentration means the concentration of the dispersoid of the linked particle dispersion. Specifically, it is the concentration based on the mass of the organic-inorganic composite microparticles (linked particles (three-dimensional linked particles and planar linked particles)) and the total mass of the single particles.

[0065] Regarding the solvent or dispersion medium of the linked particle dispersion, it may be any of water, an organic solvent, or a mixed solvent thereof. Examples of the organic solvent include water-soluble organic solvents such as alcohols (methyl alcohol, ethyl alcohol, isopropyl alcohol, etc.), ethers, esters, and ketones.

[0066] [Method for Producing Particle-Linked Organic-Inorganic Composite Particle Dispersion Liquid] <Step 1> In Step 1, a cationic organic polymer component is added to a silica particle dispersion liquid (SiO2 concentration: 0.1 mass% or more and 30 mass% or less) within the range of the following ratio (WA / WS1), and then heated to 40°C or higher and 98°C or lower and held for 0.5 hours or longer to obtain a particle-linked organic-inorganic composite particle dispersion liquid. 0.002 ≦ WA / WS1 ≦ 0.3 (Here, WS1 is the mass (g) of silica in the silica particle dispersion liquid, and WA is the mass (g) of the cationic organic polymer component.)

[0067] The silica particle dispersion liquid used in Step 1 is one in which silica particles are dispersed in a dispersion medium. Examples of the dispersion medium include the solvent or dispersion medium of the linked particle dispersion liquid. The silica particles preferably have the same shape and the same average particle diameter as the primary composite particles in the linked particles. Also, the concentrations of Ca, Mg, Al, and Fe contained in the silica particles are preferably as follows in terms of the mass of Ca, Mg, Al, and Fe per unit mass of the silica particles. Ca: 25 ppm or less Mg: 25 ppm or less Al: 150 ppm or less Fe: 50 ppm or less

[0068] The SiO2 concentration of the silica particle dispersion liquid used in Step 1 is preferably 0.1 mass% or more and 30 mass% or less. When the SiO2 concentration of the organic-inorganic composite particle dispersion liquid is less than 0.1 mass%, the low SiO2 concentration affects and makes it difficult to form a linked structure of silica particles. Also, when the SiO2 concentration exceeds 30 mass%, the linking of silica particles occurs disorderly, and thus the structure of the particles tends to become uncontrollable. The SiO2 concentration of the organic-inorganic composite particle dispersion liquid used in Step 1 is more preferably in the range of 1 mass% or more and 18 mass% or less.

[0069] In the silica fine particle dispersion used in Step 1, the SiO2 / Na2O (molar ratio) is not restricted, and a material containing no Na may be used.

[0070] As a method for desalting in Step 1, a method of exchanging Na + ions with H + ions using a cation exchange resin can be mentioned. Examples of the cation exchange resin include a strongly acidic cation exchange resin or a weakly acidic cation exchange resin, and resins having a structure substituted with -SO3H or -COOH, etc. The pH of the silica fine particle dispersion used in Step 1 only needs to be such that the silica fine particle dispersion is stable and is not particularly restricted. The pH of the silica fine particle dispersion used in Step 1 may be 2 or more and 12 or less. pH adjustment can be performed, for example, by ion exchange of Na + ions.

[0071] The cationic organic polymer component used in Step 1 is added to the silica fine particle dispersion at a ratio of WA / WS1 of 0.002 or more and 0.3 or less (where WS1 is the mass (g) of silica in the silica fine particle dispersion and WA is the mass of the cationic organic polymer component). When a pH buffer or a pH adjuster is used within the above range of WA / WS1, three-dimensional linked particles and planar linked particles are likely to be generated due to the action of the buffer or the pH adjuster. When WA / WS1 is less than 0.002, it is difficult to generate planar linked particles and three-dimensional linked particles. Also, when WA / WS1 exceeds 0.3, the pH buffer becomes excessive, and particle aggregation is likely to occur, and massive particles are likely to be generated. WA / WS1 is more preferably 0.005 or more and 0.1 or less, and particularly preferably 0.01 or more and 0.05 or less.

[0072] The cationic organic polymer component is dissolved in water and used as an aqueous solution. This organic polymer component is as described above.

[0073] In the method for producing the particle-linked organic-inorganic composite particle dispersion of the present invention, it is preferable not to use a conventionally known inorganic flocculant. By using an organic polymer component, particularly an organic polymer component containing a cationic functional group, the charge on the surface of the organic-inorganic composite particles can be controlled. And particle-linked organic-inorganic composite particles having a desired morphology can be obtained without using an inorganic flocculant. Furthermore, compared with the organic-inorganic composite particles obtained by a conventionally known method, the content of metal impurities can be reduced, and it is particularly suitable for preventing contamination of a polishing substrate or a polishing apparatus in semiconductor polishing applications.

[0074] The inventors interpret the mechanism of the present invention as follows. In step 1 of the production method of the present invention, when a cationic organic polymer is added to the raw material silica particle dispersion at a predetermined ratio, and an alkali is added as necessary to adjust the pH to an optimum value and heated and held for a predetermined time, the organic polymer adsorbs on the entire or part of the surface of the negatively charged raw material silica particles. At this time, since an adsorption equilibrium of the organic polymer occurs, the total amount of the added organic polymer is not adsorbed on the raw material silica mother particles, and a part of it also exists in the solvent. Also, when an excessive amount of the organic polymer is added with respect to the specific surface area of the raw material silica particle dispersion, the organic polymer similarly exists in the solvent. Next, in step 2, an acidic silicic acid solution is added to this solution. The added acidic silicic acid solution deposits on the particle surface, but part or all of the particle surface is covered with the organic polymer, and silica covers the organic polymer layer. Therefore, the organic polymer is included inside the particles. When the organic polymer layer is covered with silica, the surface becomes strongly anionic again, so that the organic polymer remaining in the solvent begins to adsorb on the surface. Silica further deposits on the adsorbed organic polymer layer, and the surface becomes strongly anionic again. By repeating this, an organic-inorganic composite layer composed of silica and an organic polymer is formed on the silica mother particles. Also, the inventors presume that a concentration gradient of the organic polymer layer is generated by such a mechanism. Also, depending on the molecular weight and addition amount of the organic polymer, and conditions such as temperature and concentration, the adsorption amount of the cationic organic polymer adsorbed on the mother particles varies. When the adsorption amount of the cationic organic polymer is large, the surface potential of the particles may approach zero or become positively charged. In such cases, the dispersion stability of the particles cannot be maintained, and aggregation of the particles occurs. When the acidic silicic acid solution is further added in the aggregated state, silica is deposited on the surface of the particles, the aggregated primary particles are immobilized, and linked composite fine particles are formed. When the coating of silica on the aggregated primary particles progresses to a certain extent, the surface of the particles becomes a sufficiently stable anionic surface potential, so the aggregation of the particles stops. Also, since this aggregation progresses isotropically to a certain extent, three-dimensional linking progresses and a three-dimensional branched structure is formed. Furthermore, since the organic polymer is included inside the particles, in the organic-inorganic composite layer, the siloxane bond does not progress sufficiently, 29 When measuring the Si-NMR spectrum, the peak intensity ratio of Q2 and Q3 becomes larger compared to the particles without the organic-inorganic composite layer. Also, by adjusting conditions such as the addition amount of the organic polymer so that the particles have a surface potential that can maintain dispersibility even in the state where the organic polymer is adsorbed, and growing the particles with silicic acid, organic-inorganic composite fine particles in which the primary particles are not aggregated, that is, single-particle organic-inorganic composite fine particles can be obtained. Furthermore, by connecting these single-particle organic-inorganic composite fine particles by a known method, linked organic-inorganic composite fine particles can be obtained.

[0075] In step 2 of the production method of the present invention, by adding silicic acid under predetermined conditions to the particle-linked organic-inorganic composite fine particles having the above-mentioned branched and three-dimensional structures, particle growth proceeds while filling the necks between adjacent organic-inorganic composite fine particles. In the above-mentioned silicic acid addition treatment, a silica component is deposited on the organic polymer component adsorbed on the particle surface, and as a result, particle-linked organic-inorganic composite fine particles in which an organic component derived from the organic polymer component is included inside the particles are obtained. On the other hand, the adsorption of the organic polymer component present in the solvent proceeds on the particle surface during particle growth, resulting in an increase in the surface potential. Even during particle growth, the aggregation of the organic-inorganic composite particles proceeds, leading to secondary aggregation. Therefore, the particle-linked organic-inorganic composite particles of the present invention further promote the development of a branched and three-dimensional structure. Note that not all of the organic polymer components necessarily need to be encapsulated in the particle-linked organic-inorganic composite particles, and they may also exist in an adsorbed state on the particle surface.

[0076] In Step 1, a pH buffer and a pH adjuster may be used as necessary. As the pH buffer, it is desirable to use a known inorganic or organic pH buffer. Examples of the pH buffer include ammonium acetate, sodium acetate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate, and ammonium hydroxide. Among these, ammonium acetate or sodium acetate is particularly preferred.

[0077] Also, as the pH adjuster, it is desirable to use a known inorganic or organic pH adjuster. Examples of the pH adjuster include, as acids, acetic acid, formic acid, carbonic acid, hydrochloric acid, nitric acid, phosphoric acid, hypophosphorous acid, phosphorous acid, phosphonic acid, sulfuric acid, boric acid, hydrofluoric acid, orthophosphoric acid, pyrophosphoric acid, polyphosphoric acid, metaphosphoric acid, and hexametaphosphoric acid. Examples of the base include hydroxides of alkali metals such as potassium hydroxide, hydroxides of alkaline earth metals, and ammonia. Among these, sodium hydroxide, potassium hydroxide, or ammonia is preferred in terms of availability.

[0078] The pH before heating in Step 1 is preferably in the range of 9.0 or more and 13.0 or less.

[0079] [Treatment such as heating (generation of three-dimensional linked particles)] After adjusting to a predetermined pH with a pH buffer or a pH adjuster, it is preferably heated to 40°C or higher and 98°C or lower, and held for, for example, 0.5 hours or more and 64 hours or less. By heating, aggregation of inorganic fine particles adsorbed with a cationic organic polymer is promoted, and further, a bond by SiO2 is formed between adjacent inorganic fine particles to generate linked particles. If the heating temperature is less than 40°C, the linking reaction is difficult to promote and desired particle-linked silica particles cannot be obtained, which is not preferable. If the heating temperature exceeds 98°C, agglomerates are likely to be formed and desired particle-linked organic-inorganic composite fine particles cannot be obtained, which is not preferable. Also, if the holding time is less than 0.5 hours, the linking reaction does not proceed sufficiently, which is not preferable. Further, if the holding time exceeds 64 hours, the cost of the process becomes high and it is not economically preferable. In the present invention, for convenience, the particle-linked organic-inorganic composite fine particle dispersion obtained only through Step 1 is referred to as the particle-linked organic-inorganic composite fine particle dispersion (I), and the particle-linked organic-inorganic composite fine particle dispersion obtained through Step 1 and Step 2 may be referred to as the particle-linked organic-inorganic composite fine particle dispersion (II).

[0080] <Step 2> In the linked particles obtained in Step 1, a bond by SiO2 is formed between adjacent primary composite fine particles, but the bonded portion (hereinafter also referred to as "neck") is small and brittle. Therefore, it is preferable to grow the bonded portion and strengthen the bond between adjacent primary composite fine particles. Therefore, for the purpose of growing the neck portion, it is preferable to perform Step 2, which is a step of growing particles in particular, such as aging by heating or reinforcement by silica.

[0081] In Step 2, an acidic silicic acid solution is continuously or intermittently added to the particle-linked organic-inorganic composite fine particle dispersion obtained in Step 1 so as to have the following ratio (WF / WS2), and a treatment for growing the particles is performed. 0.01 ≦ WF / WS2 ≦ 20 (Here, WS2 is the mass (g) of silica in the particulate-connected organic-inorganic composite particle dispersion liquid, and WF is the mass (g) of silica in the acidic silicic acid solution.)

[0082] Before adding the acidic silicic acid solution, an alkaline component may be added as necessary. As the alkaline component, ammonia, water glass, etc. can be used. The alkaline component can also be used in solution form. Examples of the solvent for dissolving the alkaline component include the solvent or dispersion medium of the connected particle dispersion liquid. The solvent is preferably the dispersion medium used in Step 1, and more preferably water.) The SiO2 concentration of the particulate-connected organic-inorganic composite particle dispersion liquid in Step 2 is preferably 0.1% by mass or more and 30% by mass or less.)

[0083] In Step 2, the acidic silicic acid solution is added continuously or intermittently to the particulate-connected organic-inorganic composite particle dispersion liquid in the range where WF / WS2 is 0.01 or more and 20 or less.) When WF / WS2 is less than 0.01, the growth of the connected part of the particulate-connected organic-inorganic composite particles is insufficient, or the desired polishing characteristics cannot be obtained, which is not preferable. Also, when WF / WS2 exceeds 20, the shape of the obtained particulate-connected organic-inorganic composite particles may approach a spherical shape and may not maintain the connected shape, which is not preferable.) The temperature in Step 2 is the temperature at which the added acidic silicic acid solution dissolves and deposits on the particles, and is preferably 70°C or more and 98°C or less.) The addition of the acidic silicic acid solution in Step 2 can be performed continuously or intermittently.)

[0084] The acidic silicic acid solution is obtained by dissolving an alkali metal silicate (such as sodium silicate) in water and exchanging alkali metal ions with hydrogen ions. Examples of the method for exchanging alkali metal ions with hydrogen ions include using a cation exchange resin. The acidic silicic acid solution can be used as long as its pH is 6 or less. As the SiO2 concentration of the acidic silicic acid solution, those with a concentration of 1% by mass or more and 6% by mass or less can be used.) When the SiO2 concentration is less than 1% by mass, a large amount of acidic silicic acid solution needs to be added, which is not economically preferable. Also, when it is 6% by mass or more, since the acidic silicic acid solution itself is unstable, it is not preferable. The SiO2 concentration is more preferably 1% by mass or more and 5% by mass or less.

[0085] <Step 3> From the viewpoint of further growing the particles (especially the neck part in the particles), Step 3 may be further performed. Step 3 is a step of performing a pH adjustment treatment to pH 10.0 or more on the particle-linked organic-inorganic composite fine particle dispersion liquid that has been subjected to Step 2, and then continuously or intermittently adding an acidic silicic acid solution to perform a treatment for growing the particles. The operation of Step 3 is substantially the same as the operation of Step 2. For example, by further performing Step 3 on the particle-linked organic-inorganic composite fine particle dispersion liquid (II) obtained in Step 2, the linked particles can be further grown (especially the neck part can be grown). Note that Step 3 may be repeated a plurality of times from the above viewpoint.

[0086] [Abrasive grain dispersion liquid containing a particle-linked organic-inorganic composite fine particle dispersion liquid] The abrasive grain dispersion liquid (also referred to as "polishing composition") containing the linked particle dispersion liquid of the present invention may further contain other components. As other components, one or more components selected from a polishing accelerator, a surfactant, a hydrophilic compound, a heterocyclic compound, a pH adjuster, and a pH buffer can be used.

[0087] Examples of the polishing accelerator include acids such as sulfuric acid, nitric acid, phosphoric acid, oxalic acid, and hydrofluoric acid, or sodium salts, potassium salts, ammonium salts of these acids, and mixtures thereof. In the case of a polishing composition containing these polishing accelerators, when polishing a workpiece made of a composite component, by accelerating the polishing rate of a specific component of the workpiece, a finally flat polished surface can be obtained.

[0088] When the polishing composition according to the present invention contains a polishing accelerator, its content is preferably 0.1% by mass or more and 10% by mass or less, and more preferably 0.5% by mass or more and 5% by mass or less. In order to improve the dispersibility and stability of the surfactant and / or hydrophilic compound polishing composition, a cationic, anionic, nonionic, or amphoteric surfactant or hydrophilic compound can be added.

[0089] Both the surfactant and the hydrophilic compound have the effect of reducing the contact angle with the surface to be polished and promoting uniform polishing. As the surfactant and / or hydrophilic compound, for example, those selected from the following groups can be used.

[0090] Examples of the anionic surfactant include carboxylates, sulfonates, sulfate esters, and phosphate esters. Examples of the carboxylate include soap, N-acyl amino acid salts, polyoxyethylene or polyoxypropylene alkyl ether carboxylates, and acylated peptides. Examples of the sulfonate include alkyl sulfonates, alkyl benzene and alkyl naphthalene sulfonates, naphthalene sulfonates, sulfosuccinates, α-olefin sulfonates, and N-acyl sulfonates. Examples of the sulfate ester include sulfated oils, alkyl sulfates, alkyl ether sulfates, polyoxyethylene or polyoxypropylene alkyl allyl ether sulfates, and alkyl amide sulfates. Examples of the phosphate ester include alkyl phosphates, polyoxyethylene or polyoxypropylene alkyl allyl ether phosphates.

[0091] Examples of the cationic surfactant include aliphatic amine salts, aliphatic quaternary ammonium salts, benzalkonium chloride salts, benzethonium chloride, pyridinium salts, and imidazolinium salts. Examples of the amphoteric surfactant include carboxybetaine type, sulfobetaine type, aminocarboxylates, imidazolinium betaine, lecithin, and alkylamine oxides.

[0092] Examples of nonionic surfactants include ether type, ether ester type, ester type, and nitrogen-containing type. Examples of ether type surfactants include polyoxyethylene alkyl and alkylphenyl ethers, alkyl allyl formaldehyde condensed polyoxyethylene ethers, polyoxyethylene polyoxypropylene block polymers, and polyoxyethylene polyoxypropylene alkyl ethers. Examples of ether ester type surfactants include polyoxyethylene ethers of glycerin esters, polyoxyethylene ethers of sorbitan esters, and polyoxyethylene ethers of sorbitol esters. Examples of ester type surfactants include polyethylene glycol fatty acid esters, glycerin esters, polyglycerin esters, sorbitan esters, propylene glycol esters, sucrose esters. Examples of nitrogen-containing type surfactants include fatty acid alkanolamides, polyoxyethylene fatty acid amides, and polyoxyethylene alkyl amides. Other examples include fluorosurfactants and the like.

[0093] As the surfactant, an anionic surfactant or a nonionic surfactant is preferred. Examples of salts include ammonium salts, potassium salts, sodium salts, etc., and ammonium salts and potassium salts are particularly preferred.

[0094] Furthermore, as other surfactants, hydrophilic compounds, etc., esters (such as glycerin esters, sorbitan esters, and alanine ethyl esters), ethers (such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene glycol alkyl ether, polyethylene glycol alkenyl ether, alkyl polyethylene glycol, alkyl polyethylene glycol alkyl ether, alkyl polyethylene glycol alkenyl ether, alkenyl polyethylene glycol, alkenyl polyethylene glycol alkyl ether, alkenyl polyethylene glycol alkenyl ether, polypropylene glycol alkyl ether, polypropylene glycol alkenyl ether, alkyl polypropylene glycol, alkyl polypropylene glycol alkyl ether, alkyl polypropylene glycol alkenyl ether, and alkenyl polypropylene glycol), polysaccharides (such as alginic acid, pectic acid, carboxymethyl cellulose, curdlan, and pullulan), amino acid salts (such as glycine ammonium salt and glycine sodium salt), polycarboxylic acids and their salts (such as polyaspartic acid, polyglutamic acid, polylysine, polyapple acid, polymethacrylic acid, ammonium polymethacrylate, sodium polymethacrylate, polyamic acid, polymaleic acid, polyitaconic acid, polyfumaric acid, poly(p-styrenecarboxylic acid), polyacrylic acid, polyacrylamide, aminopolyacrylamide, ammonium polyacrylate, sodium polyacrylate, polyamic acid, ammonium polyamic acid, sodium polyamic acid, and polyglyoxylate), vinyl polymers (such as polyvinyl alcohol, polyvinyl pyrrolidone, and polyacrolein), sulfonic acids and their salts (such as ammonium methyl taurate, sodium methyl taurate, sodium methyl sulfate, ammonium ethyl sulfate, ammonium butyl sulfate, sodium vinyl sulfonate, sodium 1-allyl sulfonate, sodium 2-allyl sulfonate, sodium methoxymethyl sulfonate, ammonium ethoxymethyl sulfonate, sodium 3-ethoxypropyl sulfonate), and amides (such as propionamide, acrylamide,Examples include methylurea, nicotinamide, succinamide, and sulfanilamide, etc.

[0095] In addition, when the substrate to be polished is a glass substrate or the like, any surfactant can be preferably used. However, in the case of a silicon substrate for semiconductor integrated circuits or the like, when the influence of contamination by alkali metals, alkaline earth metals, halides, etc. is to be avoided, it is desirable to use an acid or an ammonium salt-based surfactant.

[0096] When the polishing composition according to the present invention contains a surfactant and / or a hydrophilic compound, the content thereof is preferably 0.001 g or more and 10 g or less, more preferably 0.01 g or more and 5 g or less, and particularly preferably 0.1 g or more and 3 g or less per 1 L of the polishing composition as the total amount.

[0097] The content of the surfactant and / or the hydrophilic compound is preferably 0.001 g or more per 1 L of the polishing composition in order to obtain a sufficient effect, and preferably 10 g or less from the viewpoint of preventing a decrease in the polishing rate.

[0098] Only one type of surfactant or hydrophilic compound may be used, or two or more types may be used, and different types can also be used in combination.

[0099] Regarding the polishing composition of the present invention, when the substrate to be polished contains a metal, a heterocyclic compound may be contained for the purpose of forming a passive layer or a dissolution-inhibiting layer on the metal to suppress the erosion of the substrate to be polished. Here, the "heterocyclic compound" is a compound having a heterocycle containing one or more heteroatoms. The heteroatom means an atom other than a carbon atom or a hydrogen atom. The heterocycle means a cyclic compound having at least one heteroatom. The heteroatom means only an atom that forms a constituent part of the ring system of the heterocycle, and does not mean an atom that is located outside the ring system, separated from the ring system by at least one non-conjugated single bond, or a part of a further substituent of the ring system. Preferred heteroatoms include, but are not limited to, a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom. As examples of the heterocyclic compound, imidazole, benzotriazole, benzothiazole, tetrazole, etc. can be used. More specifically, 1,2,3,4-tetrazole, 5-amino-1,2,3,4-tetrazole, 5-methyl-1,2,3,4-tetrazole, 1,2,3-triazole, 4-amino-1,2,3-triazole, 4,5-diamino-1,2,3-triazole, 1,2,4-triazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, etc. can be mentioned, but are not limited thereto.

[0100] Regarding the content when a heterocyclic compound is blended in the polishing composition according to the present invention, it is preferably 0.001% by mass or more and 1.0% by mass or less, more preferably 0.001% by mass or more and 0.7% by mass or less, and even more preferably 0.002% by mass or more and 0.4% by mass or less.

[0101] If necessary, such as to enhance the effects of the above additives, an acid or a base can be added to adjust the pH of the polishing composition.

[0102] When adjusting the polishing composition according to the present invention to pH 7 or higher, an alkaline pH adjuster is used. Desirably, amines such as sodium hydroxide, aqueous ammonia, ammonium carbonate, ethylamine, methylamine, triethylamine, and tetramethylamine are used.

[0103] When adjusting the polishing composition to a pH of less than 7, an acidic pH adjuster is used. For example, hydroxy acids such as lactic acid, citric acid, malic acid, tartaric acid, and glyceric acid are used.

[0104] A pH buffer may be used to keep the pH value of the polishing composition constant. As the pH buffer, for example, phosphates and borates such as ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium tetraborate tetrahydrate, or organic acids can be used.

[0105] For the polishing composition according to the present invention, a solvent can be used as necessary. Usually, water is used as the solvent, but alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol can be used as necessary, and other water-soluble organic solvents such as ethers, esters, and ketones can also be used. Further, a mixed solvent composed of water and an organic solvent may be used.

[0106] The concentration of the polishing particles in the polishing composition according to the present invention is preferably in the range of 0.5% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 30% by mass or less. When the concentration is less than 0.5% by mass, depending on the type of the substrate or the insulating film, the concentration may be too low and the polishing rate may be slow, resulting in a problem with productivity. When the concentration of the polishing particles exceeds 50% by mass, the stability of the abrasive becomes insufficient, the polishing rate and polishing efficiency do not further improve, and a dried product may be generated and adhered in the step of supplying the dispersion for the polishing treatment, which may cause scratches.

Examples

[0107] [Analysis methods used in Examples and Comparative Examples] Preferred embodiments of the present invention are described below. Unless otherwise specified, the measurement methods of various properties in the examples and comparative examples were carried out by the methods described below.

[0108] [1] Method for measuring average particle size by dynamic light scattering method The method for measuring the average particle size (D1) of particle-linked organic-inorganic composite fine particles by the dynamic light scattering method is as follows. The sample (dispersion containing particle-linked organic-inorganic composite fine particles) is diluted with 0.58% aqueous ammonia to adjust the silica concentration to 1% by mass, and measured using a laser particle analyzer (for example, particle size measuring device (1)). [Outline of particle size measuring device (1)] Manufactured by Otsuka Electronics Co., Ltd., model number "Zeta potential / particle size measurement system ELSZ-1000" (measurement principle: dynamic light scattering method, light source wavelength: 665.70 nm, temperature adjustment range: 10 to 90 °C, cell: 10 mm square plastic cell)

[0109] [2] Method for measuring the number of particle-linked organic-inorganic composite fine particles (three-dimensional linked particles) having a three-dimensional structure in a particle-linked organic-inorganic composite fine particle dispersion (linked particle dispersion) and method for calculating the number ratio 1. Preparation of measurement sample (1) The particle-linked organic-inorganic composite fine particle dispersion was concentrated or diluted with ion-exchanged water to a solid content concentration of 0.05% by mass. (2) After applying ultrasonic waves to the dispersion having a solid content concentration of 0.05% by mass in (1) above, 0.1 g of it was used as a photographing sample. 2. Method for measuring the number ratio of linked particles and three-dimensional linked particles (1) The sample prepared in 1. above was photographed at 200,000 times using a transmission electron microscope (manufactured by Hitachi, Ltd., ultra-high resolution scanning electron microscope, model number S-5500). (2) In the obtained photograph, at least 200 particles having a shape in which particles are linked were arbitrarily selected. (3) For these particles, three-dimensional linked particles were identified and the number of them was counted. The criteria for determining three-dimensional linked particles are as follows. That is, for specific particle-linked organic-inorganic composite microparticles, it is necessary to confirm whether the following requirements 1) to 3) are met. 1) The number of linked primary composite microparticles is 5 or more and forms a chain structure 2) Among the particles constituting the main chain, there is at least one branch (branch (a)) bonded to a particle other than the terminal particle. 3) It is possible to confirm a portion with a darker shade overlapping on the particle compared to other primary particles. Particle-linked organic-inorganic composite microparticles that meet the above requirements 1) to 3) have a branch (branch (b)) extending in the three-dimensional direction or a terminal (c) extending in the three-dimensional direction with respect to branch (a), and are regarded as having a three-dimensional structure and are defined as three-dimensional linked particles. (4) The percentage of the number of three-dimensional linked particles is the number of three-dimensional linked particles per 200 linked particles expressed as a percentage. (5) The volume percentage of three-dimensional linked particles is determined as follows. Using DLa and DTa, the average particle diameter DLT by image analysis method is obtained. DLT is expressed by the following formula. DLT = (DLa + DTa) / 2 Here, when the DLT (average particle diameter) of three-dimensional linked particles is DLTt, the DLT (average particle diameter) of planar linked particles is DLTp, the volume of three-dimensional linked particles is VLTt, and the volume of planar linked particles is VLTp, VLTt and VLTp are determined as follows, respectively. VLTt = Σ(DLTt / Dp) 3 × (percentage of the number of three-dimensional linked particles), VLTp = Σ(DLTp / Dp) 3 × (percentage of the number of planar linked particles), And from the obtained VLTt and VLTp, the volume percentage (W) of three-dimensional linked particles can be determined by the following formula. W = VLTt / (VLTp + VLTt) × 100 Here, Dp is the average particle diameter [nm] of single particles.

[0110] [3] Method for measuring the average number of links of three-dimensional linked particles 1. Method for Measuring Average Number of Linked Particles in Three-Dimensional Linked Particles (1) Prepare an electron micrograph measured in the same manner as [2] above. (2) Visually count the number of linked primary composite particles in the three-dimensional linked particles in the micrograph. (3) Perform the above (2) for 50 arbitrarily selected three-dimensional linked particles, and average the number of linked primary composite particles. This average value is defined as the average number of linked particles in the three-dimensional linked particles. 2. Method for Measuring Average Particle Diameter [F] of Primary Composite Particles in Three-Dimensional Linked Particles (1) Prepare an electron micrograph measured in the same manner as [2] above. (2) Measure the particle diameters of the primary composite particles in the three-dimensional linked particles in the micrograph, and obtain their average value. (3) Perform the above (2) for 50 arbitrarily selected three-dimensional linked particles, obtain the average value of the 50 measurements, and use this value as the average particle diameter [F]. Note that the measurement of planar linked particles is performed in the same manner as above.

[0111] [4] Method for Measuring Average Longest Diameter (DLa) in the Length Direction and Average Diameter (DTa) in the Thickness Direction of Particle-Linked Organic-Inorganic Composite Microspheres (Three-Dimensional Linked Particles) with a Three-Dimensional Branch Structure 1. Preparation of Measurement Sample and Photography Using a Scanning Electron Microscope (SEM) The preparation of the measurement sample and photography using an SEM were performed according to item 1. in the method for measuring the average number of linked particles in the three-dimensional linked particles in [2] above. 2. Method for Measuring Average Longest Diameter (DLa) in the Length Direction of Three-Dimensional Linked Particles (1) Using the electron micrograph used in [2] above, in the three-dimensional linked particles, define the length of the line segment connecting two points between the outer edges of the particles that has the longest length as the longest diameter (DL). (2) Perform the above (1) for 50 arbitrarily selected three-dimensional linked particles, and use their average value ([the sum of the DL values for each of the 50 three-dimensional linked particles] / 50) as the average longest diameter DLa in the length direction. 3. Method for Measuring Average Diameter (DTa) in the Thickness Direction of Three-Dimensional Linked Particles (1) In the above [2], using the electron micrographs used, in the three-dimensional linked particles, among the line segments connecting two points between the outer edges of the particles, the direction of the line segment with the longest length is defined as the length direction, and the direction orthogonal to it is defined as the thickness direction. (2) Obtain two intersection points where the line segment orthogonal to the DL intersects the outer edge of the particle, and the distance between the two intersection points, where the line segment is the longest, is defined as DT. (3) For 50 arbitrarily selected three-dimensional linked particles, perform the measurement in (2) above, and take the average value (total of 50 DT values / 50) as the average diameter DTa in the thickness direction. 4. For 50 arbitrarily selected three-dimensional linked particles, perform the measurement in (2) above, calculate the coefficient of variation for each DT value of the 50 three-dimensional linked particles, and take the average value of them as the average coefficient of variation (C.V.).

[0112] [5] Method for Measuring Particle Size in Terms of Specific Surface Area of Particle-Connected Organic-Inorganic Composite Fine Particles with a Three-Dimensional Branch Structure Measurement of Specific Surface Area and Average Particle Size by Na Titration Method 1) After collecting a sample corresponding to 1.5 g as SiO2 in a beaker, transfer it to a constant-temperature reaction tank (25 °C), and add pure water to make the liquid volume 90 mL. (The following operations were carried out in a constant-temperature reaction tank maintained at 25 °C.) 2) Add 0.1 mol / L hydrochloric acid to adjust the pH to 3.6. 3) Add 30 g of sodium chloride, dilute it to 150 mL with pure water, and stir for 10 minutes. 4) Set the pH electrode, and while stirring, dropwise add 0.1 mol / L aqueous sodium hydroxide solution to adjust the pH to 4.0. 5) Titrate the sample adjusted to pH 4.0 with 0.1 mol / L aqueous sodium hydroxide solution, record the titration volume and pH value in the range of pH 8.7 - 9.3 at four or more points. Let the titration volume of 0.1 mol / L aqueous sodium hydroxide solution be X and the pH value at that time be Y, and create a calibration curve. 6) Calculate the consumption V (mL) of 0.1 mol / L sodium hydroxide aqueous solution required from pH 4.0 to 9.0 per 1.5 g of SiO2 according to the following formula (2), and calculate the specific surface area SA [m 2 / g] according to formula (3) below. V = (A × f × 100 × 1.5) / (W × C) ··· (2) In the above formula, A: Titration volume (mL) of 0.1 mol / L sodium hydroxide aqueous solution required from pH 4.0 to 9.0 per 1.5 g of SiO2 f: Normality of 0.1 mol / L sodium hydroxide aqueous solution W: Sampling amount (g) C: SiO2 concentration (mass%) of the sample Each represents. SA = 29.0V - 28 ··· (3)

[0113] Also, the particle size D2 (nm) in terms of specific surface area is obtained from formula (4). Particle size D2 (nm) in terms of specific surface area = 6000 / (ρ SiO2 × SA) ··· (4) (Here, ρ SiO2 represents the density of silica particles, 2.2 [g / cm 3 .) Measurement of specific surface area and average particle size by BET method (nitrogen adsorption method) For a sample obtained by adjusting 50 mL of the particle - linked silica sol to pH 3.5 with HNO3, adding 40 mL of 1 - propanol, drying at 110 °C for 16 hours, grinding in a mortar, and firing at 500 °C for 1 hour in a muffle furnace, after grinding in a mortar, the sample was fired in a muffle furnace at 500 °C for 1 hour and used as a measurement sample. Then, using a specific surface area measuring device (manufactured by Yuasa Ionics, model number Multi - sorb 12), the specific surface area was calculated by the BET one - point method from the nitrogen adsorption amount using the nitrogen adsorption method (BET method). Specifically, 0.5 g of the sample was placed in a measurement cell, degassed at 300 °C for 20 minutes in a mixed gas stream of 30 v% nitrogen and 70 v% helium, and then the sample was maintained at liquid nitrogen temperature in the above mixed gas stream, and nitrogen was allowed to adsorb on the sample in equilibrium. Next, while flowing the above mixed gas, the sample temperature was gradually raised to room temperature, the amount of nitrogen desorbed during that time was detected, and the specific surface area of the particle-linked silica sol was calculated using a calibration curve prepared in advance. Further, the obtained specific surface area (SA) was substituted into the above formula (4) to determine the particle size d1 in terms of specific surface area.

[0114] [6] Method for measuring the content ratios of Ca, Mg, Al, and Fe 1. Preparation of sample 80 g of a particle-linked organic-inorganic composite fine particle dispersion adjusted to a solid content concentration of 20% by mass was used as the sample. 2. Method for measuring the content ratios of Ca, Mg, Al, and Fe (1) Weigh accurately about 1 g of the particle-linked organic-inorganic composite fine particle dispersion into a platinum dish. (2) To the above (1), add 3 mL of phosphoric acid, 5 mL of nitric acid, and 10 mL of hydrofluoric acid, and heat on a sand bath. (3) After drying to dryness, add a small amount of water and 50 mL of nitric acid to dissolve, transfer to a 100 mL volumetric flask, and add water to make up to 100 mL. (4) Next, the operation of taking 10 mL of aliquot from the solution made up to 100 mL into a 20 mL volumetric flask is repeated 5 times to obtain 5 aliquots of 10 mL. (5) Using this, measurement is carried out by the standard addition method with an ICP plasma emission spectrometer (manufactured by SII, model number SPS5520). (6) Measure the blank in the same way, subtract the blank value for adjustment, and use the measured values for each element. (7) From the above measured values, the mass ratios of each element (Ca, Mg, and Al) contained per unit mass of the organic-inorganic composite fine particles contained in the particle-linked organic-inorganic composite fine particle dispersion were determined.

[0115] [7] Method for measuring COD (chemical oxygen demand) when the particle-linked organic-inorganic composite fine particles are dissolved The oxygen consumption (COD) by potassium permanganate was measured according to the following procedure. An appropriate amount of the sample was taken into a 300 mL Erlenmeyer flask, water was added to make it 100 mL, 10 mL of sulfuric acid (1+2) (sulfuric acid 1: water 2 by volume ratio) was added, 5 mL of silver nitrate solution (200 g / L) was added and shaken well, then 10 mL of 5 mmol / L potassium permanganate solution was added, and the flask was placed in a boiling water bath and heated for 30 minutes. At this time, the surface of the boiling water bath was always above the sample surface. Next, 10 mL of sodium oxalate solution (12.5 mmol / L) was added, and while maintaining the temperature at 50 - 60 °C, back titration was carried out with 5 mmol / L potassium permanganate solution, and the point at which the color of the solution showed a light pink color was taken as the end point. Separately, a blank test using water was carried out under the same conditions. The mgO / L of the oxygen consumption by potassium permanganate was calculated by the following formula. COD=(a - b)×f×1000 / V×0.2 COD: Oxygen consumption by potassium permanganate (mgO / L) a: Volume of 5 mmol / L potassium permanganate solution required for titration (mL) b: Volume of 5 mmol potassium permanganate solution required for titration in the blank test (mL) f: Factor of 5 mmol / L potassium permanganate solution V: Sample volume (mL) 0.2: Oxygen equivalent amount (mg) of 1 mL of 5 mmol / L potassium permanganate solution

[0116] [8] For the particle - linked organic - inorganic composite microparticles 29 Measurement of Si - NMR spectrum 29 For the measurement of the Si CPMAS NMR spectrum, an Agilent VNMRS - 600 (14.1 T, 1 H resonance frequency: 600 MHz) was used. The measurement sample was ground using a mortar, filled into a 5 mm solid NMR sample tube so as to be uniform, and then rotated at 6 kHz at the magic angle (54.7°) with respect to the external magnetic field. At this time, 29The Si resonance frequency was 119.2 MHz, 1 The H 90° pulse width was 5.0 μs, the contact time was 7 ms, the waiting time after FID was 5 s, and the number of integrations of FID was about 10,000 times. The peak of polydimethylsilane at -34.44 ppm was used as the secondary standard of chemical shift, and the obtained spectrum was approximated with a Gaussian function using Origin for waveform separation. As described above, 29 The Si-NMR spectrum was measured, and from this spectrum, the peak intensities and peak areas of Q2, Q3, and Q4 were read. Then, the ratio of the peak intensity of Q3 to the peak intensity of Q4 (Q3 / Q4), and the ratio of the sum of the peak areas of Q2 and Q3 to the peak area of Q4 [(Q2 + Q3) / Q4)] were calculated.

[0117] [9] Confirmation of the presence of the mother particles, the organic-inorganic composite layer, and the outermost layer, and confirmation of the concentration gradient of the organic component in the organic-inorganic composite layer A silica sol with a known particle size in terms of specific surface area (particle size before dissolution) was diluted with 4.8% sodium hydroxide and adjusted to a SiO2 concentration of 5.0%. This solution was heated at 70 °C and held for 1 hour for dissolution treatment. The solution after the dissolution treatment was separated by an ultrafiltration membrane, and the silica concentration and COD in the separated liquid were analyzed. The particle size after dissolution was calculated based on the following formula. Particle size after dissolution = {(5.0 - silica concentration in the solution separated by the ultrafiltration membrane) / 5.0} 1 / 3 × particle size before dissolution The thickness of the dissolution layer can be calculated by subtracting the particle size after dissolution from the particle size before dissolution, and the thickness of the organic-inorganic composite layer was calculated based on the following formula. Thickness of the organic-inorganic composite layer = particle size before dissolution - (particle size of the mother particles + thickness of the outermost layer consisting only of inorganic components) Also, the thickness of the dissolution layer can be adjusted by adjusting the amount of sodium hydroxide added, the heating time, and the temperature in the dissolution treatment, and it can be dissolved in units of several nanometers. When the dissolution operation in units of several nm is repeated, first, when the thickness of the dissolution layer is small, the COD value is not detected in the dissolution solution, or is detected at an extremely low concentration. The layer where COD is not detected is the outermost layer composed of inorganic components. When dissolution is continued, COD is detected in the dissolution solution, and the thickness corresponding to the dissolution solution in which the COD value is detected is the organic-inorganic composite layer. Subsequently, when the dissolution treatment is repeated, the COD value contained in the dissolution solution gradually increases. When the COD concentration in the dissolution layer changes in this way, it is determined that there is a concentration gradient of the organic component. When the dissolution treatment is further continued, the COD value is no longer detected in the dissolution solution. The particle size after dissolution when the COD value is no longer detected is the mother particle size. More specifically, as shown in FIG. 2, by creating a graph showing the relationship between the distance from the center of the organic-inorganic composite fine particles and the COD value, the presence of the mother particles, the organic-inorganic composite layer, and the outermost layer can be confirmed. Looking from the side where the distance from the center of the fine particles is large, the portion where the COD value is not detected is the outermost layer. Next, the portion where the COD value is detected is the organic-inorganic composite layer. Then, the portion where the COD value is no longer detected is the mother particle. In addition, when the size of the raw material inorganic particles used for preparation as a raw material in advance during production is known, it shows a good match with the size of the raw material inorganic particles. When measuring the thickness of the organic-inorganic composite fine particles, the particle size in terms of specific surface area conversion shall be used.

[0118]

[10] Method for evaluating polishing characteristics of SiO2 insulating film (thickness 1 μm) substrate and method for preparing polishing abrasive dispersion [Preparation of polishing abrasive dispersion] For the particle-linked organic-inorganic composite fine particle dispersion or the organic-inorganic composite fine particle dispersion obtained in each of the examples and comparative examples, ion-exchanged water was added and diluted respectively, and the solid content concentration was adjusted to 1.0% by mass for all. A nitric acid aqueous solution (concentration 5%) was added to adjust the pH to 6.0, and a polishing abrasive dispersion was obtained. [Polishing test method] As the substrate to be polished, a SiO2 insulating film (thickness 1 μm) substrate prepared by a thermal oxidation method was prepared. This substrate to be polished was set in a polishing apparatus (manufactured by Nanofactor Co., Ltd., NF300), and a polishing pad (manufactured by Nitta Haas, "IC-1000 / SUBA400 concentric circle type") was used. The polishing abrasive grain dispersion liquid was supplied at a rate of 200 mL / min for 1 minute at a substrate load of 0.04 MPa and a table rotation speed of 90 rpm to perform polishing. Then, the weight change of the substrate to be polished before and after polishing was determined to calculate the polishing rate (nm / min). Also, the smoothness (surface roughness [Ra]) of the surface of the polishing substrate was measured using an atomic force microscope (AFM, manufactured by Hitachi High-Technologies Corporation). Since the smoothness and the surface roughness are generally in a proportional relationship, the surface roughness is described in the table.

[0119] [Average particle diameter of the inorganic fine particles used as raw materials] The method for measuring the average particle diameter of the inorganic fine particles in the inorganic fine particle dispersion liquid used as a raw material for producing the particle-linked organic-inorganic composite fine particle dispersion liquid of the present invention is as follows. [Measurement method] A sample prepared using an inorganic fine particle dispersion liquid (solid content concentration: 0.05 mass%) was photographed with a transmission electron microscope (magnification: 200,000 times). Using the photograph, 50 primary particles were arbitrarily selected. When each of the arbitrarily selected primary particles was projected in the photograph (plan view), for those that were circular, the diameter was taken as the particle diameter. Also, for primary particles other than circular, when projected in the photograph (plan view), for the distance between the outer edges of the particles, the average value of the longest and the shortest was taken as the particle diameter. For the 50 particles, the particle diameters were totaled and divided by the number of particles, and the average value was taken as the average particle diameter of silica.

[0120] [Acidic silicic acid solution] An aqueous sodium silicate solution (SiO2 concentration 5 mass%) was passed through a cation exchange resin column to prepare an acidic silicic acid solution (SiO2 concentration 4.6 mass%, pH 2.3, SiO2 / Na2O [molar ratio] = 1200). Hereinafter, in the examples and comparative examples, this acidic silicic acid solution was used.

[0121] <Preparation of Particle-Linked Organic-Inorganic Composite Particle Dispersion>

[0122] [Example 1] 124 g of a silica particle dispersion “Cataloid SI-50” (particle diameter in terms of specific surface area: 25 nm, solid content concentration: 48% by mass, manufactured by Nichi-Ei Shokubai Kasei Co., Ltd.) was diluted with pure water to a solid content concentration of 2.4% by mass. 71 g of an aqueous sodium hydroxide solution (concentration: 5.0% by mass) was added to this diluted silica particle dispersion as a pH adjuster. Next, 1500 g of an aqueous polyethyleneimine solution (concentration: 0.1% by mass, weight average molecular weight: 600) as a cationic organic polymer was added to this silica particle dispersion with adjusted pH. The pH after addition was 12.1. Subsequently, the silica particle dispersion containing this cationic organic polymer was heated to 98°C and held at 98°C for 30 minutes. Subsequently, 5518 g of an acidic silicic acid solution (SiO2 concentration: 4.6% by mass) was added over 16 hours. After the addition was completed, aging was carried out for 1 hour while maintaining the temperature. By this operation, particle growth was achieved, and at the same time, the neck portions between the primary particles were also grown. A particle-linked organic-inorganic composite particle dispersion (solid content concentration: 3.3% by mass) was obtained. It was confirmed that the obtained particle-linked organic-inorganic composite particle dispersion contained particle-linked organic-inorganic composite particles having a three-dimensional branched structure by the above measurement method. The proportion of the number of particle-linked organic-inorganic composite particles (three-dimensional linked particles) having a three-dimensional branched structure (three-dimensional branching structure) was 23%. This particle-linked organic-inorganic composite particle dispersion was concentrated with an ultrafiltration device to adjust the SiO2 concentration to 12%. Furthermore, this particle-linked organic-inorganic composite particle dispersion was concentrated with a rotary evaporator to adjust the SiO2 concentration to 40% by mass, and various measurements were carried out.

[0123] [Example 2] 83 g of a silica particle dispersion “Cataloid SI-50” was diluted with pure water to a solid content concentration of 1.9% by mass. 61 g of an aqueous sodium hydroxide solution (concentration: 5.0% by mass) was added to this diluted silica particle dispersion as a pH adjuster. Next, 360 g of an aqueous solution of polyethyleneimine with a weight average molecular weight of 600 (concentration: 0.3% by mass) as a cationic organic polymer was added to the silica fine particle dispersion with the adjusted pH. The pH after addition was 11.9. Subsequently, the silica fine particle dispersion containing the cationic organic polymer was heated to 98°C and held at 98°C for 120 minutes. Subsequently, 7,610 g of an acidic silicic acid solution (SiO2 concentration: 4.6% by mass) was added over 20 hours. After the addition was completed, aging was performed for 1 hour while maintaining the temperature. By this operation, particle growth was achieved, and the neck portions between the primary particles were also grown. A particle-linked organic-inorganic composite fine particle dispersion (solid content concentration: 3.8% by mass) was obtained. It was confirmed that the obtained particle-linked organic-inorganic composite fine particle dispersion contained particle-linked organic-inorganic composite fine particles having a three-dimensional branched structure by the above measurement method. The proportion of the number of particle-linked organic-inorganic composite fine particles having a three-dimensional branched structure (three-dimensional branched structure) was 23%. Concentration and various measurements of the obtained particle-linked organic-inorganic composite fine particle dispersion were carried out in the same manner as in Example 1.

[0124] [Example 3] 111 g of a silica fine particle dispersion “Cataloid SI-40” (particle diameter in terms of specific surface area: 18 nm, solid content concentration: 40.5% by mass, manufactured by Nichi-Ei Catalyst Kasei Co., Ltd.) was diluted with pure water to a solid content concentration of 1.9% by mass. 62 g of an aqueous sodium hydroxide solution (concentration: 5.0% by mass) was added to this diluted silica fine particle dispersion as a pH adjuster. Next, 375 g of an aqueous solution of polyethyleneimine with a weight average molecular weight of 600 (concentration: 0.3% by mass) as a cationic organic polymer was added to the silica fine particle dispersion with the adjusted pH. The pH after addition was 12.2. Subsequently, the silica fine particle dispersion containing the cationic organic polymer was heated to 98°C and held at 98°C for 120 minutes. Subsequently, 9,106 g of an acidic silicic acid solution (SiO2 concentration: 4.6% by mass) was added over 24 hours. After the addition was completed, aging was performed for 1 hour while maintaining the temperature. By this operation, particle growth was achieved, and the neck portions between the primary particles were also grown. A particle-linked organic-inorganic composite fine particle dispersion (solid content concentration: 3.9% by mass) was obtained. The obtained particulate-linked organic-inorganic composite particle dispersion was confirmed to contain particulate-linked organic-inorganic composite particles having a three-dimensional branched structure by the above measurement method. The proportion of the number of particulate-linked organic-inorganic composite particles having a three-dimensional branched structure (three-dimensional branched structure) was 42%. Concentration of the obtained particulate-linked organic-inorganic composite particle dispersion and various measurements were carried out in the same manner as in Example 1.

[0125] [Comparative Example 1] For the silica particle dispersion "Cataloid SI-50" (solid content concentration: 48% by mass, manufactured by Nichi-Kai Shokubai Kasei Co., Ltd.), various measurements were carried out in the same manner as in Example 1.

[0126] [Comparative Example 2] For the silica particle dispersion "Cataloid SI-45P" (particle diameter in terms of specific surface area: 45 nm, solid content concentration: 40.5% by mass, manufactured by Nichi-Kai Shokubai Kasei Co., Ltd.), various measurements were carried out in the same manner as in Example 1.

[0127] [Comparative Example 3] To 300 g of fumed silica (manufactured by Nippon Aerosil Co., Ltd., AEROSIL 50), ion-exchanged water and 5% sodium hydroxide were added, and the mixture was adjusted to a SiO2 concentration of 2.5% by mass at pH 10.0. Then, using zirconia beads with a diameter of φ0.5 mm, wet grinding was performed using a beads mill LMZ06 manufactured by Asazawa Fine Tech Co., Ltd. After separating the beads and the grinding liquid, wet grinding was further performed using high-purity silica beads with a diameter of φ0.25 mm. The obtained grinding liquid was concentrated to a SiO2 concentration of 40% by mass using a rotary evaporator to obtain a silica particle dispersion. For the obtained silica particle dispersion, various measurements were carried out in the same manner as in Example 1.

[0128] [Manufacturing Conditions and Results of Various Measurements] The manufacturing conditions in the examples are shown in Table 1. Also, the results of various measurements in the examples and comparative examples are shown in Table 2.

[0129]

Table 1

[0130]

Table 2

[0131] As is also clear from the results shown in Table 2, according to the particle-linked organic-inorganic composite particle dispersion liquids obtained in Examples 1 to 3, it was confirmed that they had excellent polishing properties.

Claims

1. An organic-inorganic composite particle dispersion liquid containing particle-linked organic-inorganic composite particles having a structure in which primary organic-inorganic composite particles are linked, where the primary organic-inorganic composite particles are organic-inorganic composite fine particles satisfying the requirements of the following [1], [2], [3], [A], [B], [C], [D], [4], [5], and [6] and having an average particle diameter (D1) measured by the dynamic light scattering method of 156 nm or more and 177 nm or less. [1] The organic-inorganic composite fine particles have a mother particle made of silica containing no organic component, and an organic-inorganic composite layer containing a cationic organic polymer component having a weight average molecular weight in the range of 300 or more and 100,000 or less on the surface of the mother particle. [2] The COD value per silica of the organic-inorganic composite fine particles is 300 ppm or more and 5% or less. [3] The thickness of the organic-inorganic composite layer is 31 nm or more and 45 nm or less. [A] In the cationic organic polymer component in the organic-inorganic composite layer, the concentration of the organic component decreases from the center of the particle toward the outside. [B] The outermost layer consisting only of silica is further provided on the surface of the organic-inorganic composite layer. [C] The particle-linked organic-inorganic composite particles include particle-linked organic-inorganic composite particles having a three-dimensional branched structure and particle-linked organic-inorganic composite particles other than particle-linked organic-inorganic composite particles having a three-dimensional branched structure. [D] The particle-linked organic-inorganic composite particles having a three-dimensional branched structure are contained in an amount of 5% by number or more and 50% by number or less. [4] 85 nm ≤ DLa ≤ 144 nm DLa: The average value of the longest diameter (DL) in the longitudinal direction of the particle-linked organic-inorganic composite particles having a three-dimensional branched structure. [5] 54 nm ≤ DTa ≤ 94 nm DTa: The average value of the diameter (DT) in the thickness direction of the particle-linked organic-inorganic composite particles having a three-dimensional branched structure. [6] 15% ≤ C.V. ≤ 18% C.V.: The average coefficient of variation of the diameter (DT) in the thickness direction of the particle-linked organic-inorganic composite particles having a three-dimensional branched structure.

2. An organic-inorganic composite particle dispersion liquid in which particle-linked organic-inorganic composite particles satisfying the requirements of the following [1A], [2], [3], [B], [C], [D], [4], [5], and [6] and having an average particle diameter (D1) measured by the dynamic light scattering method of 156 nm or more and 177 nm or less are dispersed in a solvent. [1A] The particle-linked organic-inorganic composite fine particles are formed by linking primary organic-inorganic composite fine particles having a mother particle made of silica containing no organic component and an organic-inorganic composite layer containing a cationic organic polymer component having a weight average molecular weight in the range of 300 or more and 100,000 or less on the surface of the mother particle, or by linking mother particles made of silica containing no organic component, and having an organic-inorganic composite layer containing a cationic organic polymer component having a weight average molecular weight in the range of 300 or more and 100,000 or less on the surface of the linked mother particles. [2] The particle-linked organic-inorganic composite fine particles have a COD value per silica of 300 ppm or more and 5% or less. [3] The thickness of the organic-inorganic composite layer is 31 nm or more and 45 nm or less. [B] The surface of the organic-inorganic composite layer further has an outermost layer made of only silica. [C] The particle-linked organic-inorganic composite fine particles are composed of particle-linked organic-inorganic composite fine particles having a three-dimensional branched structure and particle-linked organic-inorganic composite fine particles other than the particle-linked organic-inorganic composite fine particles having a three-dimensional branched structure. [D] The particle-linked organic-inorganic composite fine particles having a three-dimensional branched structure are contained in an amount of 5% by number or more and 50% by number or less. [4] 85 nm ≤ DLa ≤ 144 nm DLa: The average value of the longest diameter (DL) in the length direction of the particle-linked organic-inorganic composite fine particles having a three-dimensional branched structure [5] 54 nm ≤ DTa ≤ 94 nm DTa: The average value of the diameter (DT) in the thickness direction of the particle-linked organic-inorganic composite fine particles having a three-dimensional branched structure [6] 15% ≤ C.V. ≤ 18% C.V.: The average coefficient of variation of the diameter (DT) in the thickness direction of the particle-linked organic-inorganic composite fine particles having a three-dimensional branched structure

3. The cationic organic polymer component is at least one selected from the group consisting of poly(diethylaminoethyl methacrylate), poly(dimethyldiallylammonium chloride), polyalkyleneimine, and those in which these organic polymer compounds are provided with an imino group, an amino group or a cyano group. The organic-inorganic composite fine particle dispersion liquid according to Claim 1 or Claim 2.

4. The particle-linked organic-inorganic composite fine particles have at least one branched structure and further have a three-dimensional branched structure with respect to the branched structure. The organic-inorganic composite fine particle dispersion liquid according to Claim 1 or Claim 2.

5. The organic-inorganic composite particle dispersion liquid according to claim 4, wherein the three-dimensional branched structure is at least one of the following structures (1) and (2). (1) A branch (b) extending in a three-dimensional direction with respect to the branch (a). (2) A terminal (c) extending in a three-dimensional direction with respect to the branch (a).

6. When the ２９ Si-NMR spectrum of the particle-linked organic-inorganic composite microparticles is measured, the ratio ((Q2 + Q3) / Q4) of the peak intensity of Q3 to the peak intensity of Q4 is in the range of 1.0 or more and 2.0 or less. The organic-inorganic composite microparticle dispersion liquid according to any one of claims 1 to 5.

7. The organic-inorganic composite particle dispersion liquid according to any one of claims 1 to 6, wherein the average number of connections of the primary organic-inorganic composite particles having the three-dimensional branched structure is in the range of 5 or more and 20 or less.

8. The organic-inorganic composite particle dispersion liquid according to any one of claims 1 to 7, wherein the ratios of Ca, Mg, Fe, and Al contained in the organic-inorganic composite particles are as follows. Ca: 25 ppm or less Mg: 25 ppm or less Al: 150 ppm or less Fe: 50 ppm or less

9. An abrasive grain dispersion liquid containing the organic-inorganic composite particle dispersion liquid according to any one of claims 1 to 8.

10. A method for producing the organic-inorganic composite particle dispersion liquid according to claim 1 or claim 2, including the following step 1 and step 2. Step 1: SiO ２ To a silica particle dispersion having a concentration of 0.1% by mass or more and 30% by mass or less, a cationic organic polymer component having a weight average molecular weight in the range of 300 or more and 100,000 or less is added in the following ratio (WA / WS １ ), the pH is adjusted to be in the range of 9.0 or more and 13.0 or less, and then heated to 40°C or more and 98°C or less and held for 0.5 hours or more and 64 hours or less to obtain a particle-linked type organic-inorganic composite particle dispersion. 0.01 ≤ WA / WS １ ≤ 0.05 (Here, WS １ is the mass of silica in the silica particle dispersion, and WA is the mass of the cationic organic polymer component.) Step 2: The particulate-connected organic-inorganic composite particle dispersion obtained in Step 1 is held in the range of 70°C or higher and 98°C or lower, and an acidic silicic acid solution is continuously or intermittently added so as to have the following ratio (WF / WS ２ ), and a process of growing the particles is performed 0.01 ≤ WF / WS ２ ≤ 20 (Here, WS ２ is the silica mass in the particulate-linked organic-inorganic composite particle dispersion liquid, WF (wherein is the silica mass in the acidic silicic acid solution.)

11. The method for producing an organic-inorganic composite particle dispersion liquid according to claim 10, wherein the cationic organic polymer component is at least one selected from the group consisting of poly(diethylaminoethyl methacrylate), poly(dimethyldiallylammonium chloride), polyalkyleneimine, and those in which these organic polymer compounds are provided with an imino group, an amino group, or a cyano group.

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