Diblock copolymers, methods of making diblock copolymers, and uses of diblock copolymers

Abstract

The present invention provides a surface treatment agent for powder which imparts a dispersion excellent in dispersibility, fluidity, and stability over time, and a dispersion containing a powder treated with the surface treatment agent for powder. A diblock copolymer which constitutes a main chain of a silicone graft copolymer block represented by formula [I] and a polar copolymer block represented by formula [II], a terminal structure at one end of the main chain is a structure represented by formula [III], and a terminal structure at the other end of the main chain is a structure represented by formula [IV]. (In the formulae, R 1 represents a hydrogen atom or a methyl group, A represents a group containing an organopolysiloxane, n 1 represents 1 ≤ n 1 ≤ 50, B represents a monovalent hydrocarbon group having a carbon atom number of 1 to 20 having a polar group, an amino group, or a hydroxyl group, n 2 represents 1 ≤ n 2 ≤ 50, R 6 represents an alkyl group having a carbon atom number of 1 to 4, R 7 independently represents a hydrogen atom or an alkyl group having a carbon atom number of 1 to 4, and X represents a group represented by A in formula [I] or B in formula [II]).

Description

Technical Field

[0001] This invention relates to surface treatment agents for powders that exhibit excellent dispersibility, flowability, and storage stability, and particularly to surface treatment agents for powders based on organosilicon diblock copolymers of (meth)acrylic acid. Background Technology

[0002] Typically, agglomeration occurs due to the charge, polarity, and trace impurities inherent in powders, hindering dispersibility and stability. Consequently, it is difficult to stably and at high concentrations disperse microparticle powders in liquids. For example, dispersions containing pigments with fine particles exhibit significant viscosity increases over time, making product transport difficult and sometimes resulting in gelation that renders them unusable.

[0003] Methods for improving the dispersion stability of microparticle powders include mixing using mechanical forces such as homogeneous mixers, grinders, kneaders, and rolling mills. However, dispersion by mechanical force alone is limited; even if uniform dispersion is achieved initially, agglomeration often occurs over time. Therefore, to improve the dispersibility and stability of powders, a scheme has been proposed to treat the powder surface with various polymer materials. These polymer materials possess both adsorption sites on the powder and sites with high affinity for the solvent, which serves as the dispersion medium, and the performance of the polymer material is determined by the balance between these two functional sites.

[0004] Polymer materials that are effective for dispersing powders in solvents are typically AB-type copolymers or BAB-type copolymers, and these polymer materials can impart dispersions to powders used in various compositions. As polymer materials, AB block copolymers having polar groups such as acids or amines that integrate with the surface of the powder pigment are frequently used, and Patent Document 1 shows an example of block copolymerization of an acrylic resin having carboxyl groups.

[0005] In addition, AB block copolymers, BAB block copolymers, or ABC block copolymers are also known for dispersing powder pigments in inks.

[0006] However, while these block copolymers are effective in improving powder precipitation and agglomeration, their effects are not yet sufficient. Furthermore, due to differences in processing methods and agents, there are also drawbacks such as thickening of the dispersion over time, powder agglomeration and precipitation, and damage to product quality.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Patent Application Publication No. 2005-194487 Summary of the Invention

[0010] The problem the invention aims to solve

[0011] Therefore, the object of the present invention is to provide a copolymer that is useful as a surface treatment agent for powders, imparting excellent dispersibility, flowability, and stability over time. Furthermore, the object of the present invention is to provide a dispersion that is highly dispersed using this surface treatment agent for powders.

[0012] Problem Solving Methods

[0013] The inventors conducted in-depth research to achieve the above objectives and discovered that a diblock copolymer containing hydrophobic organosilicon graft copolymer blocks and polar copolymer blocks with specific polar groups as functional groups can solve the above problems, thus completing the present invention.

[0014] Therefore, the present invention provides a diblock copolymer containing an organosilicon graft copolymer block (segment [I]) represented by the following formula [I] and a (meth)acrylic acid copolymer block (segment [II]) represented by the following formula [II], wherein one end of the end structure of the main chain is represented by the following formula [III] and the other end of the end structure is represented by the following formula [IV].

[0015] <1>

[0016] A diblock copolymer, wherein the main chain of the diblock copolymer is composed of organosilicon graft copolymer blocks represented by formula [I] and polar copolymer blocks represented by formula [II].

[0017] The end structure at one end of the main chain is represented by the following formula [III], and the end structure at the other end is represented by the following formula [IV].

[0018]

[0019] (in equation [I],

[0020] R 1 It can be a hydrogen atom or a methyl group.

[0021] A is a group containing an organopolysiloxane, represented by the following general formula (1) or a group containing an organopolysiloxane, represented by the following general formula (2).

[0022] n 1 The number representing the repeating unit, where 1 ≤ n 1 ≤50.

[0023]

[0024] (The groups containing organopolysiloxanes represented by general formula (1) have a linear organopolysiloxane structure with a repeating unit number m of 0 to 100,

[0025] In general formula (1),

[0026] Z represents a divalent organic group.

[0027] R 2 Each can be independently represented as a saturated hydrocarbon group or phenyl group with 1 to 10 carbon atoms.

[0028] R 3 Represented as a saturated hydrocarbon group with 1 to 10 carbon atoms.

[0029] m represents a number between 0 and 100.

[0030] -OL i (2)

[0031]

[0032] (The groups containing organopolysiloxanes represented by general formula (2) have a dendritic organopolysiloxane structure with a hierarchical number c of 1 to 10,

[0033] In general formulas (2) and (3), i represents the number of each level of the dendritic structure, which is an integer from 1 to c.

[0034] In general formula (2),

[0035] L i The silyl organic group is represented by general formula (3), where i is 1.

[0036] In general formula (3),

[0037] Z represents a divalent organic group.

[0038] R 4 Represented as a saturated hydrocarbon group or phenyl group with 1 to 10 carbon atoms.

[0039] R 5 Each can be independently represented as an alkyl or phenyl group having 1 to 8 carbon atoms.

[0040] L i+1 When level i is less than c (below the top level), it is a silyl organic group L represented by general formula (3). i L i +1 At level i = c (top level), it consists of hydrogen atoms, saturated hydrocarbon groups with 1 to 10 carbon atoms, or phenyl groups.

[0041] a i Represented as OR in level i4 The number of functional groups is in the range of 0 to 3.

[0042]

[0043] (in equation [II],

[0044] R 1 Represented as a hydrogen atom or a methyl group,

[0045] B represents any group selected from -OB', -NH2, and -OH, n 2 Let n be a number of repeating units, where 1 ≤ n. 2 ≤50, where B' represents a monovalent hydrocarbon group having one or more divalent groups selected from polyoxyalkylene, -C(O)-, -O-, -S-, and -NR- with 1 to 20 carbon atoms, and R in -NR- represents a hydrogen atom or a monovalent hydrocarbon group with 1 to 20 carbon atoms.

[0046]

[0047] (in equation [III],

[0048] R 6 It is represented as an alkyl group having 1 to 4 carbon atoms.

[0049] R 7 (These can be independently represented as alkyl groups having 1 to 4 hydrogen atoms or carbon atoms.)

[0050]

[0051] (in equation [IV],

[0052] R 1 It can be a hydrogen atom or a methyl group.

[0053] X represents a group represented by A in formula [I] or B in formula [II].

[0054] <2>

[0055] According to the diblock copolymer described in <1>, wherein,

[0056] In formula [II], B is a group represented by general formula (8') or general formula (9').

[0057] -O-CH2-CH2-N(R 7 )2 (8')

[0058]

[0059] (In equation (8'), R)7 Each can be independently represented as an alkyl group having 1 to 4 hydrogen atoms or carbon atoms.

[0060] In equation (9'), R 3 Represented as a saturated hydrocarbon group with 1 to 10 carbon atoms, n 3 This represents the number of repeating units, where 1 ≤ n. 3 ≤10.

[0061] <3>

[0062] According to the diblock copolymer described in <1> or <2>, wherein,

[0063] The divalent organic group represented by Z in general formula (2) and general formula (3) is a saturated hydrocarbon group with 2 to 12 carbon atoms.

[0064] <4>

[0065] The diblock copolymer according to any one of <1> to <3>, wherein...

[0066] n 2 / n 1 The range is 0.02 to 10.

[0067] <5>

[0068] The method for manufacturing a diblock copolymer according to any one of <1> to <4>, wherein,

[0069] The compound represented by general formula (4) is used as the initiator, and has

[0070] The process of group transfer polymerization of monomers represented by general formula (5), and

[0071] Group transfer polymerization is a process involving polar monomers represented by general formula (6).

[0072]

[0073] (In general formula (4),

[0074] R 6 Each can be independently represented as an alkyl group having 1 to 4 carbon atoms.

[0075] R 7 (These can be independently represented as alkyl groups having 1 to 4 hydrogen atoms or carbon atoms.)

[0076]

[0077] (In general formula (5),

[0078] R 1 Represented as a hydrogen atom or a methyl group,

[0079] A represents a group containing an organopolysiloxane, represented by general formula (1) or a group containing an organopolysiloxane, represented by general formula (2).

[0080]

[0081] (The groups containing organopolysiloxanes represented by general formula (1) have a linear organopolysiloxane structure with a repeating unit number m of 0 to 100,

[0082] In general formula (1),

[0083] Z represents a divalent organic group.

[0084] R 2 Each can be independently represented as a saturated hydrocarbon group or phenyl group with 1 to 10 carbon atoms.

[0085] R 3 Represented as a saturated hydrocarbon group with 1 to 10 carbon atoms.

[0086] m represents a number between 0 and 100.

[0087] OL i (2)

[0088]

[0089] (The groups containing organopolysiloxanes represented by general formula (2) have a dendritic organopolysiloxane structure with a hierarchical number c of 1 to 10,

[0090] In general formulas (2) and (3), i represents the number of each level of the dendritic structure, and is an integer from 1 to c.

[0091] In general formula (2),

[0092] L i The silyl organic group is represented by general formula (3), and i is 1.

[0093] In general formula (3),

[0094] Z represents a divalent organic group.

[0095] R 4 It is represented as a saturated hydrocarbon group or phenyl group with 1 to 10 carbon atoms.

[0096] R 5 Each can be independently represented as an alkyl or phenyl group having 1 to 8 carbon atoms.

[0097] When level i is less than c (below the top level), L i+1L is a silyl organic group represented by general formula (3). i When level i = c (top level), L i+1 It consists of a saturated hydrocarbon group or a phenyl group with 1 to 10 carbon atoms, containing hydrogen atoms.

[0098] a i Represented as OR in level i 4 The number of functional groups, and the number is in the range of 0 to 3.

[0099]

[0100] (In general formula (6),

[0101] R 1 To represent a hydrogen atom or a methyl group, B is any group selected from -OB', -NH2, and -OH, wherein B' represents a monovalent hydrocarbon group having one or more divalent groups selected from polyoxyalkylene, -C(O)-, -O-, -S-, and -NR- having 1 to 20 carbon atoms, and R in -NR- represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.

[0102] <6>

[0103] According to the method for manufacturing the diblock copolymer described in <5>, wherein,

[0104] The polar monomer represented by general formula (6) is the polar monomer represented by the following general formula (8) or general formula (9).

[0105]

[0106] (In general formula (8),

[0107] R 1 Represented as a hydrogen atom or a methyl group,

[0108] R 7 (These can be independently represented as alkyl groups having 1 to 4 hydrogen atoms or carbon atoms.)

[0109]

[0110] (In general formula (9),

[0111] R 1 Represented as a hydrogen atom or a methyl group,

[0112] R 3 Represented as a saturated hydrocarbon group with 1 to 10 carbon atoms.

[0113] n 3 Let n be a number of repeating units, where 1 ≤ n. 3≤10.

[0114] <7>

[0115] According to the method for manufacturing the diblock copolymer described in <6>, wherein,

[0116] The polar monomer represented by general formula (8) is the polar monomer represented by the following formula (8-1).

[0117]

[0118] <8>

[0119] A surface treatment agent for powders, wherein,

[0120] A diblock copolymer comprising any one of <1> to <4>.

[0121] <9>

[0122] A dispersion, wherein,

[0123] It includes powders and oils treated with the surface treatment agent for powders described in <8>.

[0124] <10>

[0125] A cosmetic composition, coating composition, or ink composition, wherein,

[0126] It includes the dispersion described in <9>.

[0127] The effects of the invention

[0128] The diblock copolymer of the present invention comprises a hydrophobic organosilicon graft copolymer block (segment [I]) and a polar copolymer block (segment [II]) having specific polar groups as functional groups. The diblock copolymer of the present invention can be used as a surface treatment agent for powders, enabling effective and uniform dispersion of powders in an oil. Specifically, when this diblock copolymer is used as a surface treatment agent for powders, the polar groups interact with the powder surface, thereby improving the compatibility of the organosilicon portion with the oil and preventing powder agglomeration. Therefore, a dispersion with excellent dispersibility, flowability, and long-term stability can be obtained. Detailed Implementation

[0129] The present invention will now be described in detail. Furthermore, the term "(meth)acrylic acid" as used in this specification refers to methacrylic acid and acrylic acid. Similarly, the term "(meth)acrylate" as used in this specification refers to methacrylate and acrylate.

[0130] [Diblock copolymer]

[0131] The diblock copolymer of the present invention has an organosilicon graft copolymer block unit (segment [I]) represented by the following formula [I] and a polar copolymer block unit (segment [II]) represented by the following formula [II] on the main chain, the end structure of one end of the main chain is the structure represented by the following formula [III], and the end structure of the other end is the structure represented by the following formula [IV].

[0132] Chain segment [I]

[0133]

[0134] In equation [I], R 1 It is a hydrogen atom or a methyl group. A is a group containing an organopolysiloxane represented by the following general formula (1) or a group containing an organopolysiloxane represented by the following general formula (2). 1 The number of repeating units is 1 to 50, preferably 1 to 20, and more preferably 3 to 10.

[0135] The group containing organopolysiloxane represented by general formula (1) is a group with a linear organopolysiloxane structure having a repeating number m of 0 to 100 of two organosiloxy groups.

[0136]

[0137] In general formula (1), Z is a divalent organic group, preferably a saturated hydrocarbon group with 2 to 12 carbon atoms, and more preferably a propylene group. 2 Each group is independently a saturated hydrocarbon group or phenyl group having 1 to 10 carbon atoms, preferably a saturated hydrocarbon group having 1 to 5 carbon atoms, and more preferably a methyl group. R 3 It is a saturated hydrocarbon group with 1 to 10 carbon atoms, preferably a saturated hydrocarbon group with 1 to 5 carbon atoms, and more preferably a methyl group. m is a number from 0 to 100, preferably a number from 1 to 60, and more preferably a number from 5 to 30.

[0138] The group containing organopolysiloxane represented by general formula (2) is a group with a dendritic branch structure, and the number of its branch structure (number of levels c) is an integer from 1 to 10, preferably an integer from 1 to 6, and more preferably an integer from 1 to 4.

[0139] -OL i (2)

[0140]

[0141] In general formulas (2) and (3), i represents the number of each level of the dendritic structure, which is an integer from 1 to c.

[0142] In general formula (2), L iThe silyl organic group represented by general formula (3) has a level i of 1 in general formula (2).

[0143] In general formula (3), Z is a divalent organic group, preferably a saturated hydrocarbon group with 2 to 12 carbon atoms, and more preferably a propylene group. 4 It is a saturated hydrocarbon group or phenyl group having 1 to 10 carbon atoms, preferably a saturated hydrocarbon group having 1 to 5 carbon atoms, and more preferably a methyl group. R 5 It is an alkyl or phenyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. i +1 When level i is less than c (below the top level), it is a silyl organic group L represented by general formula (3). i When L i+1 At level i = c (the top level), it is a saturated hydrocarbon group or phenyl group with 1 to 10 carbon atoms, consisting of hydrogen atoms. L at level i = c (the top level) i Preferably, it is a saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a saturated hydrocarbon group having 1 to 4 carbon atoms. i Represented as OR in level i 4 The number of groups, and the number is in the range of 0 to 3.

[0144] A dendritic organopolysiloxane with a layer number of 1 (c=1) is represented by the following general formula (3-1), where L in the formula 2 It consists of a saturated hydrocarbon group or phenyl group with 1 to 10 hydrogen atoms and carbon atoms.

[0145]

[0146] A dendritic organopolysiloxane with 2 levels (c=2) is represented by the following general formula (3-2), where L... 3 It consists of a saturated hydrocarbon group or phenyl group with 1 to 10 hydrogen atoms and carbon atoms.

[0147]

[0148] A dendritic organopolysiloxane with 3 levels (c=3) is represented by the following general formula (3-3), where L... 4 It consists of a saturated hydrocarbon group or phenyl group with 1 to 10 hydrogen atoms and carbon atoms.

[0149]

[0150] In general formulas (3-1) to (3-3), Z and R 4 and R 5 The same as above, a 1 a 2 and a 3The numbers are in the range of 0 to 3.

[0151] Chain segment [II]

[0152]

[0153] In equation [II], R 1 B is a hydrogen atom or a methyl group. B is a group selected from -OB', -NH2, and -OH (B' represents a monovalent hydrocarbon group having one or more divalent groups selected from polyoxyalkylene, -C(O)-, -O-, -S-, and -NR- (R represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms), preferably a group represented by general formula (8') or general formula (9'). Additionally, n 2 The number of repeating units is 1 to 50, preferably 1 to 20, and more preferably 3 to 10.

[0154] -O-CH2-CH2-N(R 7 )2 (8')

[0155]

[0156] (In equation (8'), R) 7 Independently represented as hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, in formula (9'), R 3 Represented as a saturated hydrocarbon group with 1 to 10 carbon atoms, n 3 Let n be a number of repeating units, where 1 ≤ n. 3 ≤10.

[0157] End structure [III]

[0158]

[0159] In equation [III], R 6 It is an alkyl group having 1 to 4 carbon atoms, preferably a methyl group. R 7 Each of the elements is independently composed of a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a methyl group.

[0160] End structure [IV]

[0161]

[0162] In equation [IV], R 1 It is a hydrogen atom or a methyl group. X represents a group represented by A in formula [I] or B in formula [II].

[0163] The chain segment [I] and chain segment [II] may each be composed of at least one unit represented by formula [I] or a unit represented by formula [II], or may be composed of multiple units represented by formula [I] or multiple units represented by formula [II]. Furthermore, the chain segment [I] and chain segment [II] sandwiched between the aforementioned end structure [III] and end structure [IV] are random.

[0164] In this invention, a diblock copolymer refers to a copolymer that links two segments [I] and [II] with different physical properties, such as polarity, water solubility, and affinity for powders. That is, the diblock copolymer of this invention is a copolymer in which segments [I] are formed by attaching units represented by formula [I], segments [II] are formed by attaching units represented by formula [II], and these segments are linked together. When segments [I] are formed by multiple units represented by formula [I], segments [I] may have a block structure consisting of units of the same type represented by formula [I], or a random structure consisting of randomly arranged units represented by different types of formula [I]. Similarly, when segments [II] are formed by multiple units represented by formula [II], segments [II] may have a block structure consisting of units of the same type represented by formula [II], or a random structure consisting of randomly arranged units represented by different types of formula [II].

[0165] The molecular weight of the diblock copolymer of the present invention is preferably 1,000 to 100,000, more preferably 2,000 to 10,000. Furthermore, the polydispersity of the diblock copolymer of the present invention is preferably 1.00 to 3.00, more preferably 1.00 to 2.00, and even more preferably 1.05 to 1.60. If the molecular weight and polydispersity are within the above ranges, when the diblock copolymer of the present invention is used as a dispersant, the hydrophilic segment [II] can have a high adsorption capacity to the powder surface, while the hydrophobic segment [I] can also be well compatible with the oiling agent, thereby effectively dispersing the powder, which is therefore preferred.

[0166] In addition, the number of repeating units in each of the chain segment [I] and chain segment [II] is 1 to 50, preferably 1 to 20, and more preferably 3 to 10.

[0167] The ratio of the number of repeating units in segment [I] to the number of repeating units in segment [II], i.e., the degree of aggregation n of segment [I]. 1 Degree of polymerization n with chain segment [II] 2 The ratio of n 2 / n 1 The preferred value is 0.02 to 10, and more preferably 0.05 to 5.

[0168] It should be noted that the molecular weight in this invention refers to the number-average molecular weight of polystyrene as a standard substance, which will be determined by gel permeation chromatography (GPC) under the following conditions.

[0169] [Measurement Conditions]

[0170] Measuring instrument: HLC-8320GPC (manufactured by Tosoh Corporation, Japan)

[0171] Development solvent: Tetrahydrofuran (THF)

[0172] Flow rate: 0.600 mL / min

[0173] Detector: Differential Refractive Index Detector (RI)

[0174] Column: TSK Guardcolumn SuperH-H

[0175] (4.6mm I.D. × 35mm)

[0176] TSKgel Super H2500

[0177] (Particle size of filler: 3.0μm, 6mm I.D. × 150mm)

[0178] TSKgel Super HM-N

[0179] (Particle size of filler: 3.0μm, 6mm I.D. × 150mm)

[0180] (All manufactured by Tosoh Corporation of Japan)

[0181] Column temperature: 40℃

[0182] Sample injection volume: 50 μL (0.3% by mass THF solution)

[0183] [Method for manufacturing diblock copolymers]

[0184] Using a compound represented by the following general formula (4) as an initiator, the diblock copolymer of the present invention can be manufactured by a method having a step of group transfer polymerization of a monomer represented by general formula (5) and a step of group transfer polymerization of a polar monomer represented by general formula (6). That is, using a compound represented by general formula (4) as an initiator, the diblock copolymer of the present invention can be synthesized by sequentially group transfer polymerization of a monomer represented by general formula (5) and a polar monomer represented by general formula (6), and is a diblock copolymer regardless of the order of group transfer polymerization of the monomer represented by general formula (5) and the polar monomer represented by general formula (6).

[0185]

[0186] In general formula (4), R 6 Each is independently represented as an alkyl group having 1 to 4 carbon atoms, R 7 They are independently represented as alkyl groups having 1 to 4 hydrogen atoms or carbon atoms.

[0187]

[0188] In general formula (5), R 1 As shown in equation [I] above.

[0189]

[0190] In general formula (6), R 1 And B is as shown in equation [II] above.

[0191] As an initiator represented by general formula (4), the following compounds can be used, for example. However, the initiators that can be used in the method for manufacturing the diblock copolymer of the present invention are not limited to the initiators exemplified below.

[0192]

[0193] In the formula, Me represents methyl, Et represents ethyl, nPr represents n-propyl, iPr represents isopropyl, and nBu represents n-butyl.

[0194] As a monomer represented by general formula (5), for example, the following monomers can be used. However, the monomers that can be used in the method for manufacturing the diblock copolymer of the present invention are not limited to the monomers exemplified below.

[0195] In the case where A in general formula (5) is a group containing an organopolysiloxane as represented by general formula (1),

[0196]

[0197] In the case where A in general formula (5) is a group containing an organopolysiloxane, represented by general formula (2).

[0198]

[0199] As a polar monomer represented by general formula (6), for example, the following monomers can be used, but the polar monomers that can be used in the method for manufacturing the diblock copolymer of the present invention are not limited to the polar monomers exemplified below.

[0200] Specifically, examples include tetrahydrofurfuryl (meth)acrylate, di(ethylene glycol) monomethyl ether (meth)acrylate, furfuryl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-(methoxyethoxy)ethyl (meth)acrylate, allyloxyethyl (meth)acrylate, 1-ethoxybutyl (meth)acrylate, tetrahydro-4H-pyrano-2-(meth)acrylate, ethyltriethylene glycol (meth)acrylate, butyl diethylene glycol (meth)acrylate, poly(propylene glycol) dimethyl ether (meth)acrylate, and (meth)acrylate. Alkylene-substituted (meth)acrylates such as poly(ethylene glycol) alkyl ethers; aminoalkyl (meth)acrylates such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; (meth)acrylamide, 4-(meth)acryloylmorpholine, N-tert-butyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-(butoxymethyl)(meth)acrylamide, N-[3-(dimethylamino)propyl] (meth)acrylamide, N-dodecyl (meth)acrylamide, N-isopropyl (meth)acrylamide, etc. (meth)acrylamide, etc.

[0201] As a polar monomer represented by general formula (6), it is preferred to be a polar monomer represented by general formula (8) or general formula (9) below.

[0202]

[0203] In general formula (8), R 1 It is a hydrogen atom or a methyl group, preferably a methyl group. R 7 The atoms are independently hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, preferably methyl and ethyl.

[0204]

[0205] In general formula (9), R 1 It is a hydrogen atom or a methyl group, preferably a methyl group. R 3 It is a saturated hydrocarbon group having 1 to 10 carbon atoms, preferably a saturated hydrocarbon group having 1 to 5 carbon atoms, and more preferably a methyl group. 3 Let n be a number of repeating units, where 1 ≤ n. 3 ≤10, preferably 2≤n 3 ≤8.

[0206] As a polar monomer represented by general formula (6), 2-(dimethylamino)ethyl methacrylate represented by formula (8-1) is particularly preferred.

[0207]

[0208] In the method for manufacturing the diblock copolymer of the present invention, group transfer polymerization is carried out in the following two steps. In the first step, polymerization is carried out on either a monomer represented by general formula (5) or a polar monomer represented by general formula (6) (hereinafter, the monomer polymerized in the first step will be referred to as the first monomer). Next, in the second step, polymerization is carried out on another monomer (hereinafter, the monomer polymerized in the second step will be referred to as the second monomer) that has not been polymerized in the first step, between the monomer represented by general formula (5) and the polar monomer represented by general formula (6).

[0209] In step 1, the polymerization of the first monomer is initiated by pre-mixing two of the three components—the compound represented by general formula (4) as the initiator, the catalyst, and the first monomer—and then adding the remaining component to the pre-mixed mixture of the two components.

[0210] Next, after confirming that the polymerization reaction of the first monomer has stopped, the polymerization of the second monomer is started by adding the second monomer to the reaction system.

[0211] After confirming that the polymerization reaction of the second monomer has stopped, a reaction terminator is added to end the reaction.

[0212] After the reaction is complete, the product is purified by conventional methods such as vacuum distillation to remove solvent and unreacted monomers, thereby obtaining a diblock copolymer of the target material.

[0213] In the group transfer polymerization reactions of steps 1 and 2 above, a solvent is preferably used.

[0214] As a more specific example of a manufacturing method, the following methods can be listed.

[0215] The catalyst was added to a thoroughly dried three-necked flask, along with a solvent. Further, after adding and mixing the initiator represented by the above general formula (4), the first monomer was added dropwise using a dropping funnel while stirring. The reaction solution was cooled according to the degree of heating, and the temperature was maintained appropriately. After the first monomer was added dropwise, the mixture was stirred until the first monomer was consumed. The cessation of the polymerization reaction of the first monomer was confirmed by confirming the increase in molecular weight depending on the charge ratio of the initiator and the first monomer using gel permeation chromatography (GPC) analysis, etc. Next, the second monomer was added dropwise to the reaction system while stirring. The reaction solution was cooled according to the degree of heating, and the temperature was maintained appropriately. After the second monomer was added dropwise, the mixture was stirred until the added second monomer was consumed, and finally, a reaction terminator was added to end the reaction. After the reaction was completed, the mixture was purified by conventional methods, such as vacuum distillation, to remove the solvent and unreacted monomers, thereby obtaining the diblock copolymer of the target compound.

[0216] As the reaction solvent, aprotic organic solvents can be used. Examples include ethyl acetate, propionitrile, toluene, xylene, bromobenzene, dimethoxyethane, diethoxyethane, diethyl ether, tetramethylene sulfone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, anisole, 2-butoxyethoxytrimethylsilane, acetic acid cellosol, crown ether, acetonitrile, and tetrahydrofuran (THF). From the viewpoint of reaction efficiency, dichloromethane, toluene, acetonitrile, and tetrahydrofuran are preferred, and tetrahydrofuran is more preferred.

[0217] The reaction temperature for the group transfer polymerization reaction is -100℃ to 150℃, preferably 0℃ to 50℃, and more preferably 10℃ to 30℃.

[0218] The temperature for removing the solvent and unreacted monomers by vacuum distillation is 80°C to 300°C, preferably 100°C to 200°C, and more preferably 120°C to 180°C. Furthermore, the pressure during stripping is 1 atm or less, preferably 0.1 atm or less, and more preferably 0.007 atm or less.

[0219] As a catalyst, it can typically be selected from anionic catalysts, Lewis acid catalysts, and organic molecular catalysts known as catalysts for group transfer polymerization.

[0220] Examples of anionic catalysts include tris(dimethylamino)sulfonium difluorotrimethylsilicate, tris(dimethylamino)cyanosulfonium, tetraphenylcyanide, tris(dimethylamino)azonium, tetraethylammonium azide, bis(dialkylaluminum) oxide, boron trifluoride ether, alkali metal fluorides, alkali metal cyanides, alkali metal azides, tris(dimethylamino)sulfonium difluorotriphenylstannate, tetrabutylammonium fluoride, tetramethylammonium fluoride, tetraethylammonium cyanide, tetrabutylammonium benzoate, tetrabutylbibenzoate, and tetrabutylm-chlorobenzoate.

[0221] Examples of Lewis acid catalysts include zinc iodide, zinc bromide, zinc chloride, monoalkyl aluminum halides and dialkyl aluminum halides, as well as dialkyl aluminum oxides.

[0222] Examples of organic molecular catalysts include, for instance, 1,3-diisopropyl-4,5-dimethylimidazol-2-ylene, 1,3-diisopropylimidazol-2-ylene, 1,3-di-tert-butylimidazol-2-ylene, 1,8-diazabicyclo[5.4.0]-7-undecene, 2,8,9-trimethyl-2,5,8,9-tetraaza-1-phosphabicyclo[3.3.3]undecane, 2,8,9-triisobutyl-2,5,8,9-tetraaza-1-phosphabicyclo[3.3.3]undecane, and 1-tert-butyl-2,2,4,4,4-penta(dimethylamino)-2λ5 ,4λ 5 -di(phosphazene), 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)-phosphine-2λ]-2λ 5 ,4λ 5 -Di(phosphazene), tris(2,4,6-trimethoxyphenyl)phosphine, tri-(pentafluorophenyl)borane, triethylsilyl trifluoromethanesulfonate, triphenylcarbazide tetra(pentafluorophenyl)borate, trifluoromethanesulfonylimide, 1-[bis(trifluoromethanesulfonyl)methyl]-2,3,4,5,6-pentafluorobenzene.

[0223] As a reaction terminator, a compound capable of donating a proton is used. Examples include methanol, isopropanol, n-butanol, and water.

[0224] [Surface treatment agent for powders]

[0225] The diblock copolymer of the present invention can be suitably used as a surface treatment agent for powders, capable of effectively and uniformly dispersing the powder in an oil. There is no particular limitation on the powder; examples include commonly used inorganic powders, organic powders, surfactant metal salt powders, colored pigments, pearlescent pigments, metallic powder pigments, tar pigments, and natural pigments.

[0226] Specific examples of inorganic powders include titanium dioxide, zirconium oxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate, calcium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc, mica, kaolin, sericite, muscovite, synthetic mica, phlogopite, red mica, biotite, lepidolite, silicic acid, silicic anhydride, aluminum silicate, magnesium silicate, magnesium aluminum silicate, calcium silicate, barium silicate, strontium silicate, tungstate metal salts, hydroxyapatite, vermiculite, aluminum hydroxide, bentonite, montmorillonite, lithium montmorillonite, zeolite, ceramic powder, calcium hydrogen phosphate, alumina, aluminum hydroxide, boron nitride, boron nitride, silicon dioxide, hydrophobic silicon dioxide, and silanized silicon dioxide, etc.

[0227] Examples of organic powders include polyamide powder, polyacrylic acid / acrylate powder, polyester powder, polyethylene powder, polypropylene powder, polystyrene powder, polyurethane powder, benzoguanamine powder, polymethylbenzoguanamine powder, tetrafluoroethylene powder, polymethyl methacrylate powder, cellulose powder, silk powder, 12 nylon powder, and 6 nylon powder; cross-linked spherical dimethyl polysiloxane micro powder with a cross-linked dimethyl polysiloxane structure, cross-linked spherical polymethyl silsesquioxane micro powder, and micro powders made by coating the surface of cross-linked spherical organic polysiloxane rubber with polymethyl silsesquioxane particles; powders of various resins such as styrene-acrylic acid copolymer, divinylbenzene-styrene copolymer, vinyl resin, urea-formaldehyde resin, phenolic resin, fluororesin, silicone resin, acrylic resin, melamine resin, epoxy resin, and polycarbonate resin; microcrystalline fiber powder, starch powder, fatty acid starch derivative powder, and lauroyl lysine powder, etc.

[0228] Examples of surfactant metal salt powders (metal soaps) include zinc undecenoate, aluminum isostearate, zinc stearate, aluminum stearate, calcium stearate, magnesium stearate, zinc myristate, magnesium myristate, zinc hexadecyl phosphate, calcium hexadecyl phosphate, sodium hexadecyl phosphate, zinc palmitate, aluminum palmitate, and zinc laurate.

[0229] Specific examples of colored pigments include inorganic red pigments such as iron oxide, iron hydroxide, and iron titanate; inorganic brown pigments such as γ-iron oxide; inorganic yellow pigments such as yellow iron oxide and loess; inorganic black pigments such as black iron oxide and carbon black; inorganic purple pigments such as manganese violet and cobalt violet; inorganic green pigments such as chromium hydroxide, chromium oxide, cobalt oxide, and cobalt titanate; inorganic blue pigments such as dark blue and ultramarine; pigments made by lake treatment of tar pigments; pigments made by lake treatment of natural pigments; and synthetic resin powders made by combining these powders.

[0230] Specific examples of pearlescent pigments include titanium oxide-coated mica, titanium oxide-coated mica, bismuth oxychloride, titanium oxide-coated bismuth oxychloride, titanium oxide-coated talc, fish scale foil, and titanium oxide-coated colored mica; examples of metallic powder pigments include aluminum powder, copper powder, and stainless steel powder.

[0231] As tar pigments, examples include Red No. 3, Red No. 104, Red No. 106, Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 227, Red No. 228, Red No. 230, Red No. 401, Red No. 505, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Yellow No. 204, Yellow No. 401, Blue No. 1, Blue No. 2, Blue No. 201, Blue No. 404, Green No. 3, Green No. 201, Green No. 204, Green No. 205, Orange No. 201, Orange No. 203, Orange No. 204, Orange No. 206, Orange No. 207, etc.; as natural pigments, examples include carmine acid, shellac acid, safflower pigment, brassicatinol, crocin, etc.

[0232] Among these powders, at least a portion of the powders used for surface treatment of the diblock copolymers of the present invention are preferably cross-linked spherical dimethyl polysiloxane micro powders, cross-linked spherical polymethyl silsesquioxane micro powders, micro powders formed by coating the surface of cross-linked spherical polysiloxane rubber with polymethyl silsesquioxane particles, micro powders formed by coating the surface of cross-linked spherical diphenyl polysiloxane rubber with polymethyl silsesquioxane particles, hydrophobic silica, and fluororesins and pigments may also be used.

[0233] Commercially available products containing these preferred powders include KMP-590, KSP-100, KSP-101, KSP-102, KSP-105, and KSP-300 (all manufactured by Shin-Etsu Chemical Co., Ltd., Japan).

[0234] Within the scope that does not impair the effects of the present invention, these powders can be composite powders or powders treated with common oils, silicone oils, fluorinated compounds, surfactants, etc. For example, they can also be pre-treated with fluorinated compounds, silicone resins, draping treatments, silane coupling agents, titanium coupling agents, oils, N-acylated lysine, polyacrylic acid, metal soaps, amino acids, inorganic compounds, plasma treatments, and mechanochemical treatments. One or more of the above can be used as needed.

[0235] Surface treatment methods

[0236] There are no particular limitations on the method of applying the diblock copolymer of the present invention, which is used as a surface treatment agent for powder, to powder, and it can be carried out in the same way as conventional powder surface treatment methods.

[0237] [Dispersions and cosmetic compositions, coating compositions, and ink compositions containing such dispersions]

[0238] The dispersion of the present invention is a dispersion containing powder and oil that have been surface-treated by a diblock copolymer used as a surface treatment agent for the powder. Such a dispersion is suitable for cosmetics, coatings, or inks, etc., and the types of powder and oil can be appropriately selected according to the intended use of the dispersion.

[0239] The powders described above can be listed as powders contained in the dispersion of the present invention.

[0240] Furthermore, there are no particular limitations on the oils contained in the dispersion; any oil can be used, including, for example, one or more types of silicone oil, hydrocarbon oil, higher fatty acids, ester oil, polar oils such as natural animal and vegetable oils, semi-synthetic oils, and / or fluorinated oils, with polar oils and silicone oils being preferred. Alternatively, the oil can be composed of one or more ester oils, natural animal and vegetable oils, and one or more silicone oils. Thus, even if the oil is composed of a high-polarity ester oil, a natural animal and vegetable oil, and a low-polarity silicone oil, since all are diblock copolymers of the present invention, they are compatible, and a dispersion with excellent dispersibility, flowability, and long-term stability can be provided.

[0241] As silicone oils, examples include linear or branched organopolysiloxanes ranging from low to high viscosity, such as dimethylpolysiloxane, octanoyl polymethylsiloxane, phenyl polytrimethylsiloxane, methylphenyl polysiloxane, methylhexyl polysiloxane, methylhydropolysiloxane, and dimethylsiloxane-methylphenylsiloxane copolymer; cyclic organopolysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecylcyclohexasiloxane, tetramethyltetrahydrocyclotetrasiloxane, and tetramethyltetraphenylcyclotetrasiloxane; branched organopolysiloxanes such as tris(trimethylsiloxymethylsilane) and tetra(trimethylsiloxysilane); and amino-modified... Organosilicon rubbers including organopolysiloxanes, highly polymerized colloidal dimethylpolysiloxanes, colloidal amino-modified organopolysiloxanes, and colloidal dimethylsiloxane-methylphenylsiloxane copolymers; as well as organosilicon rubbers and cyclic siloxane solutions of rubbers; trimethylsiloxysilicic acid and cyclic organopolysiloxane solutions of trimethylsiloxysilicic acid; higher alkoxy-modified organopolysiloxanes such as stearoxysilanes; higher fatty acid-modified organopolysiloxanes; alkyl-modified organopolysiloxanes; long-chain alkyl-modified organopolysiloxanes; fluorine-modified organopolysiloxanes; organosilicon resins and solutions of organosilicon resins, etc.

[0242] As hydrocarbon oils, examples include straight-chain, branched, and volatile hydrocarbon oils. Specifically, examples include ceresin, α-olefin oligomers, light isoparaffins, isododecane, light liquid isoparaffins, squalane, synthetic squalane, plant-derived squalane, squalene, pure ceresin, paraffin wax, solid paraffin wax, polyethylene wax, polyethylene-polypropylene wax, (ethylene / propylene / styrene) copolymer, (butene / propylene / styrene) copolymer, liquid paraffin, liquid isoparaffin, pterostilbene, polyisobutylene, hydrogenated polyisobutylene, microcrystalline wax, petrolatum, etc.

[0243] Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, sorbic acid, undecenoic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), isostearic acid, and 12-hydroxystearic acid. Examples of higher alcohols include lauryl alcohol, myristic alcohol, palmitol, stearyl alcohol, sorbitol, hexadecyl alcohol, oleyl alcohol, isostearyl alcohol, hexyldodecyl alcohol, octyldodecyl alcohol, cetearyl alcohol, 2-decyltetradecyl alcohol, cholesterol, phytosterols, POE cholesterol ether, monostearate glyceryl ether (squalene), and monooleyl glyceryl ether (squalene).

[0244] Examples of ester oils include diisobutyl adipate, 2-hexyldecyl adipate, di-2-heptylundecyl adipate, N-alkyl diol monoisostearate, isocetyl isostearate, trimethylolpropane triisostearate, ethylene glycol di-2-ethylhexanoate, cetyl 2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, pentaerythritol tetra-2-ethylhexanoate, cetyl octanoate, octyl dodecyl gum, oleic acid ester, octyl dodecyl oleate, decyl oleate, neopentyl glycol dioctanoate, neopentyl glycol didecanoate, triethyl citrate, 2-ethylhexyl succinate, amyl acetate, ethyl acetate, butyl acetate, and isocetyl stearate. Butyl stearate, diisopropyl sebacate, di-2-ethylhexyl sebacate, cetyl lactate, myristyl lactate, isononyl isononanoate, isotriadecyl isononanoate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-hexyldecyl palmitate, 2-heptylundecyl palmitate, 12-hydroxystearic acid cholesterol ester, dipentaerythritol fatty acid ester, isopropyl myristate, octyldodecyl myristate, 2-hexyldecyl myristate, myristyl myristate, hexyldecyl dimethyl octanoate, ethyl laurate, hexyl laurate, N-lauroyl-L-glutamic acid-2-octyldodecyl, isopropyl lauroyl sarcosine, diisostearate malate, etc. Examples of glyceryl ester oils include acetylated glyceryl triisooctanoate, triisostearate, triisopalmitoate, glyceryl monostearate, di-2-heptylundecanoate, trimyristate, and myristate isostearate diglyceride.

[0245] In addition, natural animal and vegetable oils and semi-synthetic oils include avocado oil, flaxseed oil, almond oil, insect wax, perilla oil, olive oil, cocoa butter, kapok wax, coconut oil, carnauba wax, cod liver oil, candelilla wax, refined candelilla wax, butter, beef hoof oil, beef bone oil, hydrogenated butter, almond oil, cetacean wax, hydrogenated oil, wheat germ oil, sesame oil, rice germ oil, rice bran oil, sugarcane wax, camellia oil, safflower oil, shea butter, Chinese tung oil, cinnamon oil, jojoba wax, squalane, squalene, shellac wax, turtle oil, soybean oil, tea seed oil, camellia oil, evening primrose oil, corn oil, lard, rapeseed oil, Japanese tung oil, rice bran wax, wheat germ oil, and horse oil. Peach kernel oil, palm oil, palm kernel oil, castor oil, hydrogenated castor oil, castor oil fatty acid methyl ester, sunflower oil, grape oil, bay leaf wax, jojoba oil, hydrogenated jojoba oil, macadamia nut oil, beeswax, mink oil, meadowfoam seed oil, cottonseed oil, cotton wax, wood wax, wood wax kernel oil, lignite wax, coconut oil, hydrogenated coconut oil, tri-coconut oil fatty acid glycerides, lanolin, peanut oil, lanolin, liquid lanolin, reduced lanolin, lanolin alcohol, hard lanolin, lanolin acetate, lanolin alcohol acetate, lanolin fatty acid isopropyl ester, POE lanolin alcohol ether, POE lanolin alcohol acetate, lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin alcohol ether, egg yolk oil, etc. POE stands for polyoxyethylene.

[0246] Fluorinated oils include perfluoropolyethers, perfluoronaphthenes, and perfluorooctane.

[0247] The dispersion of the present invention can be manufactured by mixing powder treated with the powder surface treatment agent of the present invention and an oil using a known method. Furthermore, when the dispersion is used in cosmetics, coatings, or inks, cosmetic compositions, coating compositions, or ink compositions can be obtained by mixing various ingredients known and commonly used in these fields. These compositions are also embodiments of the present invention.

[0248] [Example]

[0249] The present invention will be further described in detail below through embodiments, but the present invention is not limited to the following embodiments. It should be noted that, unless otherwise specified in the following examples, the "%" in the composition refers to the percentage by mass.

[0250] [Synthesis example 1]

[0251] 39.8 mg of tetrabutyl-m-chlorobenzoate, dried under reduced pressure, was dissolved in 50 mL of THF. Under a nitrogen atmosphere, 872.0 mg of 1-methoxy-1-(trimethylsilyloxy)-2-methyl-1-propene, acting as an initiator, was added to the THF solution of the tetrabutyl-m-chlorobenzoate, and 22.5 g of the following organosilicon macromonomer (a) was added dropwise over 1 hour to prepare the reaction solution. The reaction solution was further stirred at room temperature for 2 hours. Then, 3.93 g of 2-(dimethylamino)ethyl methacrylate was added dropwise to the reaction solution over 5 minutes, and after stirring at room temperature for 1 hour, 10 mL of methanol was added, and the reaction was stopped. The reaction solution was then stripped under reduced pressure at 105 °C for 1 hour at a temperature below 0.007 atm to obtain the target diblock copolymer.

[0252] It should be noted that when gel permeation chromatography (GPC) analysis was performed at two time points, one at the completion of group transfer polymerization of organosilicon macromonomer (a) and the other at the cessation of the reaction, an increase in molecular weight depending on the charge ratio of the initiator and monomer was confirmed at each stage, and the target diblock copolymer was confirmed to have been obtained.

[0253] The number-average molecular weight and polydispersity of the diblock copolymer of Synthetic Example 1 are shown below.

[0254] Number average molecular weight (Mn) = 4126, polydispersity (Mw / Mn) = 1.24, degree of polymerization ratio (n) 2 / n 1 ) = 1.00

[0255]

[0256] (A represents a residue of the organosilicon macromonomer (a), and B represents a residue of 2-(dimethylamino)ethyl methacrylate. The average degree of polymerization of the organosilicon macromonomer (a) is q = 3.9, and the average degree of polymerization of 2-(dimethylamino)ethyl methacrylate is p = 3.9.)

[0257] [Synthesis example 2]

[0258] 39.8 mg of tetrabutyl-m-chlorobenzoate, dried under reduced pressure, was dissolved in 50 mL of THF. Under a nitrogen atmosphere, 872.0 mg of 1-methoxy-1-(trimethylsiloxy)-2-methyl-1-propene, acting as an initiator, was added to the THF solution of the tetrabutyl-m-chlorobenzoate, and 22.5 g of organosilicon macromonomer (a) was added dropwise over 30 minutes to prepare the reaction solution. The reaction solution was further stirred at room temperature for 1 hour. Then, 4.6 g of 2-(diethylamino)ethyl methacrylate was added dropwise to the reaction solution over 30 minutes, and after stirring at room temperature for 1 hour, 10 mL of methanol was added, and the reaction was stopped. The reaction solution was then stripped under reduced pressure at 105 °C for 1 hour at a temperature below 0.007 atm to obtain the target diblock copolymer.

[0259] Similar to Synthesis Example 1, the product was identified as a diblock copolymer. The number-average molecular weight and polydispersity of the diblock copolymer of Synthesis Example 2 are shown below.

[0260] Number average molecular weight (Mn) = 4187, polydispersity (Mw / Mn) = 1.18, degree of polymerization ratio (n) 2 / n 1 ) = 1.00

[0261]

[0262] (A represents a residue of the organosilicon macromonomer (a), and B represents a residue of 2-(diethylamino)ethyl methacrylate. The average degree of polymerization of the organosilicon macromonomer (a) is q = 3.8, and the average degree of polymerization of 2-(diethylamino)ethyl methacrylate is p = 3.8.)

[0263] [Synthesis example 3]

[0264] 19.9 mg of tetrabutyl-m-chlorobenzoate, dried under reduced pressure, was dissolved in 25 mL of THF. Under a nitrogen atmosphere, 436.0 mg of 1-methoxy-1-(trimethylsilyloxy)-2-methyl-1-propene, acting as an initiator, was added to the THF solution of the tetrabutyl-m-chlorobenzoate, and 7.5 g of organosilicon macromonomer (a) was added dropwise over 30 minutes to prepare the reaction solution. The reaction solution was further stirred at room temperature for 1 hour. Then, 7.5 g of 2-ethoxyethyl (meth)acrylate was added dropwise to the reaction solution over 30 minutes, and after stirring at room temperature for 1 hour, 5 mL of methanol was added, and the reaction was stopped. The reaction solution was then stripped under reduced pressure at 105 °C for 1 hour at a temperature below 0.007 atm to obtain the target diblock copolymer.

[0265] Similar to Synthesis Example 1, the product was identified as a diblock copolymer. The number-average molecular weight and polydispersity of the diblock copolymer of Synthesis Example 3 are shown below.

[0266] Number average molecular weight (Mn) = 10568, polydispersity (Mw / Mn) = 1.10, degree of polymerization ratio (n) 2 / n 1 ) = 0.18

[0267]

[0268] (A represents a residue of the organosilicon macromonomer (a), and B represents a residue of 2-ethoxyethyl (meth)acrylate. The average degree of polymerization of the organosilicon macromonomer (a) is q = 32.8, and the average degree of polymerization of 2-ethoxyethyl (meth)acrylate is p = 6.0.)

[0269] [Synthesis Example 4]

[0270] 19.9 mg of tetrabutyl-m-chlorobenzoate, dried under reduced pressure, was dissolved in 25 mL of THF. Under a nitrogen atmosphere, 436.0 mg of 1-methoxy-1-(trimethylsilyloxy)-2-methyl-1-propene, acting as an initiator, was added to the THF solution of the tetrabutyl-m-chlorobenzoate, and 7.3 g of organosilicon macromonomer (a) was added dropwise over 30 minutes to prepare the reaction solution. The reaction solution was further stirred at room temperature for 1 hour. Then, 7.7 g of 2-(methoxyethoxy)ethyl methacrylate was added dropwise to the reaction solution over 30 minutes, and after stirring at room temperature for 1 hour, 5 mL of methanol was added, and the reaction was stopped. The reaction solution was then stripped under reduced pressure at 105 °C for 1 hour at a temperature below 0.007 atm to obtain the target diblock copolymer.

[0271] Similar to Synthesis Example 1, the product was identified as a diblock copolymer. The number-average molecular weight and polydispersity of the diblock copolymer of Synthesis Example 4 are shown below.

[0272] Number average molecular weight (Mn) = 7985, polydispersity (Mw / Mn) = 1.11, degree of polymerization ratio (n) 2 / n 1 ) = 0.23

[0273]

[0274] (A represents a residue of the organosilicon macromonomer (a), and B represents a residue of 2-(methoxyethoxy)ethyl acrylate. The average degree of polymerization of the organosilicon macromonomer (a) is q = 20.2, and the average degree of polymerization of 2-(methoxyethoxy)ethyl acrylate is p = 4.6.)

[0275] [Synthesis Example 5]

[0276] 19.9 mg of tetrabutyl-m-chlorobenzoate, dried under reduced pressure, was dissolved in 25 mL of THF. Under a nitrogen atmosphere, 436.0 mg of 1-methoxy-1-(trimethylsilyloxy)-2-methyl-1-propene, acting as an initiator, was added to the THF solution of the tetrabutyl-m-chlorobenzoate, and 7.5 g of organosilicon macromonomer (a) was added dropwise over 30 minutes to prepare the reaction solution. The reaction solution was further stirred at room temperature for 1 hour. Then, 6.9 g of monomer (b) was added dropwise to the reaction solution over 15 minutes, and after stirring at room temperature for 2 hours, 5 mL of methanol was added to stop the reaction. The reaction solution after the reaction was stopped was stripped under reduced pressure at 105 °C for 1 hour at a temperature below 0.007 atm to obtain the target diblock copolymer.

[0277] Similar to Synthesis Example 1, the product was identified as a diblock copolymer. The number-average molecular weight and polydispersity of the diblock copolymer of Synthesis Example 5 are as follows: Number-average molecular weight (Mn) = 8150, polydispersity (Mw / Mn) = 1.13, degree of polymerization ratio (n... 2 / n 1 ) = 1.00

[0278]

[0279] (A represents the residues of organosilicon macromonomer (a), and B represents the residues of monomer (b). The average degree of polymerization of organosilicon macromonomer (a) is q = 6.9, and the average degree of polymerization of monomer (b) is p = 6.9.)

[0280] [Synthesis example 6]

[0281] 39.8 mg of tetrabutyl-m-chlorobenzoate, dried under reduced pressure, was dissolved in 50 mL of THF. Under a nitrogen atmosphere, 872.0 mg of 1-methoxy-1-(trimethylsiloxy)-2-methyl-1-propene, acting as an initiator, was added to the THF solution of the tetrabutyl-m-chlorobenzoate, and 22.5 g of organosilicon macromonomer (a) was added dropwise over 1 hour to prepare the reaction solution. The reaction solution was further stirred at room temperature for 2 hours. Then, 12.4 g of the monomer (c) was added dropwise to the reaction solution over 30 minutes, and after stirring at room temperature for 5 hours, 10 mL of methanol was added to stop the reaction. The reaction solution after the reaction was stopped was stripped under reduced pressure at 105 °C for 1 hour at a temperature below 0.007 atm to obtain the target diblock copolymer.

[0282] Similar to Synthesis Example 1, the product was identified as a diblock copolymer. The number-average molecular weight and polydispersity of the diblock copolymer of Synthesis Example 6 are as follows: Number-average molecular weight (Mn) = 9294, polydispersity (Mw / Mn) = 1.13, degree of polymerization ratio (n... 2 / n 1 ) = 1.00

[0283]

[0284] (A represents the residues of organosilicon macromonomer (a), and B represents the residues of monomer (c). The average degree of polymerization of organosilicon macromonomer (a) is q = 6.7, and the average degree of polymerization of monomer (c) is p = 6.7.)

[0285] [Synthesis Example 7]

[0286] 39.8 mg of tetrabutyl-m-chlorobenzoate, dried under reduced pressure, was dissolved in 50 mL of THF. Under a nitrogen atmosphere, 872.0 mg of 1-methoxy-1-(trimethylsiloxy)-2-methyl-1-propene, acting as an initiator, was added to the THF solution of the tetrabutyl-m-chlorobenzoate, and 57.5 g of the following organosilicon macromonomer (b) was added dropwise over 30 minutes to prepare the reaction solution. The reaction solution was further stirred at room temperature for 1 hour. Then, 3.93 g of 2-(dimethylamino)ethyl methacrylate was added dropwise to the reaction solution over 30 minutes, and after stirring at room temperature for 1 hour, 10 mL of methanol was added, and the reaction was stopped. The reaction solution was then stripped under reduced pressure at 105 °C for 1 hour at a temperature below 0.007 atm to obtain the target diblock copolymer.

[0287] Similar to Synthesis Example 1, the product was identified as a diblock copolymer. The number-average molecular weight and polydispersity of the diblock copolymer of Synthesis Example 7 are shown below.

[0288] Number average molecular weight (Mn) = 7070, polydispersity (Mw / Mn) = 1.94, degree of polymerization ratio (n) 2 / n 1 ) = 1.00

[0289]

[0290] (A represents a residue of the organosilicon macromonomer (b), and B represents a residue of 2-(dimethylamino)ethyl methacrylate. The average degree of polymerization of the organosilicon macromonomer (b) is q = 2.9, and the average degree of polymerization of 2-(dimethylamino)ethyl methacrylate is p = 2.9.)

[0291] [Synthesis example 8]

[0292] 19.9 mg of tetrabutyl-m-chlorobenzoate, dried under reduced pressure, was dissolved in 25 mL of THF. Under a nitrogen atmosphere, 436.0 mg of 1-methoxy-1-(trimethylsiloxy)-2-methyl-1-propene, acting as an initiator, was added to the THF solution of the tetrabutyl-m-chlorobenzoate, and 6.4 g of the following organosilicon macromonomer (c) was added dropwise over 10 minutes to prepare the reaction solution. The reaction solution was further stirred at room temperature for 1 hour. Then, 0.94 g of 2-(diethylamino)ethyl methacrylate was added dropwise to the reaction solution over 1 minute, and after stirring at room temperature for 1 hour, 5 mL of methanol was added to stop the reaction. The reaction solution after the reaction was stopped was stripped under reduced pressure at 105 °C for 1 hour at a temperature below 0.007 atm to obtain the target diblock copolymer.

[0293] Similar to Synthesis Example 1, the product was identified as a diblock copolymer. The number-average molecular weight and polydispersity of the diblock copolymer of Synthesis Example 8 are shown below.

[0294] Number average molecular weight (Mn) = 2545, polydispersity (Mw / Mn) = 1.17, degree of polymerization ratio (n) 2 / n 1 ) = 0.36

[0295]

[0296]

[0297] (A represents a residue of the organosilicon macromonomer (c), and B represents a residue of 2-(diethylamino)ethyl methacrylate. The average degree of polymerization of the organosilicon macromonomer (c) is q = 5.0, and the average degree of polymerization of 2-(diethylamino)ethyl methacrylate is p = 1.8.)

[0298] [Comparative Synthesis Example 1]

[0299] 39.8 mg of tetrabutyl-m-chlorobenzoate, dried under reduced pressure, was dissolved in 50 mL of THF. Under a nitrogen atmosphere, 872.0 mg of 1-methoxy-1-(trimethylsilyloxy)-2-methyl-1-propene, acting as an initiator, was added to the THF solution of the tetrabutyl-m-chlorobenzoate, and 22.5 g of organosilicon macromonomer (a) was added dropwise over 30 minutes to prepare the reaction solution. The reaction solution was further stirred at room temperature for 2 hours. Then, 3.6 g of isobutyl methacrylate was added dropwise to the reaction solution over 5 minutes, and after stirring at room temperature for 1 hour, 10 mL of methanol was added to stop the reaction. The reaction solution was then subjected to reduced pressure stripping at 105 °C for 1 hour at a temperature below 0.007 atm to obtain the target diblock copolymer.

[0300] Similar to Synthesis Example 1, the product was identified as a diblock copolymer. The number-average molecular weight and polydispersity of the diblock copolymer of Synthesis Example 1 are compared as follows.

[0301] Number average molecular weight (Mn) = 5302, polydispersity (Mw / Mn) = 1.32, degree of polymerization ratio (n) 2 / n 1 ) = 1.00

[0302]

[0303] (A represents a residue of the organosilicon macromonomer (a), and B represents a residue of isobutyl methacrylate. The average degree of polymerization of the organosilicon macromonomer (a) is q = 5.1, and the average degree of polymerization of isobutyl methacrylate is p = 5.1.)

[0304] [Comparative Synthesis Example 2]

[0305] 19.9 mg of tetrabutyl-m-chlorobenzoate, dried under reduced pressure, was dissolved in 25 mL of THF. Under a nitrogen atmosphere, 436.0 mg of 1-methoxy-1-(trimethylsilyloxy)-2-methyl-1-propene, acting as an initiator, was added to the THF solution of the tetrabutyl-m-chlorobenzoate, and 13.99 g of organosilicon macromonomer (a) was added dropwise over 30 minutes to prepare the reaction solution. The reaction solution was further stirred at room temperature for 1 hour. Then, 1.57 g of 2-(trimethylsilyloxy)ethyl methacrylate was added dropwise to the reaction solution over 30 minutes, and after stirring at room temperature for 1 hour, 5 mL of methanol was added to stop the reaction. The reaction solution was then stripped under reduced pressure at 105 °C for 1 hour at a temperature below 0.007 atm to obtain the target diblock copolymer.

[0306] Similar to Synthesis Example 1, the product was identified as a diblock copolymer. The number-average molecular weight and polydispersity of the diblock copolymer of Synthesis Example 2 are shown below.

[0307] Number average molecular weight (Mn) = 9418, polydispersity (Mw / Mn) = 1.11, degree of polymerization ratio (n) 2 / n 1 ) = 2.00

[0308]

[0309] (A represents a residue of the organosilicon macromonomer (a), and B represents a residue of 2-(trimethylsilyloxy)ethyl methacrylate. The average degree of polymerization of the organosilicon macromonomer (a) is q = 3.1, and the average degree of polymerization of 2-(trimethylsilyloxy)ethyl methacrylate is p = 6.2.)

[0310] [Comparative Synthesis Example 3]

[0311] 39.8 mg of tetrabutyl-m-chlorobenzoate, dried under reduced pressure, was dissolved in 50 mL of THF. Under a nitrogen atmosphere, 436.0 mg of 1-methoxy-1-(trimethylsiloxy)-2-methyl-1-propene, acting as an initiator, was added to the THF solution of the tetrabutyl-m-chlorobenzoate, followed by the dropwise addition of 22.5 g of organosilicon macromonomer (a) over 30 minutes to prepare the reaction solution. The reaction solution was further stirred at room temperature for 1 hour. Then, 4.2 g of cyclohexyl methacrylate was added dropwise to the reaction solution over 30 minutes, and after stirring at room temperature for 1 hour, 5 mL of methanol was added to stop the reaction. The reaction solution was then subjected to vacuum stripping at 105 °C for 1 hour at a temperature below 0.007 atm to obtain the target diblock copolymer.

[0312] Similar to Synthesis Example 1, the product was identified as a diblock copolymer. The number-average molecular weight and polydispersity of the diblock copolymer of Synthesis Example 3 are shown below.

[0313] Number average molecular weight (Mn) = 15046, polydispersity (Mw / Mn) = 1.10, degree of polymerization ratio (n) 2 / n 1 ) = 1.00

[0314]

[0315] (A represents a residue of the organosilicon macromonomer (a), and B represents a residue of cyclohexyl methacrylate. The average degree of polymerization of the organosilicon macromonomer (a) is q = 14.1, and the average degree of polymerization of cyclohexyl methacrylate is p = 14.1.)

[0316] [Comparative Synthesis Example 4]

[0317] 39.8 mg of tetrabutyl-m-chlorobenzoate, dried under reduced pressure, was dissolved in 50 mL of THF. Under a nitrogen atmosphere, 873.0 mg of 1-methoxy-1-(trimethylsiloxy)-2-methyl-1-propene, acting as an initiator, was added to the THF solution of the tetrabutyl-m-chlorobenzoate, and 11.3 g of organosilicon macromonomer (a) was added dropwise over 30 minutes to prepare the reaction solution. The reaction solution was further stirred at room temperature for 2 hours. Then, 3.93 g of 2-(dimethylamino)ethyl methacrylate was added dropwise to the reaction solution over 15 minutes, and the mixture was stirred at room temperature for 1 hour. Next, 11.3 g of organosilicon macromonomer (a) was added dropwise over 30 minutes, and the mixture was stirred further at room temperature for 2 hours. Then, 10 mL of methanol was added to stop the reaction. The reaction solution was stripped under reduced pressure at 105 °C for 1 hour at a temperature below 0.007 atm to obtain the target triblock copolymer.

[0318] At three time points—the completion of the first group transfer polymerization of the organosilicon macromonomer (a), the completion of the group transfer polymerization of 2-(dimethylamino)ethyl methacrylate, and the point after the reaction stopped—GPC analysis, similar to that in Synthesis Example 1, showed an increase in molecular weight depending on the charge ratio of the initiator and monomer at each step, confirming it as a triblock copolymer. The number-average molecular weight and polydispersity of the triblock copolymer in Synthesis Example 4 are compared as follows.

[0319] Number-average molecular weight (Mn) = 4690, polydispersity (Mw / Mn) = 1.61

[0320]

[0321] (A represents a residue of the organosilicon macromonomer (a), and B represents a residue of 2-(dimethylamino)ethyl methacrylate. The average degree of polymerization of the organosilicon macromonomer (a) is q1 = q2 = 2.2, and the average degree of polymerization of 2-(dimethylamino)ethyl methacrylate is p = 4.4.)

[0322] [Comparative Synthesis Example 5]

[0323] 39.8 mg of tetrabutyl-m-chlorobenzoate, dried under reduced pressure, was dissolved in 50 mL of THF. Under a nitrogen atmosphere, 873.0 mg of 1-methoxy-1-(trimethylsiloxy)-2-methyl-1-propene, acting as an initiator, was added to the THF solution of the tetrabutyl-m-chlorobenzoate, followed by the dropwise addition of 1.97 g of 2-(dimethylamino)ethyl methacrylate over 10 minutes to prepare the reaction solution. The reaction solution was further stirred at room temperature for 1 hour. Then, 22.5 g of organosilicon macromonomer (a) was added dropwise to the reaction solution over 1 hour, and the mixture was stirred at room temperature for 2 hours. Next, 1.97 g of 2-(dimethylamino)ethyl methacrylate was added dropwise over 10 minutes, and the mixture was stirred further at room temperature for 1 hour. Then, 10 mL of methanol was added, and the reaction was stopped. The reaction solution was then stripped under reduced pressure at 105 °C for 1 hour at a temperature below 0.007 atm to obtain the target triblock copolymer.

[0324] At three time points—the completion of the first group transfer polymerization of 2-(dimethylamino)ethyl methacrylate, the completion of the group transfer polymerization of the organosilicon macromonomer (a), and the point after the reaction stopped—GPC analysis, similar to that in Synthesis Example 1, confirmed an increase in molecular weight depending on the charge ratio of the initiator and monomer at each step, and confirmed it to be a triblock copolymer. The number-average molecular weight and polydispersity of the triblock copolymer in Synthesis Example 5 are shown below.

[0325] Number-average molecular weight (Mn) = 4570, polydispersity (Mw / Mn) = 1.50

[0326]

[0327] (A represents a residue of the organosilicon macromonomer (a), and B represents a residue of 2-(dimethylamino)ethyl methacrylate. The average degree of polymerization of 2-(dimethylamino)ethyl methacrylate is q1 = q2 = 2.2, and the average degree of polymerization of the organosilicon macromonomer (a) is p = 4.4.)

[0328] [Comparative Synthesis Example 6]

[0329] 39.8 mg of tetrabutyl-m-chlorobenzoate, dried under reduced pressure, was dissolved in 50 mL of THF. Under a nitrogen atmosphere, 872.0 mg of 1-methoxy-1-(trimethylsilyloxy)-2-methyl-1-propene, acting as an initiator, was added to the THF solution of the tetrabutyl-m-chlorobenzoate, and a monomer mixture (22.5 g of organosilicon macromonomer (a) and 3.93 g of 2-(dimethylamino)ethyl methacrylate) was added dropwise over 1 hour to prepare the reaction solution. The reaction solution was further stirred at room temperature for 2 hours, and then 10 mL of methanol was added to stop the reaction. The reaction solution was then subjected to reduced pressure stripping at 105 °C for 1 hour at a temperature below 0.007 atm to obtain the random copolymer. The number-average molecular weight and polydispersity of the random copolymer of Comparative Synthesis Example 6 are shown below.

[0330] Number-average molecular weight (Mn) = 4059, polydispersity (Mw / Mn) = 1.80

[0331]

[0332] (A represents a residue of the organosilicon macromonomer (a), and B represents a residue of 2-(dimethylamino)ethyl methacrylate. The average degree of polymerization of the organosilicon macromonomer (a) is q = 3.8, and the average degree of polymerization of 2-(dimethylamino)ethyl methacrylate is p = 3.8. Furthermore, X represents either a residue of the organosilicon macromonomer (a) or 2-(dimethylamino)ethyl methacrylate. Regarding the degree of polymerization of a unit having X, if X is a residue of the organosilicon macromonomer (a), it is included in the average degree of polymerization expressed as q (i.e., 3.8); if X is a residue of 2-(dimethylamino)ethyl methacrylate, it is included in the average degree of polymerization expressed as p (i.e., 3.8).)

[0333] [Dispersion Assessment]

[0334] After preparing the slurry using a bead mill according to the mixing ratios shown in Tables 1 and 2, the viscosity was measured. The unit is mPa·s.

[0335] It should be noted that the viscosity is the value measured at 25°C using a type B viscometer (TVB-10 type, manufactured by Toki Sangyo, Japan) according to the method described in JIS K7117-1:1999.

[0336] [Table 1]

[0337]

[0338] (*1) MTR07 (manufactured by TAYCA CORPORATION)

[0339] (*2)MZ506X (manufactured by TAYCA CORPORATION)

[0340] [Table 2]

[0341]

[0342] (*1) MTR07 (manufactured by TAYCA CORPORATION)

[0343] (*2)MZ506X (manufactured by TAYCA CORPORATION)

[0344] *A viscosity of × for the copolymer after 1 month of preparation means that it has lost its flowability and cannot be measured.

[0345] As can be seen from the results in Tables 1 and 2 above, the diblock copolymer of the present invention has high dispersibility compared with triblock copolymers or random copolymers, and can be used to prepare low-viscosity dispersions with better storage stability.

[0346] Furthermore, as shown in Tables 1 and 2 above, by using diblock copolymers as surface treatment agents for powders, dispersions with low viscosity immediately after preparation can be produced. Comparative Examples 7-9 and 10-12, which used surface treatment agents with non-polar monomers as structural units, lost their flowability one month after preparation; on the other hand, Examples 1-10, which used surface treatment agents with polar monomers as structural units, were able to produce low-viscosity dispersions. In particular, Examples 1 and 10, which used surface treatment agents with highly polar monomers as structural units, were able to produce dispersions with exceptionally low viscosity.

[0347] The results above clearly demonstrate that diblock copolymers with polar monomers as structural units are particularly useful as surface treatment agents for powders.

Claims

1. A diblock copolymer, wherein the main chain of the diblock copolymer is composed of organosilicon graft copolymer blocks represented by formula [I] and polar copolymer blocks represented by formula [II], The terminal structure at one end of the main chain is represented by formula [III], and the terminal structure at the other end is represented by formula [IV]. The number-average molecular weight of this diblock copolymer is 2000~10000, wherein... In equation [I], R 1 It can be a hydrogen atom or a methyl group. A represents a group containing an organopolysiloxane as represented by the following general formula (1) or a group containing an organopolysiloxane as represented by the following general formula (2). n 1 The number representing the repeating unit, where 1 ≤ n 1 ≤50, The groups containing organopolysiloxanes represented by general formula (1) have a linear organopolysiloxane structure with a repeating unit number m of 0 to 100. In general formula (1), Z represents a divalent organic group. R 2 Each can be independently represented as a saturated hydrocarbon group or phenyl group with 1 to 10 carbon atoms. R 3 Represented as a saturated hydrocarbon group with 1 to 10 carbon atoms. m represents a number between 0 and 100. The organopolysiloxane group represented by general formula (2) has a dendritic organopolysiloxane structure with a hierarchical number c of 1 to 10. In general formula (3), i represents the number of each level of the dendritic structure, and c represents integers from 1 to c. In general formula (2), L 1 For silyl organic groups represented by general formula (3), the group where i is 1, In general formula (3), Z represents a divalent organic group. R 4 Represented as a saturated hydrocarbon group or phenyl group with 1 to 10 carbon atoms. R 5 Each can be independently represented as an alkyl or phenyl group having 1 to 8 carbon atoms. L i+1 When level i is less than c (level i is lower than the top level), it is a silyl organic group L represented by general formula (3). i L i+1 When level i = c (level i is the top level), it consists of hydrogen atoms, saturated hydrocarbon groups with 1 to 10 carbon atoms, or phenyl groups. a i Represented as OR in level i 4 The number of groups is in the range of 0 to 3. In equation [II], R 1 Represented as a hydrogen atom or a methyl group, B represents any group selected from -OB', -NH2, and -OH, n 2 The number is represented by repeating units, and 1 ≤ n. 2 ≤50, where B' represents a monovalent hydrocarbon group having one or more divalent groups selected from polyoxyalkylene, -C(O)-, -O-, -S-, and -NR- with 1 to 20 carbon atoms, and R in -NR- represents a hydrogen atom or a monovalent hydrocarbon group with 1 to 20 carbon atoms. In equation [III], R 6 Represented as alkyl groups having 1 to 4 carbon atoms. R 7 Each can be independently represented as an alkyl group having 1 to 4 hydrogen atoms. In equation [IV], R 1 It can be a hydrogen atom or a methyl group. X represents a group represented by A in formula [I] or B in formula [II].

2. The diblock copolymer according to claim 1, wherein, In formula [II], B is a group represented by general formula (8') or general formula (9'). In equation (8'), R 7 Independently represented as hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, in formula (9'), R 3 Represented as a saturated hydrocarbon group with 1 to 10 carbon atoms, n 3 Represents the number of repeating units, where 1 ≤ n. 3 ≤10.

3. The diblock copolymer according to claim 1, wherein, The divalent organic group represented by Z in general formula (2) and general formula (3) is a saturated hydrocarbon group with 2 to 12 carbon atoms.

4. The diblock copolymer according to claim 1, wherein, n 2 / n 1 The value ranges from 0.02 to 10.

5. The method for manufacturing the diblock copolymer according to any one of claims 1 to 4, wherein, The compound represented by general formula (4) is used as the initiator, and has The process of group transfer polymerization of monomers represented by general formula (5), and Group transfer polymerization is a process involving polar monomers represented by general formula (6). In general formula (4), R 6 Each can be independently represented as an alkyl group having 1 to 4 carbon atoms. R 7 Each can be independently represented as an alkyl group having 1 to 4 hydrogen atoms. In general formula (5), R 1 Represented as a hydrogen atom or a methyl group, A represents a group containing an organopolysiloxane, represented by general formula (1) or a group containing an organopolysiloxane, represented by general formula (2). The groups containing organopolysiloxanes represented by general formula (1) have a linear organopolysiloxane structure with a repeating unit number m of 0 to 100. In general formula (1), Z represents a divalent organic group. R 2 Each can be independently represented as a saturated hydrocarbon group or phenyl group with 1 to 10 carbon atoms. R 3 Represented as a saturated hydrocarbon group with 1 to 10 carbon atoms. m represents a number between 0 and 100. The organopolysiloxane group represented by general formula (2) has a dendritic organopolysiloxane structure with a hierarchical number c of 1 to 10. In general formula (3), i represents the number of each level of the dendritic structure, and is an integer from 1 to c. In general formula (2), L 1 For silyl organic groups represented by general formula (3), the group where i is 1, In general formula (3), Z represents a divalent organic group. R 4 It is represented as a saturated hydrocarbon group or phenyl group with 1 to 10 carbon atoms. R 5 Each can be independently represented as an alkyl or phenyl group having 1 to 8 carbon atoms. When level i is less than c (level i is lower than the top level), L i+1 L is a silyl organic group represented by general formula (3). i When level i = c (level i is the top level), L i+1 It consists of a saturated hydrocarbon group or a phenyl group with 1 to 10 carbon atoms, containing hydrogen atoms. a i Represented as OR in level i 4 The number of groups, and the number is in the range of 0 to 3. In general formula (6), R 1 To represent a hydrogen atom or a methyl group, B is any group selected from -OB', -NH2, and -OH, wherein B' represents a monovalent hydrocarbon group having one or more divalent groups selected from polyoxyalkylene, -C(O)-, -O-, -S-, and -NR- with 1 to 20 carbon atoms, and R in -NR- represents a hydrogen atom or a monovalent hydrocarbon group with 1 to 20 carbon atoms.

6. The method for manufacturing the diblock copolymer according to claim 5, wherein, The polar monomer represented by general formula (6) is the polar monomer represented by the following general formula (8) or general formula (9). In general formula (8), R 1 Represented as a hydrogen atom or a methyl group, R 7 Each can be independently represented as an alkyl group having 1 to 4 hydrogen atoms. In general formula (9), R 1 Represented as a hydrogen atom or a methyl group, R 3 Represented as a saturated hydrocarbon group with 1 to 10 carbon atoms. n 3 Let n be a number of repeating units, where 1 ≤ n. 3 ≤10.

7. The method for manufacturing the diblock copolymer according to claim 6, wherein, The polar monomer represented by general formula (8) is the polar monomer represented by the following formula (8-1). 。 8. A surface treatment agent for powders, wherein, The diblock copolymer comprising any one of claims 1 to 4.

9. A dispersion, wherein, It includes powders and oils treated with the surface treatment agent for powders as described in claim 8.

10. A cosmetic composition, coating composition, or ink composition, wherein, It comprises the dispersion as described in claim 9.

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