JP2017171834A - Method for producing polyrotaxane-crosslinked polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To stably produce a polyrotaxane-crosslinked polymer having functions derived from polyrotaxane crosslinking, the polymer being generally applicable to various polymer seeds, as a water dispersion having high stability at desired particle diameters.SOLUTION: This invention relates to a method for producing a polyrotaxane-crosslinked polymer (C), comprising: using modified polyrotaxane (A) and a monomer (B) having a radical-polymerizable carbon-carbon double bond, partially or altogether to form a mini-emulsion in an aqueous solvent; and then copolymerizing the modified polyrotaxane (A) and the monomer (B). The modified polyrotaxane (A) is the one modified by reacting a functional monomer (b) with the cyclic molecules of polyrotaxane (a) in which straight chain molecules are passed through the opening parts of the cyclic molecules and both the terminals of the straight chain molecules are provided with block groups.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for producing a polyrotaxane crosslinked polymer which is a polymer crosslinked via a polyrotaxane.

  A polyrotaxane in which a linear molecule is inserted like a skewer into the opening of a cyclic molecule and a blocking group is arranged at both ends of the linear molecule so that the cyclic molecule is not detached. Can move on linear molecules. Polyrotaxane cross-linked polymers in which various polymers are cross-linked through such polyrotaxanes can be applied to various fields such as paints, sheets, films, pressure-sensitive adhesives and resin modifiers due to the properties derived from the movement of cyclic molecules. Expected. For example, in coatings, it can be used as a softening agent for coatings and as an anti-scratch agent, and as a sheet, film, and resin modifier, it is expected to provide impact resistance, vibration damping, and slidability. Is done.

  As such a polyrotaxane crosslinked polymer, for example, Patent Document 1 discloses a crosslinked polyrotaxane in which a photopolymerizable group is introduced into a polyrotaxane and the polyrotaxanes are directly crosslinked via a cyclic molecule. Patent Document 2 discloses a pressure-sensitive adhesive composition in which a polyrotaxane and a polyacrylic acid ester having a hydroxyl group are crosslinked with a compound having an isocyanate group.

  On the other hand, from the viewpoints of low impact on the global environment, safety, hygiene, and the like, in recent years, organic solvents have been replaced by aqueous solvents in various functional materials. Here, the polyrotaxane crosslinked polymer expected for various uses as described above is also required to be dispersed in an aqueous solvent, and Patent Documents 3 and 4 have already been reported.

  In addition, when the polyrotaxane crosslinked polymer and the aqueous dispersion thereof are used for paints, resin modifiers, cosmetics, etc., the polymer composition is suitable for expressing its function, and its particle size is for the function expression. It is required to be able to control to a desired particle size.

International publication WO2011 / 105532 pamphlet JP 2013-203854 A International Publication WO2005 / 080469 Pamphlet International Publication WO2009 / 145073 Pamphlet

In the methods of Patent Documents 1, 3, and 4, since the polyrotaxanes are cross-linked via a cyclic molecule in the polyrotaxane, only a cross-linked structure that can maintain the function as a polyrotaxane after the cross-linking is employed in the cross-linked portion. It cannot be used and lacks versatility.
On the other hand, in the method of Patent Document 2, although a polymer such as polyacrylic acid ester can be used, it is difficult to crosslink in an aqueous system because an isocyanate compound that easily reacts with water is used for crosslinking. Since the polymer is crosslinked with polyrotaxane, it is difficult to obtain an aqueous dispersion having a desired particle size.

  Moreover, in order to express the characteristic derived from the movement of the cyclic molecule, the linear molecule needs to have a certain length, and the polyrotaxane is often a high molecular weight substance. For this reason, even if it tried to obtain the water dispersion which used the polyrotaxane for bridge | crosslinking, the coagulated material etc. were easy to generate | occur | produce at the time of manufacture, and there existed a problem that manufacturing stability was bad.

  From the above, there is a need for a polyrotaxane crosslinked polymer that can be applied universally to various polymer species and that can provide a stable aqueous dispersion having a desired particle size and a method for producing the same.

  The present invention is a cross-linked polymer having a function derived from polyrotaxane cross-linking, and a polyrotaxane cross-linked polymer that can be widely used for various polymer species as a highly stable aqueous dispersion with a desired particle size. It aims at providing the manufacturing method of the polyrotaxane crosslinked polymer which can be manufactured stably.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor has made radical-polymerizable carbon-carbon into a modified polyrotaxane (A) modified by reacting a functional monomer (b) with a cyclic molecule of polyrotaxane. When the monomer (B) having a double bond is copolymerized, the modified polyrotaxane (A) and a part or all of the monomer (B) are copolymerized after forming a miniemulsion in an aqueous solvent. It has been found that the above-mentioned problems can be solved by doing so.

  The present invention has been achieved based on such findings, and the gist thereof is as follows.

[1] A method for producing a polyrotaxane crosslinked polymer (C) by copolymerizing a modified polyrotaxane (A) and a monomer (B) having a carbon-carbon double bond capable of radical polymerization, In the modified polyrotaxane (A), a linear molecule penetrates through the opening of the cyclic molecule, and a functional monomer () is added to the cyclic molecule of the polyrotaxane (a) having a blocking group at both ends of the linear molecule. a polyrotaxane cross-link having a structure in which b) is reacted, wherein the modified polyrotaxane (A) and the monomer (B) are partly or wholly formed into a miniemulsion in an aqueous solvent and then copolymerized. Production method of polymer (C).

[2] In [1], a high shear device is used for a mixture of the modified polyrotaxane (A), a part or all of the monomer (B), an emulsifier, an aqueous solvent, and a hydrophobic stabilizer. A polyrotaxane crosslinked polymer (C) comprising: a miniemulsion step for forming a miniemulsion by applying shear; and a copolymerization step for carrying out polymerization in the presence of a radical initiator in the obtained miniemulsion. ) Manufacturing method.

[3] In [2], the high shear device is any one of a pressure homogenizer, an emulsifying device including a high-pressure pump and an interaction chamber, an emulsifying device for applying ultrasonic energy, and an emulsifying device for applying high frequency. A method for producing a crosslinked polyrotaxane polymer (C).

[4] In any one of [1] to [3], the functional monomer (b) is selected from a carbon-carbon double bond, an isocyanate group, an isothiocyanate group, an epoxy group, and a dicarboxylic anhydride group. A method for producing a crosslinked polyrotaxane polymer (C), which is a compound having a reactive functional group.

[5] In [4], the functional monomer (b) is 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, glycidyl acrylate, glycidyl methacrylate, allyl isocyanate, allyl isothiocyanate, and maleic anhydride. A method for producing a crosslinked polyrotaxane polymer (C), which is one or more selected from the group consisting of:

[6] In any one of [1] to [5], the modified polyrotaxane (A) is a functional group containing 100 parts by mass of the polyrotaxane (a) and the functional monomer (b). A process for producing a crosslinked polyrotaxane polymer (C), wherein the polymer (b) is reacted at a ratio of 0.1 to 99.9 parts by mass.

[7] In any one of [1] to [6], the modified polyrotaxane (A) is a functional solution in which the polyrotaxane (a) is dissolved in at least a part of the monomer (B). A method for producing a crosslinked polyrotaxane polymer (C), which is obtained by reacting a functional monomer (b).

[8] In any one of [1] to [7], the monomer (B) is one or more selected from the group consisting of conjugated dienes and (meth) acrylic acid esters. A process for producing a polyrotaxane crosslinked polymer (C) characterized by

[9] In any one of [1] to [8], the amount of the monomer (B) copolymerized with the modified polyrotaxane (A) is such that the modified polyrotaxane (A), the monomer (B), and The manufacturing method of the polyrotaxane crosslinked polymer (C) characterized by being 50-99.9 mass% with respect to a total of 100 mass%.

[10] The production of the polyrotaxane crosslinked polymer (C) according to any one of [1] to [9], wherein the obtained polyrotaxane crosslinked polymer (C) has a gel content of 30 to 100% by mass. Method.

[11] The method for producing a crosslinked polyrotaxane polymer (C) according to any one of [1] to [10], wherein the obtained polyrotaxane crosslinked polymer (C) has a volume average particle diameter of 5 to 3000 nm. .

According to the present invention, various polymer cross-linked polymers having a function derived from polyrotaxane cross-linking can be stably produced as an aqueous dispersion having a desired particle diameter.
The polyrotaxane crosslinked polymer (C) produced according to the present invention is obtained by copolymerizing a monomer (B) having a carbon-carbon double bond capable of radical polymerization with a modified polyrotaxane (A) obtained by modifying a cyclic molecule. Therefore, by selecting the type of the monomer (B), it can be applied universally to various polymer types. In addition, since the copolymerization reaction proceeds via a cyclic molecule of polyrotaxane and no linear molecule is involved, the mobility of the cyclic molecule on the linear molecule is hardly inhibited even after crosslinking. And the function as a polyrotaxane can be maintained.
Further, when the polyrotaxane crosslinked polymer (C) is produced, a combination of the functional monomer (b) that forms the modifying group of the modified polyrotaxane (A) and the monomer (B) that forms the polymer portion is selected. Thus, copolymerization in an aqueous system is possible. At that time, by controlling the amount of the monomer (B) to be copolymerized or performing an enlargement treatment after the copolymerization, a polyrotaxane crosslinked polymer ( By adjusting the molecular weight, viscosity and the like of C), an aqueous dispersion having a desired dispersed particle size can be obtained.

  After copolymerization of the modified polyrotaxane (A) and the monomer (B), after forming a miniemulsion of the modified polyrotaxane (A) and a part or all of the monomer (B) in an aqueous solvent By carrying out the copolymerization, the modified polyrotaxane (A), which is a high molecular weight substance, is efficiently taken into the micelles of the miniemulsion, so that stability during production is improved and control of the particle size is facilitated.

  The polyrotaxane crosslinked polymer (C) produced according to the present invention is useful for various applications such as paints, sheets, films, pressure-sensitive adhesives and resin modifiers. For example, paints using the aqueous dispersion are coated with Excellent effect in softening the film and preventing scratches.

2 is a measurement chart of storage elastic modulus E ′ of the polyrotaxane crosslinked polymer (C-1) produced in Example 1. 10 is a measurement chart of storage elastic modulus E ′ of the polymer (C′-4) produced in Comparative Example 4.

  Hereinafter, embodiments of the present invention will be described in detail.

  The method for producing the polyrotaxane crosslinked polymer (C) of the present invention comprises a polyrotaxane crosslinked polymer obtained by copolymerizing a modified polyrotaxane (A) and a monomer (B) having a carbon-carbon double bond capable of radical polymerization. (C) is a method for producing the modified polyrotaxane (A), wherein the linear molecule penetrates through the opening of the cyclic molecule, and the polyrotaxane (a) has a blocking group at both ends of the linear molecule. The cyclic molecule is a structure in which the functional monomer (b) is reacted, and the modified polyrotaxane (A) and a part or all of the monomer (B) are converted into a miniemulsion in an aqueous solvent. After the formation, the copolymerization is performed.

  Hereinafter, the polyrotaxane crosslinked polymer (C) produced by the method for producing the polyrotaxane crosslinked polymer (C) of the present invention may be referred to as “polyrotaxane crosslinked polymer (C) of the present invention”.

[Modified Polyrotaxane (A)]
First, the modified polyrotaxane (A) according to the present invention (hereinafter sometimes referred to as “modified polyrotaxane (A) of the present invention”) will be described.
In the modified polyrotaxane (A) of the present invention, the linear molecule penetrates through the opening of the cyclic molecule, and the cyclic molecule of the polyrotaxane (a) having a blocking group at both ends of the linear molecule has a functional monomer. The body (b) has been modified by reaction.

<Polyrotaxane (a)>
The polyrotaxane (a) is usually a resin in which a linear molecule penetrates through openings of at least two cyclic molecules and has a blocking group at both ends of the linear molecule.
In the polyrotaxane (a), the cyclic molecule can freely move on the linear molecule, but has a structure in which the cyclic molecule cannot escape from the linear molecule due to the blocking group.

  The cyclic molecule of the polyrotaxane (a) in the present invention can include a linear molecule and move on the linear molecule, and has reactivity with the functional monomer (b). For example, what has a hydroxyl group, a carboxyl group, an amino group, a thiol group, a silanol group etc. which can react with a functional monomer (b) should just be mentioned, and a typical thing is crown ether, cyclic siloxane, and cyclic Examples include oligosaccharides. Various substituents and polymer parts may be introduced into these cyclic molecules. Among the above-mentioned cyclic molecules, cyclic oligosaccharides are easily available, can be selected with an appropriate ring diameter, and have a hydroxyl group, so that various substituents and polymer parts can be introduced. This is preferable in terms of points.

Examples of the cyclic oligosaccharide as the cyclic molecule include α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, and among them, α-cyclodextrin is particularly preferable.
The polyrotaxane (a) may have only one kind of cyclic molecule, and the cyclic structure, presence / absence of substituent, kind of substituent, presence / absence of polymer part, kind of polymer part, etc. It may have two or more of.

  Examples of the polymer part introduced into the cyclic molecule of the polyrotaxane (a) include polyether, polyester, polysiloxane, polycarbonate, poly (meth) acrylate or polyene, a copolymer thereof, or a mixture thereof. Can be mentioned. More specifically, polyethylene glycol diol, polyethylene glycol dicarboxylic acid terminal (carboxylic acid modification of polyethylene glycol), polyethylene glycol dithiol acid terminal, polypropylene diol, polytetrahydrofuran, poly (tetrahydrofuran) bis (3-aminopropyl) terminal, polypropylene Polyethers such as glycol bis (2-aminopropyl ether), glycerol propoxylate, glycerol tris [poly (propylene glycol) amino terminus], pentaerythritol ethoxylate, pentaerythritol propoxylate; poly (ethylene adipate), poly (1 , 3-propylene adipate) diol end, poly (1,4-butylene adipate) diol end, polylactone, etc. Reesters; polyenes such as modified polybutadiene and modified polyisoprene; polydimethylsiloxane disilanol end, polydimethylsiloxane hydrogenated end, polydimethylsiloxane bis (aminopropyl) end, polydimethylsiloxane diglycidyl ether end, polydimethylsiloxane di Examples thereof include, but are not limited to, siloxanes such as carbinol ends, polydimethylsiloxane divinyl ends, polydimethylsiloxane dicarboxylic acid ends; In particular, the polymer part is preferably a polyether or a polyester.

  The method for introducing the polymer moiety into the cyclic molecule is not particularly limited, and polymerization may be performed directly from the cyclic molecule, or it may react with both the polymer constituting the polymer moiety and the functional group of the cyclic molecule. It may be introduced through a compound having two or more reactive functional groups (hereinafter sometimes referred to as “reactive functional group I”).

  Examples of the reactive functional group include an isocyanate group, a thioisocyanate group, an oxirane group, an oxetane group, a carbodiimide group, a silanol group, an oxazoline group, an aziridine group, an epoxy group, and a maleic anhydride group. Examples of the compound having two or more of these reactive functional groups include hexamethylene diisocyanate, hexamethylene diisocyanate biuret type, isocyanurate type, adduct type, tolylene-2,4-diisocyanate, isophorone diisocyanate, trimethylhexamethylene. Polyfunctional isocyanates such as diisocyanate, xylylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, (4,4′-methylenedicyclohexyl) diisocyanate, oxirane compounds such as epichlorohydrin, epibromohydrin, 3- Examples thereof include, but are not limited to, oxetane compounds such as (chloromethyl) -3-methyloxetane, 2,2′-bis (2-oxazoline), and the like.

  The linear molecule of polyrotaxane (a) is a molecule that is included in a cyclic molecule and can be integrated by physical bonds rather than chemical bonds such as covalent bonds. If it is, it will not specifically limit. The “linear” in the present invention may be substantially linear, and the linear molecule may have a branched chain as long as the cyclic molecule can move.

  Examples of the linear molecule of polyrotaxane (a) include polyethylene glycol, polypropylene glycol, polyisoprene, polyisobutylene, polybutadiene, polytetrahydrofuran, polyacrylic acid ester, polydimethylsiloxane, polyethylene, polypropylene, and the like. Of these, one or more may be used in combination.

  The number average molecular weight of the linear molecule is more preferably 3,000 to 300,000, 10,000 to 200,000, and particularly preferably 20,000 to 100,000. When the number average molecular weight of the linear molecule is within the above range, the cyclic molecule is easily moved, and the dispersibility with the monomer (B) is improved during the miniemulsion described later. These functions are easily expressed.

The blocking group at both ends of the linear molecule of the polyrotaxane (a) is not particularly limited as long as it is a group capable of maintaining a state where the linear molecule penetrates the cyclic molecule. Examples of such blocking groups include bulky groups and ionic groups, such as dinitrobenzenes (dinitrophenyl group), cyclodextrins, adamantanes, triarylmethyls (trityl group), fluoresceins, pyrene. And groups derived from cyclic compounds such as anthracenes, or groups in which polymers such as polyamide, polyimide, polyurethane, polydimethylsiloxane, and polyacrylic acid ester are bonded in the main chain or side chain.
The blocking groups at both ends of the linear molecule may be the same or different.

The number of cyclic molecules relative to the linear molecule penetrating through the opening of the cyclic molecule is the number of cyclic molecules that can penetrate between the blocking groups at both ends of the linear molecule. The maximum is 100%, and the ratio of the cyclic molecule to the maximum 100% (hereinafter, this ratio may be referred to as “inclusion rate”) is 0.1 to 60%, particularly 1 to 50%. In particular, 5 to 40% is preferable.
If the inclusion rate of the cyclic molecule is within the above range, the cyclic molecule can easily move on the linear molecule, and the functionality due to having the cyclic molecule is also effectively exhibited. Note that the maximum number of cyclic molecules that can penetrate the linear molecule and exist on the linear molecule is determined by the length of the linear molecule and the thickness of the cyclic molecule. This maximum amount is determined experimentally when polyethylene glycol and the cyclic molecule is α-cyclodextrin (see Macromolecules, 1993, 26, 5698).

  The number average molecular weight of the polyrotaxane (a) is not particularly limited, but the number average molecular weight of the polyrotaxane (a) that satisfies the above-mentioned number average molecular weight of the linear molecule and the inclusion ratio of the cyclic molecule is usually 3, 500 to 5,000,000, preferably 15,000 to 2,000,000.

  As the polyrotaxane (a), for example, “Celum Superpolymer SH3400P”, “Celum Superpolymer SH2400P” manufactured by Advanced Soft Materials Co., Ltd. can be used as commercially available products.

<Functional monomer (b)>
The modified polyrotaxane (A) of the present invention has a structure in which the cyclic molecule of the polyrotaxane (a) and the functional monomer (b) are reacted, and the functional monomer (b) It is a compound having a reactive functional group capable of reacting with a carbon-carbon double bond and a cyclic molecule of polyrotaxane (a). Preferably, it is a monomer having a reactive functional group capable of electrophilic addition reaction to the hydroxyl group of the cyclic molecule of polyrotaxane (a).

  Examples of the reactive functional group of the functional monomer (b) include those similar to the reactive functional group I described above, for example, an isocyanate group, a thioisocyanate group, an oxirane group, an oxetane group, a carbodiimide group, and a silanol. Group, oxazoline group, aziridine group, epoxy group, dicarboxylic anhydride group and the like. Preferred are an isocyanate group, a thioisocyanate group, an epoxy group, and a dicarboxylic anhydride group (carboxylic anhydride group), and particularly preferred is an isocyanate group.

  Examples of the functional monomer (b) include 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isothiocyanate, 2-methacryloyloxyethyl isothiocyanate, allyl isocyanate, allyl isocyanate. Thiocyanate, glycidyl acrylate, glycidyl methacrylate, allyl isocyanate, allyl isothiocyanate, maleic anhydride, etc., preferably 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, glycidyl acrylate, glycidyl methacrylate, allyl isocyanate, allyl isothiocyanate And maleic anhydride, but is not limited thereto. These may be used alone or in combination of two or more.

<Reaction of polyrotaxane (a) and functional monomer (b)>
The amount of the functional monomer (b) used in the production of the modified polyrotaxane (A) by reacting the polyrotaxane (a) with the functional monomer (b) is the polyrotaxane crosslinked polymer (C) to be obtained. Since it is easy to adjust the gel content of 30 to 100% by mass, which is a preferable range described later, 0.1 to 99 parts per 100 parts by mass in total of the polyrotaxane (a) and the functional monomer (b). .9 parts by mass, particularly 1 to 50 parts by mass is preferable.

  As a method for producing the modified polyrotaxane (A) by reacting the polyrotaxane (a) with the functional monomer (b), known methods can be used, and the polyrotaxane can be used in a solvent or in the monomer (B) described later. Examples include a method in which (a) is dissolved and reacted with the functional monomer (b) by adding a catalyst or the like as necessary. Among these, a functional group having an isocyanate group, a thioisocyanate group, an epoxy group, or a dicarboxylic anhydride group as a reactive functional group in which the polyrotaxane (a) is dissolved in part or all of the monomer (B). The method of reacting the monomer (b) is more preferable because the reactivity is high and the reaction can be performed without using a catalyst or the like and without using a solvent.

<Commercially available modified polyrotaxane (A)>
As the modified polyrotaxane (A), for example, “Celum Superpolymer SM3405P”, “Celum Superpolymer SA3405P”, “Celum Superpolymer SA2405P” manufactured by Advanced Soft Materials Co., Ltd. can be used as commercially available products.

[Monomer (B)]
Next, the monomer (B) having a carbon-carbon double bond capable of radical polymerization and copolymerized with the modified polyrotaxane (A) of the present invention will be described.

  The monomer (B) in the present invention may be a compound having a carbon-carbon double bond capable of radical polymerization, and a polyfunctional compound or a monofunctional compound can be used. Although there is no restriction | limiting in particular, It is preferable to use a monofunctional compound as a monomer (B) from a viewpoint of the expressibility of the characteristic derived from the movement of a cyclic molecule. Moreover, only 1 type may be used for a monomer (B) and it may use it in combination of 2 or more type.

  Examples of the monomer (B) include, but are not limited to, (meth) acrylic acid esters, conjugated dienes, aromatic vinyls, vinyl cyanides, N-substituted maleimides, dicarboxylic acids, and the like. Examples include acid derivatives, fluorinated vinyls, (meth) acrylic acids, and (meth) acrylamides (where “(meth) acrylic” means one or both of “acrylic” and “methacrylic”). This also applies to “(meth) acrylate”. More specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, (meth) I-butyl acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, octyl (meth) acrylate, (meth) acrylate-2-ethylhexyl, (meth) acryl Decyl acid, lauryl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, pentyl (meth) acrylate, (meth) acrylic acid Phenyl, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid 2 (Meth) acrylic acid esters such as hydroxypropyl; conjugated dienes such as butadiene and isoprene; styrene, α-methylstyrene, o-, m- or p-methylstyrene, vinylxylene, pt-butylstyrene, ethyl Aromatic vinyls such as styrene; vinyl cyanides such as acrylonitrile and methacrylonitrile; N-substituted maleimides such as N-cyclohexylmaleimide and N-phenylmaleimide; dicarboxylic acid derivatives such as maleic anhydride; tetrafluoroethylene, Fluorinated vinyls such as perfluoropropylene and vinylidene fluoride; (meth) acrylic acids such as (meth) acrylic acid and (meth) acrylates; N, N-dimethyl (meth) acrylamide, N, N-diisopropyl ( (Meth) acrylamide, isopropyl (meth) Monofunctional compounds such as (meth) acrylamides such as acrylamide may be mentioned, and one of these may be used, or two or more may be used in combination. Among these, a combination in which the glass transition temperature after polymerization is not more than room temperature is preferable because it is difficult to inhibit the movement of the cyclic molecule on the linear molecule, and the hydrophobic one is a water having a desired particle size. Since it is easy to obtain a dispersion, conjugated dienes and (meth) acrylic acid esters are particularly preferable.

Moreover, you may use a polyfunctional compound as needed in the range which does not inhibit the movement on the linear molecule of a cyclic molecule. Examples of the polyfunctional compound include divinylbenzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-butylene di (meth) acrylate, and 1,4-butylene glycol. Di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetradecaethylene glycol di (meth) acrylate, triallyl cyanurate, triallyl isocyanurate, pentaerythritol tetra (meth) acrylate, polybutadiene having a molecular weight of 10,000 or less Etc.
These polyfunctional compounds may be used alone or in combination of two or more.

  By using a polyfunctional compound as the monomer (B), the effect of improving the strength of the polyrotaxane crosslinked polymer by chemical crosslinking and making the polyrotaxane crosslinked polymer further denatureable such as graft reaction can be obtained. If the amount is too large, the characteristics derived from the movement of the cyclic molecule are difficult to be exhibited. Therefore, the ratio of the polyfunctional compound in the monomer (B) is preferably 30% by mass or less.

[Ratio of modified polyrotaxane (A) and monomer (B)]
The ratio of the modified polyrotaxane (A) when the modified polyrotaxane (A) of the present invention is copolymerized with the monomer (B) to obtain the crosslinked polyrotaxane polymer (C) of the present invention is not particularly limited. 0.01 to 50% by mass, preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and further preferably 5 to 100% by mass of the total of the polyrotaxane (A) and the monomer (B). The proportion of the monomer (B) is 50 to 99.9% by mass, preferably 70 to 99.9% by mass, more preferably 80 to 99.0% by mass, and still more preferably 80 to 20% by mass. It is 95.0 mass%. When the ratio of the modified polyrotaxane (A) monomer (B) is within the above range, the polyrotaxane crosslinking function and the performance derived from the polymer of the monomer (B) are easily obtained.

[Production Method of Polyrotaxane Crosslinked Polymer (C)]
In the present invention, when the modified polyrotaxane (A) and the monomer (B) are copolymerized, a part or all of the modified polyrotaxane (A) and the monomer (B) are in an aqueous solvent. In the presence of an emulsifier, preferably in the presence of an emulsifier and a hydrophobic stabilizer, shear is applied to form a miniemulsion, followed by copolymerization in the presence of a radical initiator. A polymer (C) is produced. The radical initiator may be added before or after forming the mini-emulsion, and the radical initiator, the modified polyrotaxane (A) and the monomer (B), the emulsifier, and the hydrophobic stabilizer may be added at once. , Divided or continuous. The emulsifier added in the miniemulsification step also functions as an emulsifier for emulsion polymerization in the copolymerization step after the miniemulsion step.

  Any known method can be used to apply shear when forming a mini-emulsion, which may be batch, divided, continuous or circulating, and generally forms droplets with a particle size of about 10 to 2000 nm. A mini-emulsion can be formed by using a high shearing device. The high-shear device that forms the mini-emulsion is not limited to these. For example, an emulsifier comprising a pressure homogenizer, a high-pressure pump, and an interaction chamber, and emulsification that forms a mini-emulsion using ultrasonic energy and high frequency. There are devices. Examples of the pressure homogenizer include a piston gap homogenizer and a Manton gorin homogenizer. Examples of the emulsifying apparatus including a high-pressure pump and an interaction chamber include a microfluidizer manufactured by POWREC Co., Ltd. Examples of the apparatus for forming a mini-emulsion by high frequency include a Sonic Dismulator manufactured by Fisher Scientific, and ULTRASONIC HOMOGENIZER manufactured by Nippon Seiki Seisakusho.

  After forming a mini-emulsion as in the present invention, by performing radical copolymerization, the modified polyrotaxane (A), which is a high molecular weight substance, is efficiently taken into the micelle, and the stability during production is improved and the particles The diameter can be easily controlled.

  Examples of the emulsifier used for forming the miniemulsion include anionic surfactants, nonionic surfactants, and amphoteric surfactants. For example, sulfates of higher alcohols, alkylbenzene sulfonates, fatty acid sulfonates, phosphorus Anionic surfactants such as acid salts (for example, monoglyceride ammonium phosphate), fatty acid salts (for example, dipotassium alkenyl succinate), amino acid derivative salts, ordinary polyethylene glycol alkyl ester type, alkyl ether type, alkyl phenyl ether Type nonionic surfactant, carboxylate, sulfate ester salt, sulfonate salt, phosphate ester salt etc. in the anion part, amphoteric surfactant having amine salt, quaternary ammonium salt etc. in the cation part Agents. These may be used alone or in combination of two or more.

  The amount of the emulsifier added is usually 10 parts by mass or less, for example, 0.01 to 10 parts by mass with respect to 100 parts by mass in total of the modified polyrotaxane (A) and the monomer (B).

  When forming a miniemulsion, if a hydrophobic stabilizer is added, the production stability of the miniemulsion tends to be further improved. Hydrophobic stabilizers include non-polymerizable hydrophobic compounds such as hydrocarbons having 10 to 30 carbon atoms, alcohols having 10 to 30 carbon atoms (preferably 10 to 24 carbon atoms), and mass average molecular weight (Mw). Hydrophobic polymer of less than 10,000, tetraalkylsilane, hydrophobic monomer, for example, vinyl ester of alcohol having 10 to 30 carbon atoms, vinyl ether of alcohol having 12 to 30 carbon atoms, alkyl acrylate having 12 to 22 carbon atoms, carbon number of 10 To 30 (preferably 10 to 22 carbon atoms) carboxylic acid vinyl ester, (meth) acrylic acid ester having 8 to 30 carbon atoms, p-alkylstyrene, hydrophobic chain transfer agent, hydrophobic peroxide, etc. Can be mentioned. These may be used alone or in combination of two or more.

  Specific examples of the hydrophobic stabilizer include decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, olive oil, polystyrene having a weight average molecular weight (Mw) of 500 to 5,000, and a weight average molecular weight (Mw). 500-5000 siloxane, cetyl alcohol, stearyl alcohol, palmityl alcohol, behenyl alcohol, p-methylstyrene, (meth) acrylate-2-ethylhexyl, decyl (meth) acrylate, stearyl (meth) acrylate, (meth) Lauryl acrylate, stearyl methacrylate, lauryl mercaptan (normal dodecyl mercaptan), and hydrophobic peroxides include benzoyl peroxide (BPO), lauroyl peroxide (LPO), dimethyl bis (te t-butylperoxy) hexyne-3, bis (tert-butylperoxyisopropyl) benzene, bis (tert-butylperoxy) trimethylcyclohexane, butyl-bis (tert-butylperoxy) valerate, 2-ethylhexaneperoxy acid Examples include tert-butyl, dibenzoyl peroxide, paramentane hydroperoxide, and tert-butyl peroxybenzoate.

  When a hydrophobic stabilizer is used, the amount added is usually 0.05 to 8 parts by mass, preferably 0.3 with respect to 100 parts by mass in total of the modified polyrotaxane (A) and the monomer (B). -5 parts by mass, more preferably 0.3-3 parts by mass. When the amount of the hydrophobic stabilizer added is less than the above range, an aqueous dispersion of the polyrotaxane crosslinked polymer (C) having a desired particle size may not be obtained or the production stability may be inferior. When it exceeds, the original characteristic of the obtained polyrotaxane crosslinked polymer (C) may be difficult to obtain.

  Known radical initiators used for emulsion polymerization can be used, for example, azo polymerization initiators, photopolymerization initiators, inorganic peroxides, organic peroxides, organic peroxides, transition metals, and reducing agents. A combined redox initiator and the like can be mentioned. Of these, azo polymerization initiators, inorganic peroxides, organic peroxides, and redox initiators that can initiate polymerization by heating are preferred. These may be used alone or in combination of two or more.

  Examples of the azo polymerization initiator include 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), and 2,2′-. Azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl) Azo] formamide, 4,4′-azobis (4-cyanovaleric acid), dimethyl 2,2′-azobis (2-methylpropionate), dimethyl 1,1′-azobis (1-cyclohexanecarboxylate) ), 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis (N-butyl-2-methylpropionamide) ), 2,2′-azobis (N-cyclohexyl-2-methylpropionamide), 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis (2,4 , 4-trimethylpentane) and the like.

  Examples of inorganic peroxides include potassium persulfate, sodium persulfate, ammonium persulfate, and hydrogen peroxide.

  Examples of the organic peroxide include peroxyester compounds, and specific examples thereof include α, α′-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3, 3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1- Cyclohexyl-1-methylethylperoxy-2-ethylhexano , T-hexylperoxy 2-hexylhexanoate, t-butylperoxy 2-hexylhexanoate, t-butylperoxyisobutyrate, t-hexylperoxyisopropylmonocarbonate, t-butylperoxymaleic acid, t- Butyl peroxy 3,5,5-trimethylhexanoate, t-butyl peroxylaurate, 2,5-dimethyl-2,5-bis (m-toluoyl peroxy) hexane, t-butyl peroxyisopropyl monocarbonate, t- Butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxy-m-toluoyl Nzoate, t-butylperoxybenzoate, bis (t-butylperoxy) isophthalate, 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 2, 2-bis (t-butylperoxy) butane, n-butyl 4,4-bis (t-butylperoxy) valerate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, α, α '-Bis (t-butyl peroxide) diisopropylbenzene, dicumyl peroxide, 2,5- Methyl-2,5-bis (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, t-butyl hydroperoxide, benzoyl peroxide (BPO) , Lauroyl peroxide (LPO), dimethylbis (tert-butylperoxy) hexyne-3, bis (tert-butylperoxyisopropyl) benzene, bis (tert-butylperoxy) trimethylcyclohexane, butyl-bis (tert-butyl) Peroxy) valerate, tert-butyl 2-ethylhexaneperoxyate, dibenzoyl peroxide, paramentane hydroperoxide, tert-butyl peroxybenzoate, etc. And the like.

  As the redox initiator, a combination of an organic peroxide, ferrous sulfate, a chelating agent and a reducing agent is preferable. Examples include cumene hydroperoxide, ferrous sulfate, sodium pyrophosphate, and dextrose, and those used in the examples described later.

  The addition amount of the radical initiator is 5 parts by mass or less, preferably 3 parts by mass or less, for example, 0.001 to 3 parts by mass with respect to 100 parts by mass in total of the modified polyrotaxane (A) and the monomer (B). It is.

You may add a chain transfer agent as needed at the time of manufacture of a polyrotaxane crosslinked polymer (C). Examples of chain transfer agents include mercaptans (octyl mercaptan, n- or t-dodecyl mercaptan, n-hexadecyl mercaptan, n- or t-tetradecyl mercaptan, etc.), allyl compounds (allylsulfonic acid, methallylsulfonic acid, these Sodium salts, etc.), α-methylstyrene dimers, and the like, and mercaptans are preferred from the viewpoint of easy adjustment of the molecular weight. A chain transfer agent may be used individually by 1 type, and may be used in combination of 2 or more type.
The method for adding the chain transfer agent may be any of batch, split, and continuous.
The addition amount of the chain transfer agent is preferably 2.0 parts by mass or less, for example, 0.01 to 2.0 parts by mass with respect to 100 parts by mass in total of the modified polyrotaxane (A) and the monomer (B).

  The miniemulsification step is preferably performed at room temperature, for example, 0 to 65 ° C without heating, so that copolymerization does not proceed before a uniform miniemulsion is obtained. In particular, when a radical initiator is also added during the formation of the miniemulsion, the temperature is preferably 50 ° C. or lower. In order to prevent the progress of copolymerization in the miniemulsion step, it may be preferable to add the radical initiator after the miniemulsion is formed.

  The copolymerization of the modified polyrotaxane (A) and the monomer (B) after the miniemulsion step is usually carried out at 30 to 120 ° C. for about 0.5 to 20 hours.

  The copolymerization of the modified polyrotaxane (A) and the monomer (B) in the miniemulsion is preferably performed in an aqueous reaction solvent having a solid content concentration of about 5 to 50% by mass. An aqueous dispersion containing about 5 to 49% by mass of the polyrotaxane crosslinked polymer (C) can be obtained.

<Gel content>
The gel content of the polyrotaxane crosslinked polymer (C) of the present invention produced by the method for producing the polyrotaxane crosslinked polymer (C) of the present invention is not particularly limited, but is usually 30 to 100% by mass, particularly 40 to 100%. It is preferable to adjust to a desired gel content depending on the application in the range of mass%, particularly 60 to 98 mass%. When the gel content of the polyrotaxane crosslinked polymer (C) is within the above range, the polyrotaxane crosslinking function is easily exhibited.

  The gel content of the polyrotaxane crosslinked polymer (C) includes the amount of the functional monomer (b) to be reacted with the polyrotaxane (a), the amount of the modified polyrotaxane (A) added to the reaction system, and the monomer (B). The amount of the functional monomer (b) and the amount of the modified polyrotaxane (A) added are larger, and the molecular weight of the polymer of the monomer (B) is larger. The gel content tends to be high.

  In addition, the gel content rate of the polyrotaxane crosslinked polymer (C) in the present invention indicates the degree of crosslinking of the polyrotaxane crosslinked polymer (C), and specifically, 20% of the weighed polyrotaxane crosslinked polymer (C) is used as a solvent. Dissolved over time, then separated with a 200 mesh wire mesh, dried insoluble matter remaining in the wire mesh, weighed, and dried insoluble matter for the polyrotaxane crosslinked polymer (C) before being dissolved in the solvent It is calculated | required by a ratio (mass%). The solvent for dissolving the polyrotaxane crosslinked polymer (C) may be any solvent that dissolves the polymer of the monomer (B). For example, the polymer of the monomer (B) may be polybutadiene, polyisoprene, or the like. In the case of conjugated dienes and their copolymers, toluene is preferred, and in the case of polyacrylates and their copolymers, acetone is preferred.

<Volume average particle diameter>
According to the method for producing a polyrotaxane crosslinked polymer (C) of the present invention, the polyrotaxane crosslinked polymer (C) is produced as an aqueous dispersion in which the polyrotaxane crosslinked polymer (C) is dispersed in an aqueous solvent. The volume average particle diameter in the aqueous dispersion of the obtained polyrotaxane crosslinked polymer (C) (volume average particle diameter of the dispersed particles of the polyrotaxane crosslinked polymer (C)) is usually 5 to 3000 nm, preferably 10 to 2000 nm. Preferably it is 10-1200 nm, More preferably, it is 70-600 nm, Most preferably, it is 100-200 nm. When the volume average particle diameter of the aqueous dispersion of the polyrotaxane crosslinked polymer (C) is within the above range, the production stability and long-term stability of the aqueous dispersion of the obtained polyrotaxane crosslinked polymer (C) are excellent.

  The volume average particle diameter of the aqueous dispersion of the polyrotaxane crosslinked polymer (C) may be adjusted to the desired volume average particle diameter in the above range depending on the application. Although it does not specifically limit as a method of adjusting the volume average particle diameter of the water dispersion of a polyrotaxane crosslinked polymer (C), The method of adjusting with the addition amount of the emulsifier added at the time of manufacture by an emulsion polymerization method, It manufactured by emulsion polymerization. A method of adding an acid or the like to an aqueous dispersion of the polyrotaxane crosslinked polymer (C), a method of adding an aqueous dispersion of an acid group-containing copolymer (acid group-containing copolymer latex) after adding a condensed acid salt And a method of physically aggregating the aqueous dispersion of the crosslinked polyrotaxane polymer (C) produced by emulsion polymerization with mechanical shearing. In general, the smaller the added amount of the emulsifier, the larger the added amount of the acid, the larger the added amount of the aqueous dispersion of the condensed acid salt and the acid group-containing copolymer, the larger the volume average particle size. There is a tendency.

  When the polyrotaxane crosslinked polymer (C) is enlarged, the acid used may be either a strong acid or a weak acid, and may be either an organic acid or an inorganic acid. However, since the volume average particle diameter can be easily adjusted, dodecylbenzenesulfone In a system using an emulsifier that is stable in an acidic region such as an acid salt, it is preferable to use a weak acid such as formic acid or acetic acid. Further, a base or the like may be added after the reaction.

When the polyrotaxane crosslinked polymer (C) is enlarged, when the acid group-containing copolymer latex is added after the condensation acid salt is added, as the condensation acid salt added before mixing the acid group-containing copolymer latex, A salt of a condensed acid and an alkali metal is preferred. The condensed acid is a polynuclear acid condensed with an oxo acid. Examples of the condensed acid include polyphosphoric acid (such as pyrophosphoric acid). As the condensed acid salt, a salt of a condensed acid such as phosphoric acid or silicic acid and an alkali metal and / or alkaline earth metal is used, and a salt of pyrophosphoric acid and an alkali metal, which is a condensed acid of phosphoric acid, is preferable. Sodium pyrophosphate or potassium pyrophosphate is particularly preferred.
The addition amount of the condensed acid salt is preferably 0.1 to 10 parts by mass, and 0.5 to 7 parts by mass with respect to 100 parts by mass (as solid content) of the acid group-containing copolymer latex. More preferred. If the addition amount of the condensed acid salt is less than the above lower limit, the enlargement does not proceed sufficiently. If the above upper limit is exceeded, enlargement may not proceed sufficiently, or the rubber latex may become unstable and a large amount of agglomerates may be generated.

The acid group-containing copolymer latex is 5-30% by mass of an acid group-containing monomer, 95-70% by mass of (meth) acrylic acid esters, and other copolymerizable with these in water. It is the aqueous dispersion of the acid group containing copolymer obtained by superposing | polymerizing the monomer mixture containing 0-25 mass% of these monomers.
As the acid group-containing monomer, an unsaturated compound having a carboxy group is preferable. Examples of the compound include (meth) acrylic acid, itaconic acid, crotonic acid and the like, and (meth) acrylic acid is particularly preferable. An acid group containing monomer may be used individually by 1 type, and may use 2 or more types together.
Examples of the (meth) acrylic acid esters include those similar to the (meth) acrylic acid esters shown for the monomer (B). (Meth) acrylic acid esters may be used alone or in combination of two or more.
The other monomer is a monomer copolymerizable with an acid group-containing monomer and (meth) acrylic acid esters, and is a single monomer excluding the acid group-containing monomer and (meth) acrylic acid esters. It is a mer. Examples of the other monomer include conjugated dienes, aromatic vinyls, vinyl cyanides, N-substituted maleimides, maleic anhydride, and fluorinated vinyls shown in the monomer (B). Another monomer may be used individually by 1 type and may use 2 or more types together.

  The use ratio of the acid group-containing monomer in producing the acid group-containing copolymer latex is preferably 5 to 30% by mass in the monomer mixture (100% by mass). When the ratio of the acid group-containing monomer is 5% by mass or more, the aqueous dispersion of the polyrotaxane crosslinked polymer (C) can be sufficiently enlarged. When the ratio of the acid group-containing monomer is 30% by mass or less, the production of an agglomerate is suppressed when an aqueous dispersion of the acid group-containing copolymer is produced.

<Recovery of polyrotaxane crosslinked polymer (C)>
The aqueous dispersion of the polyrotaxane crosslinked polymer (C) produced by the method for producing the polyrotaxane crosslinked polymer (C) of the present invention may be used as it is, or the polyrotaxane crosslinked polymer (C) may be recovered and used. May be. As a method for recovering the polyrotaxane crosslinked polymer (C) from the aqueous dispersion of the polyrotaxane crosslinked polymer (C), the aqueous dispersion is poured into hot water in which a coagulant is dissolved, and coagulated in a slurry state. A method of recovering the polyrotaxane crosslinked polymer (C) by spraying an aqueous dispersion of the polyrotaxane crosslinked polymer (C) in a heated atmosphere, and a method of recovering the polyrotaxane crosslinked polymer (C) semi-directly in a heated atmosphere. Examples thereof include a method of evaporating and drying water such as an aqueous dispersion of the polymer (C).

  Examples of the coagulant include inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid; metal salts such as calcium chloride, calcium acetate and aluminum sulfate. The coagulant is selected according to the emulsifier used in the polymerization, that is, the emulsifier added in the miniemulsification step. That is, when only carboxylic acid soaps such as fatty acid soaps and rosin acid soaps are used, any coagulant may be used, but emulsifiers exhibiting stable emulsifying power in acidic regions such as sodium dodecylbenzenesulfonate are included. If so, it is necessary to use a metal salt.

[Usage]
According to the present invention, it becomes possible to obtain a crosslinked polymer of various polymers having a function derived from polyrotaxane crosslinking, and the obtained polyrotaxane crosslinked polymer (C) is an aqueous dispersion having a desired gel content and particle size. Since the polyrotaxane crosslinked polymer (C) of the present invention and its aqueous dispersion can be obtained in the form of a coating, an adhesive, a sheet, a film, an electrical and electronic material, a resin modifier, their raw materials and modified materials. It can be used effectively as a quality agent.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated concretely, this invention is not limited to the following Example.

[Evaluation of physical properties and characteristics]
Evaluation methods of physical properties and characteristics in the following examples and comparative examples are as follows.

[Gel content]
The weighed polyrotaxane cross-linked polymer (C) or polymer (C ′) is dissolved in a solvent for 20 hours, then separated by a 200 mesh wire mesh, and the insoluble matter remaining in the wire mesh is dried and weighed. It calculated | required by the ratio (mass%) of the insoluble matter dried with respect to the polyrotaxane crosslinked polymer (C) (or polymer (C ')) before making it melt | dissolve in a solvent. As the solvent, acetone was used when an acrylic ester such as butyl acrylate was used as the monomer (B), and toluene was used when 1,3-butadiene was used.

[Mobility of cyclic molecules]
In polyrotaxanes in which cyclic molecules move on linear molecules, the transition associated with the movement of cyclic molecules on linear molecules is observed between the glass transition point and the rubbery flat region in the viscoelasticity measurement chart. (Polymer Society of Polymer Science, 11-6 Polymer Frontier 21 “Network Polymer” Abstract), polyrotaxane crosslinked polymer (C) or polymer (C ′) was press-molded at 150 ° C. The storage elastic modulus E ′ was measured at 1 Hz and −105 ° C. to 80 ° C. using a viscoelasticity measuring device “Physic MCR301” manufactured by Anton Paar, and between the glass transition point and the rubbery flat region in the measurement chart. Observe whether or not the transition associated with the movement of the cyclic molecule on the linear molecule is observed, and evaluate as follows. There was to have the property of moving on a linear molecule.
○: Transition associated with the movement of a cyclic molecule on a linear molecule is clearly seen.
(Triangle | delta): The transition accompanying a cyclic molecule moving on a linear molecule is seen slightly.
X: No transition associated with the movement of the cyclic molecule on the linear molecule is observed.

[Volume average particle diameter]
Volume average particle diameter (MV) in an aqueous dispersion of polyrotaxane crosslinked polymer (C) or polymer (C ′) using Microtrac (manufactured by Nikkiso Co., Ltd., “Nanotrack 150”) using pure water as a measurement solvent ) Was measured.

[Stability of water dispersion]
Whether an aqueous dispersion of the polyrotaxane crosslinked polymer (C) or the polymer (C ′) is filtered through a 100-mesh wire net and left to stand at 25 ° C. for 10 days and 60 days. This was evaluated as follows, and “Δ”, “◯”, or “」 ”was regarded as stable in the polyrotaxane crosslinked polymer (C) or the aqueous dispersion of the polymer (C ′).
(Double-circle): A deposit is not seen even if it is left for 60 days.
◯: No precipitate is observed after standing for 10 days.
Δ: Slight precipitate is observed.
X: Many precipitates are seen.

[Manufacturing stability]
The polyrotaxane crosslinked polymer (C) or the aqueous dispersion of the polymer (C ′) is filtered through a 100-mesh wire mesh, and the solidified material remaining on the 100-mesh wire mesh is dried and weighed to obtain a polyrotaxane crosslinked polymer (C). The ratio (mass%) to (or polymer (C ′)) was determined. The smaller the amount of coagulum, the better the production stability of the polyrotaxane crosslinked polymer (C) or the aqueous dispersion of the polymer (C ′).

[Production of Polyrotaxane Crosslinked Polymer (C) or Polymer (C ′)]
[Example 1: Polyrotaxane crosslinked polymer (C-1)]
In 94.8 parts by mass of butyl acrylate, 0.2 part by mass of 2-acryloyloxyethyl isocyanate and 5 parts by mass of polyrotaxane (manufactured by Advanced Soft Materials Co., Ltd., “Celum Superpolymer SH3400P”) are dissolved at 60 ° C. A butyl acrylate solution in which the modified polyrotaxane was dissolved was obtained by reacting for 8 hours.
The details of “Celum Superpolymer SH3400P” used here are as follows.
Linear molecule: Polyethylene glycol having an adamantane group at both ends as a blocking group and having a number average molecular weight of 35,000 Cyclic molecule: α-cyclodextrin Polymer part of the cyclic molecule: Polycaprolactone Hydroxyl value of polyrotaxane: 72 mg-KOH / g
Number average molecular weight of polyrotaxane: 700,000

  Mixing of 310 parts by weight of deionized water, 1 part by weight of dipotassium alkenyl succinate, 0.2 parts by weight of t-butyl hydroperoxide, and 2.5 parts by weight of hexadecane with a butyl acrylate solution of the modified polyrotaxane obtained above While stirring, the solution was subjected to ultrasonic irradiation with an amplitude 35 μm for 20 minutes using ULTRASONIC HOMOGENIZER US-600 manufactured by Nippon Seiki Seisakusho to obtain a mini-emulsion of a modified polyrotaxane in butyl acrylate. In addition, this miniemulsion process was performed at 25 degreeC. The same applies to Examples and Comparative Examples described later.

A reaction vessel equipped with a reagent injection vessel, a cooling tube, a jacket heater and a stirrer is charged with the mini-emulsion of the modified polyrotaxane butyl acrylate solution obtained above, and after the reaction vessel is purged with nitrogen, the temperature is raised to 55 ° C. Warm up. Next, 0.3 parts by mass of sodium formaldehyde sulfoxylate, 0.0001 parts by mass of ferrous sulfate heptahydrate, 0.0003 parts by mass of disodium ethylenediaminetetraacetate and 10 parts by mass of deionized water were added to initiate polymerization. I let you. After the polymerization exotherm is confirmed, the jacket temperature is set to 75 ° C., the polymerization is continued until the polymerization exotherm is not confirmed, and further maintained for 1 hour to obtain an aqueous dispersion of the polyrotaxane crosslinked polymer (C-1). It was.
The volume average particle diameter of the aqueous dispersion of the obtained polyrotaxane crosslinked polymer (C-1) was 143 nm.
Subsequently, the aqueous dispersion of the polyrotaxane crosslinked polymer (C-1) was coagulated, washed with water and dried using a 5% by mass sulfuric acid aqueous solution to obtain a polyrotaxane crosslinked polymer (C-1).

[Example 2: Polyrotaxane crosslinked polymer (C-2)]
By reacting under the same conditions as in Example 1 except that the amount of butyl acrylate used in the production of the modified polyrotaxane was 81.8 parts by mass and the amount of polyrotaxane used was 18 parts by mass, a polyrotaxane crosslinked polymer (C -2) and its aqueous dispersion were obtained. The volume average particle diameter of the aqueous dispersion of the polyrotaxane crosslinked polymer (C-2) was 155 nm.

[Example 3: Polyrotaxane crosslinked polymer (C-3)]
A polyrotaxane crosslinked polymer (C) was prepared by carrying out the reaction under the same conditions as in Example 1 except that the amount of butyl acrylate used in the production of the modified polyrotaxane was 74.8 parts by mass and the amount of polyrotaxane used was 25 parts by mass. -3) and an aqueous dispersion thereof were obtained. The volume average particle diameter of the aqueous dispersion of the polyrotaxane crosslinked polymer (C-3) was 157 nm.

[Example 4: Polyrotaxane crosslinked polymer (C-4)]
By reacting under the same conditions as in Example 1 except that the amount of butyl acrylate used in the production of the modified polyrotaxane was 67.8 parts by mass and the amount of polyrotaxane used was 32 parts by mass, a crosslinked polyrotaxane polymer (C -4) and an aqueous dispersion thereof. The volume average particle diameter of the aqueous dispersion of the polyrotaxane crosslinked polymer (C-4) was 163 nm.

[Example 5: Polyrotaxane crosslinked polymer (C-5)]
By reacting under the same conditions as in Example 1 except that the amount of butyl acrylate used in the production of the modified polyrotaxane was 47.8 parts by mass and the amount of polyrotaxane used was 52 parts by mass, a crosslinked polyrotaxane polymer (C -5) and an aqueous dispersion thereof were obtained. The volume average particle diameter of the aqueous dispersion of the polyrotaxane crosslinked polymer (C-5) was 182 nm.

[Example 6: Polyrotaxane crosslinked polymer (C-6)]
By reacting under the same conditions as in Example 1 except that the amount of butyl acrylate used in the production of the modified polyrotaxane was 98.8 parts by mass and the amount of polyrotaxane used was 1 part by mass, a polyrotaxane crosslinked polymer (C -6) and an aqueous dispersion thereof were obtained. The volume average particle diameter of the aqueous dispersion of the polyrotaxane crosslinked polymer (C-6) was 147 nm.

[Example 7: Polyrotaxane crosslinked polymer (C-7)]
Example except that the amount of butyl acrylate used in the production of the modified polyrotaxane was 99.8 parts by mass, the amount of 2-acryloyloxyethyl isocyanate used was 0.1 parts by mass, and the amount of polyrotaxane used was 0.1 parts by mass. By carrying out the reaction under the same conditions as in Example 1, a polyrotaxane crosslinked polymer (C-7) and an aqueous dispersion thereof were obtained. The volume average particle diameter of the aqueous dispersion of the polyrotaxane crosslinked polymer (C-7) was 138 nm.

[Example 8: Polyrotaxane crosslinked polymer (C-8)]
Example except that the amount of butyl acrylate used in the production of the modified polyrotaxane was 99.9 parts by mass, the amount of 2-acryloyloxyethyl isocyanate used was 0.05 parts by mass, and the amount of polyrotaxane used was 0.05 parts by mass. By carrying out the reaction under the same conditions as in Example 1, a polyrotaxane crosslinked polymer (C-8) and an aqueous dispersion thereof were obtained. The volume average particle diameter of the aqueous dispersion of the polyrotaxane crosslinked polymer (C-8) was 135 nm.

[Example 9: Polyrotaxane crosslinked polymer (C-9)]
By carrying out the reaction under the same conditions as in Example 1 except that the amount of butyl acrylate used in the production of the modified polyrotaxane was 94.4 parts by mass and the amount of 2-acryloyloxyethyl isocyanate used was 0.6 parts by mass. Polyrotaxane cross-linked polymer (C-9) and an aqueous dispersion thereof were obtained. The volume average particle diameter of the aqueous dispersion of the polyrotaxane crosslinked polymer (C-9) was 140 nm.

[Example 10: Polyrotaxane crosslinked polymer (C-10)]
By performing the reaction under the same conditions as in Example 1 except that the amount of butyl acrylate used in the production of the modified polyrotaxane was 93.5 parts by mass and the amount of 2-acryloyloxyethyl isocyanate used was 1.5 parts by mass. Polyrotaxane cross-linked polymer (C-10) and an aqueous dispersion thereof were obtained. The volume average particle diameter of the aqueous dispersion of the polyrotaxane crosslinked polymer (C-10) was 143 nm.

[Example 11: Polyrotaxane crosslinked polymer (C-11)]
In the production of the modified polyrotaxane, a polyrotaxane crosslinked polymer (C-11) was prepared by carrying out the reaction under the same conditions as in Example 1 except that 0.2 parts by mass of glycidyl methacrylate was used instead of 2-acryloyloxyethyl isocyanate. And an aqueous dispersion thereof. The volume average particle diameter of the aqueous dispersion of the polyrotaxane crosslinked polymer (C-11) was 145 nm.

[Example 12: Polyrotaxane crosslinked polymer (C-12)]
In the production of the modified polyrotaxane, a polyrotaxane crosslinked polymer (C--) was prepared by reacting under the same conditions as in Example 1 except that 0.2 parts by mass of maleic anhydride was used instead of 2-acryloyloxyethyl isocyanate. 12) and an aqueous dispersion thereof were obtained. The volume average particle diameter of the aqueous dispersion of the polyrotaxane crosslinked polymer (C-12) was 157 nm.

[Example 13: Polyrotaxane crosslinked polymer (C-13)]
72.55 parts by mass of 2-ethylhexyl acrylate, 20.05 parts by mass of acrylonitrile, 0.2 parts by mass of allyl methacrylate, 0.2 parts by mass of 2-acryloyloxyethyl isocyanate, polyrotaxane (manufactured by Advanced Soft Materials Co., Ltd.) , “Celum Superpolymer SH3400P”) was dissolved in 5 parts by mass and reacted at 60 ° C. for 8 hours, and then 2 parts by mass of acrylic acid was added to obtain a monomer mixture in which the modified polyrotaxane was dissolved.

  In a monomer mixture in which 310 parts by weight of deionized water, 0.9 parts by weight of sodium dodecylbenzenesulfonate, 0.2 parts by weight of ammonium persulfate, and 2.5 parts by weight of hexadecane were dissolved in the modified polyrotaxane obtained above. While stirring, ultrasonic irradiation was performed for 20 minutes with an amplitude of 35 μm using ULTRASONIC HOMOGENIZER US-600 manufactured by Nippon Seiki Seisakusho to obtain a mini-emulsion of a monomer mixture in which the modified polyrotaxane was dissolved.

Dispersion of polyrotaxane cross-linked polymer (C-13) in water by charging the obtained mini-emulsion into a reaction vessel equipped with a reagent injection vessel, a cooling tube, a jacket heater and a stirrer and reacting at 60 ° C. for 3 hours. Got the body. The volume average particle diameter of the aqueous dispersion of the obtained polyrotaxane crosslinked polymer (C-13) was 162 nm.
Next, the aqueous dispersion of the polyrotaxane crosslinked polymer (C-13) was coagulated, washed with water and dried using a 32% by mass calcium chloride aqueous solution to obtain a polyrotaxane crosslinked polymer (C-13).

[Example 14: Polyrotaxane crosslinked polymer (C-14)]
2 parts by mass of 2-acryloyloxyethyl isocyanate and 1 part by mass of polyrotaxane (manufactured by Advanced Soft Materials, “Celum Superpolymer SH3400P”) are dissolved in 5 parts by mass of xylene and reacted at 60 ° C. for 8 hours. And 25 parts by mass of the resulting solution and liquid polybutadiene (Aldrich Polybutadiene, number average molecular weight of about 3000), 25 parts by mass of isoprene, 0.3 parts by mass of t-dodecyl mercaptan, 0.15 parts by mass of potassium persulfate, While mixing with a mixed solution of 1.5 parts by mass of sodium rosinate, 0.02 parts by mass of sodium hydroxide, and 200 parts by mass of deionized water, using ULTRASONIC HOMOGENIZER US-600 manufactured by Nippon Seiki Seisakusho Co., Ltd. Ultrasonic irradiation for 20 minutes with an amplitude of 35 μm To give a mini-emulsion of the taxane. The obtained miniemulsion and 48.8 parts by mass of 1,3-butadiene are added to a pressure-resistant reaction vessel equipped with a jacket heater and a stirrer and reacted at 60 ° C. for 15 hours, whereby a polyrotaxane crosslinked polymer (C An aqueous dispersion of -14) was obtained. The volume average particle diameter of the aqueous dispersion of the obtained polyrotaxane crosslinked polymer (C-14) was 157 nm.
Subsequently, the aqueous dispersion of the polyrotaxane crosslinked polymer (C-14) was coagulated, washed with water and dried using a 5% by mass sulfuric acid aqueous solution to obtain a polyrotaxane crosslinked polymer (C-14).

[Example 15: Polyrotaxane crosslinked polymer (C-15)]
A polyrotaxane crosslinked polymer (C-15) and an aqueous dispersion thereof were obtained by carrying out the reaction under the same conditions as in Example 14 except that isoprene was changed to 25 parts by mass of styrene. The volume average particle diameter of the aqueous dispersion of the polyrotaxane crosslinked polymer (C-15) was 142 nm.

[Example 16: Polyrotaxane crosslinked polymer (C-16)]
By carrying out the reaction under the same conditions as in Example 1 except that the amount of dipotassium alkenyl succinate was 0.5 parts by mass and the amplitude of ultrasonic irradiation was 20 μm, the polyrotaxane crosslinked polymer (C-16) and An aqueous dispersion was obtained. The volume average particle diameter of the aqueous dispersion of the polyrotaxane crosslinked polymer (C-16) was 342 nm.

[Example 17: Polyrotaxane crosslinked polymer (C-17)]
In a reaction vessel equipped with a reagent injection vessel, a condenser, a jacket heater and a stirrer, 200 parts by mass of deionized water, 2.1 parts by mass of potassium oleate, 4.2 parts by mass of sodium dioctylsulfosuccinate, ferrous sulfate After adding 0.003 part by mass of heptahydrate, 0.009 part by mass of sodium ethylenediaminetetraacetate and 0.3 part by mass of sodium formaldehyde sulfoxylate, the reaction vessel was purged with nitrogen, and then the temperature was raised to 60 ° C. Next, 81.4 parts by mass of butyl acrylate, 18.6 parts by mass of acrylic acid, and 0.5 parts by mass of cumene hydroperoxide were added dropwise over 2 hours, followed by further reaction for 2 hours, thereby producing an acid group-containing copolymer. An aqueous dispersion was obtained.
Into the reactor, 2.4 parts by mass of sodium pyrophosphate was added as a 5% by mass aqueous solution to 100 parts by mass (in terms of solid content) of the aqueous dispersion of the polyrotaxane crosslinked polymer (C-1) obtained in Example 1. After sufficiently stirring, 1.8 parts by mass (in terms of solid content) of an aqueous dispersion of the acid group-containing copolymer obtained above was added. An aqueous dispersion of the polyrotaxane crosslinked polymer (C-17) was obtained by stirring for 30 minutes while maintaining the internal temperature of 30 ° C. The volume average particle diameter of the aqueous dispersion of the polyrotaxane crosslinked polymer (C-17) was 573 nm.
Next, the polyrotaxane crosslinked polymer (C-17) was solidified, washed with water and dried in the same manner as in Example 1 to obtain a polyrotaxane crosslinked polymer (C-17).

[Example 18: Polyrotaxane crosslinked polymer (C-18)]
A polyrotaxane crosslinked polymer (C-18) and an aqueous dispersion thereof were obtained by performing the reaction under the same conditions as in Example 17 except that the amount of sodium pyrophosphate used was 3.1 parts by mass. The volume average particle diameter of the aqueous dispersion of the polyrotaxane crosslinked polymer (C-18) was 658 nm.

[Example 19: Polyrotaxane crosslinked polymer (C-19)]
After adding 0.15 parts by mass of sodium dodecylbenzenesulfonate to 100 parts by mass (in terms of solid content) of the aqueous dispersion of the polyrotaxane crosslinked polymer (C-1) obtained in Example 1, a 5% by mass acetic acid aqueous solution. 50 parts by mass were added dropwise over 30 minutes. After completion of dropping, a 10% by mass aqueous sodium hydroxide solution was added dropwise over 10 minutes to obtain a polyrotaxane crosslinked polymer (C-19) and an aqueous dispersion thereof. The volume average particle diameter of the aqueous dispersion of the polyrotaxane crosslinked polymer (C-19) was 1178 nm.

[Example 20: Polyrotaxane crosslinked polymer (C-20)]
A polyrotaxane crosslinked polymer (C-20) and an aqueous dispersion thereof were obtained by carrying out the reaction under the same conditions as in Example 19 except that the amount of 5% aqueous acetic acid used was 60 parts by mass. The volume average particle diameter of the aqueous dispersion of the polyrotaxane crosslinked polymer (C-20) was 1266 nm.

[Example 21: Polyrotaxane crosslinked polymer (C-21)]
After adding 0.15 parts by mass of sodium dodecylbenzenesulfonate to 100 parts by mass (in terms of solid content) of the aqueous dispersion of the polyrotaxane crosslinked polymer (C-1) obtained in Example 1, a 20% by mass acetic acid aqueous solution. 20 parts by mass was added dropwise over 40 minutes. After completion of dropping, a 10% by mass aqueous sodium hydroxide solution was added dropwise over 10 minutes to obtain a polyrotaxane crosslinked polymer (C-21) and an aqueous dispersion thereof. The volume average particle diameter of the aqueous dispersion of the polyrotaxane crosslinked polymer (C-21) was 1895 nm.

[Example 22: Polyrotaxane crosslinked polymer (C-22)]
A polyrotaxane cross-linked polymer (C-22) and a polyrotaxane “Celum superpolymer SH3400P” were prepared by performing the reaction under the same conditions as in Example 1 except that 5 parts by mass of the polyrotaxane “Celum superpolymer SH2400P” was used. An aqueous dispersion was obtained. The volume average particle diameter of the aqueous dispersion of the polyrotaxane crosslinked polymer (C-22) was 138 nm.
The details of “Celum Superpolymer SH2400P” used here are as follows.
Linear molecule: Polyethylene glycol having a number average molecular weight of 20,000 having an adamantane group at both ends as a blocking group Cyclic molecule: α-cyclodextrin Polymer part of cyclic molecule: Polycaprolactone Hydroxyl value of polyrotaxane: 76 mg-KOH / g
Number average molecular weight of polyrotaxane: 400,000

[Example 23: Polyrotaxane crosslinked polymer (C-23)]
In 94.8 parts by mass of butyl acrylate, 5.2 parts by mass (in terms of solid content) of a modified polyrotaxane (manufactured by Advanced Soft Materials Co., Ltd., “Celum Superpolymer SM3405P”) was dissolved.
The details of “Celum Superpolymer SM3405P” used here are as follows.
Linear molecule: polyethylene glycol having a number average molecular weight of 35,000 having adamantane groups at both ends as a blocking group Cyclic molecule: methacryl-modified α-cyclodextrin Polymer part of cyclic molecule: polycaprolactone Methacrylic group weight: 0.48 mmol / g
Number average molecular weight of polyrotaxane: 1,000,000
This corresponds to a product obtained by reacting polyrotaxane with 2-methacryloyloxyethyl isocyanate as the functional monomer (b).

  Mixing of 310 parts by weight of deionized water, 1 part by weight of dipotassium alkenyl succinate, 0.2 parts by weight of t-butyl hydroperoxide, and 2.5 parts by weight of hexadecane with a butyl acrylate solution of the modified polyrotaxane obtained above While stirring, the solution was subjected to ultrasonic irradiation with an amplitude 35 μm for 20 minutes using ULTRASONIC HOMOGENIZER US-600 manufactured by Nippon Seiki Seisakusho to obtain a mini-emulsion of a modified polyrotaxane in butyl acrylate.

A reaction vessel equipped with a reagent injection vessel, a cooling tube, a jacket heater and a stirrer is charged with the mini-emulsion of the modified polyrotaxane butyl acrylate solution obtained above, and after the reaction vessel is purged with nitrogen, the temperature is raised to 55 ° C. Warm up. Next, 0.3 parts by mass of sodium formaldehyde sulfoxylate, 0.0001 parts by mass of ferrous sulfate heptahydrate, 0.0003 parts by mass of disodium ethylenediaminetetraacetate and 10 parts by mass of deionized water were added to initiate polymerization. I let you. After the polymerization exotherm is confirmed, the jacket temperature is set to 75 ° C., the polymerization is continued until the polymerization exotherm is not confirmed, and further maintained for 1 hour to obtain an aqueous dispersion of the polyrotaxane crosslinked polymer (C-1). It was. The volume average particle diameter of the aqueous dispersion of the obtained polyrotaxane crosslinked polymer (C-23) was 147 nm.
Next, the aqueous dispersion of the polyrotaxane crosslinked polymer (C-23) was coagulated, washed with water and dried using a 5% by mass sulfuric acid aqueous solution to obtain a polyrotaxane crosslinked polymer (C-23).

[Example 24: Polyrotaxane crosslinked polymer (C-24)]
In 94.8 parts by mass of butyl acrylate, 0.2 part by mass of 2-acryloyloxyethyl isocyanate and 5 parts by mass of polyrotaxane (manufactured by Advanced Soft Materials Co., Ltd., “Celum Superpolymer SH3400P”) are dissolved at 60 ° C. A butyl acrylate solution in which the modified polyrotaxane was dissolved was obtained by reacting for 8 hours.

  While stirring a mixed solution of 310 parts by weight of deionized water, 1 part by weight of dipotassium alkenyl succinate, 0.2 parts by weight of lauroyl peroxide and the butyl acrylate solution of the modified polyrotaxane obtained above, Ultrasonic irradiation was performed at an amplitude of 35 μm for 20 minutes using an ULTRASONIC HOMOGENIZER US-600 manufactured by Nippon Seiki Seisakusho to obtain a mini-emulsion of a modified polyrotaxane in butyl acrylate.

A reaction vessel equipped with a reagent injection vessel, a cooling tube, a jacket heater and a stirrer is charged with the mini-emulsion of the modified polyrotaxane butyl acrylate solution obtained above and reacted at a jacket temperature of 70 ° C. for 3 hours. Thus, an aqueous dispersion of the polyrotaxane crosslinked polymer (C-24) was obtained.
The volume average particle diameter of the aqueous dispersion of the obtained polyrotaxane crosslinked polymer (C-24) was 140 nm.
Next, the aqueous dispersion of the polyrotaxane crosslinked polymer (C-24) was coagulated, washed with water and dried using a 5% by mass sulfuric acid aqueous solution to obtain a polyrotaxane crosslinked polymer (C-24).

[Example 25: Polyrotaxane crosslinked polymer (C-25)]
A polyrotaxane crosslinked polymer (C-25) and an aqueous dispersion thereof were obtained in the same manner as in Example 24 except that 0.2 parts by mass of lauroyl peroxide was changed to 5 parts by mass of lauroyl peroxide. The volume average particle diameter of the aqueous dispersion of the obtained polyrotaxane crosslinked polymer (C-25) was 149 nm.

[Example 26: Polyrotaxane crosslinked polymer (C-26)]
92.8 parts by mass of butyl acrylate, 2.0 parts by mass of stearyl acrylate, 0.2 parts by mass of 2-acryloyloxyethyl isocyanate, polyrotaxane (manufactured by Advanced Soft Materials Co., Ltd., “Celum Superpolymer SH3400P”) 5 The butyl acrylate solution in which the modified polyrotaxane was dissolved was obtained by dissolving parts by mass and reacting at 60 ° C. for 8 hours.

  While stirring a mixed solution of 310 parts by mass of deionized water, 1 part by mass of dipotassium alkenyl succinate, 0.2 part by mass of t-butyl hydroperoxide and the butyl acrylate solution of the modified polyrotaxane obtained above, ( Ultrasonic irradiation was performed at an amplitude of 35 μm for 20 minutes using an ULTRASONIC HOMOGENIZER US-600 manufactured by Nippon Seiki Seisakusho to obtain a mini-emulsion of a butyl acrylate solution of a modified polyrotaxane.

A reaction vessel equipped with a reagent injection vessel, a cooling tube, a jacket heater and a stirrer is charged with the mini-emulsion of the modified polyrotaxane butyl acrylate solution obtained above, and after the reaction vessel is purged with nitrogen, the temperature is raised to 55 ° C. Warm up. Next, 0.3 parts by mass of sodium formaldehyde sulfoxylate, 0.0001 parts by mass of ferrous sulfate heptahydrate, 0.0003 parts by mass of disodium ethylenediaminetetraacetate and 10 parts by mass of deionized water were added to initiate polymerization. I let you. After the polymerization exotherm is confirmed, the jacket temperature is set to 75 ° C., the polymerization is continued until the polymerization exotherm is not confirmed, and further maintained for 1 hour to obtain an aqueous dispersion of the polyrotaxane crosslinked polymer (C-1). It was.
The volume average particle diameter of the aqueous dispersion of the obtained polyrotaxane crosslinked polymer (C-26) was 145 nm.
Next, the aqueous dispersion of the polyrotaxane crosslinked polymer (C-26) was coagulated, washed with water and dried using a 5% by mass aqueous sulfuric acid solution to obtain a polyrotaxane crosslinked polymer (C-26).

[Comparative Example 1: Polyrotaxane crosslinked polymer (C′-1)]
In 94.8 parts by mass of butyl acrylate, 0.2 part by mass of 2-acryloyloxyethyl isocyanate and 5 parts by mass of polyrotaxane (manufactured by Advanced Soft Materials Co., Ltd., “Celum Superpolymer SH3400P”) are dissolved at 60 ° C. A butyl acrylate solution in which the modified polyrotaxane was dissolved was obtained by reacting for 8 hours.

In a reaction vessel equipped with a reagent injection vessel, a condenser, a jacket heater and a stirrer, 310 parts by mass of deionized water, 1 part by mass of dipotassium alkenyl succinate, and 0.2 parts by mass of t-butyl hydroperoxide, The resulting modified polyrotaxane in butyl acrylate was charged, and the reaction vessel was purged with nitrogen, and then heated to 55 ° C. Next, 0.3 parts by mass of sodium formaldehyde sulfoxylate, 0.0001 parts by mass of ferrous sulfate heptahydrate, 0.0003 parts by mass of disodium ethylenediaminetetraacetate and 10 parts by mass of deionized water were added to initiate polymerization. I let you. After the polymerization exotherm is confirmed, the jacket temperature is set to 75 ° C., and the polymerization is continued until the polymerization exotherm is not confirmed, and further maintained for 1 hour, whereby the polyrotaxane crosslinked polymer (C′-1) aqueous dispersion is obtained. Obtained.
The volume average particle diameter of the aqueous dispersion of the obtained polyrotaxane crosslinked polymer (C′-1) was 130 nm.
Next, the aqueous dispersion of the polyrotaxane crosslinked polymer (C′-1) was coagulated, washed with water and dried using a 5 mass% sulfuric acid aqueous solution to obtain a polyrotaxane crosslinked polymer (C′-1).
This Comparative Example 1 is a production example performed in the same manner as in Example 1 except that the miniemulsion step is not performed.

[Comparative Example 2: Polymer (C′-2)]
The polymer (C′-2) and its water were prepared by carrying out the reaction under the same conditions as in Example 1 except that 2-acryloyloxyethyl isocyanate was not used and 95 parts by mass of butyl acrylate and 5 parts by mass of polyrotaxane were used. A dispersion was obtained. The volume average particle diameter of the aqueous dispersion of the polymer (C′-2) was 142 nm.

[Comparative Example 3: Polymer (C′-3)]
Example 1 except that 94.8 parts by mass of butyl acrylate and 0.2 parts by mass of 2-acryloyloxyethyl isocyanate were used, except that 94.5 parts by mass of butyl acrylate and 0.5 parts by mass of triallyl isocyanurate were used. The polymer (C′-3) and an aqueous dispersion thereof were obtained by performing the reaction under the same conditions as in Example 1. The volume average particle diameter of the aqueous dispersion of the polymer (C′-3) was 144 nm.

[Comparative Example 4: Polymer (C′-4)]
Instead of 94.8 parts by mass of butyl acrylate, 0.2 parts by mass of 2-acryloyloxyethyl isocyanate, and 5 parts by mass of polyrotaxane, 99.5 parts by mass of butyl acrylate and 0.5 parts by mass of triallyl isocyanurate were used. A polymer (C′-4) and an aqueous dispersion thereof were obtained by performing the reaction under the same conditions as in Example 1 except for the above. The volume average particle diameter of the aqueous dispersion of the polymer (C′-4) was 143 nm.

[Comparative Example 5: Polymer (C′-5)]
Implemented except that 90.5 parts by mass of butyl acrylate and 1.5 parts by mass of 2-hydroxyethyl acrylate were used instead of 94.8 parts by mass of butyl acrylate and 0.2 parts by mass of 2-acryloyloxyethyl isocyanate. After carrying out the reaction under the same conditions as in Example 1, 3 parts by mass of isophorone diisocyanate was added and reacted for 8 hours to obtain an aqueous dispersion of the polymer (C′-5). The volume average particle diameter of the aqueous dispersion of the obtained polymer (C′-5) was 135 nm.
Next, the aqueous dispersion of the polymer (C′-5) was coagulated, washed with water and dried using 5% by mass of sulfuric acid to obtain a polymer (C′-5).

[Comparative Example 6: Polymer (C′-6)]
100 parts by mass of modified polyrotaxane (manufactured by Advanced Soft Materials Co., Ltd., “Celum Superpolymer SM3405P”) (solid content conversion), 310 parts by mass of deionized water, 1 part by mass of dipotassium alkenyl succinate, t-butyl hydroperoxide While stirring a mixed solution of 0.2 part by mass and 2.5 parts by mass of hexadecane, ultrasonic irradiation was performed for 20 minutes with an amplitude of 35 μm using an ULTRASONIC HOMOGENIZER US-600 manufactured by Nippon Seiki Seisakusho Co., Ltd. A mini-emulsion of polyrotaxane was obtained.

The reaction vessel equipped with a reagent injection vessel, a cooling tube, a jacket heater and a stirrer was charged with the miniemulsion of the modified polyrotaxane obtained above, and the reaction vessel was purged with nitrogen, and then heated to 55 ° C. Next, 0.3 parts by mass of sodium formaldehyde sulfoxylate, 0.0001 parts by mass of ferrous sulfate heptahydrate, 0.0003 parts by mass of disodium ethylenediaminetetraacetate and 10 parts by mass of deionized water were added to initiate polymerization. I let you. After the polymerization exotherm is confirmed, the jacket temperature is set to 75 ° C., and the polymerization is continued until the polymerization exotherm is not confirmed, and further maintained for 1 hour, whereby an aqueous dispersion of the polyrotaxane crosslinked polymer (C′-6) is obtained. Obtained.
The volume average particle diameter of the aqueous dispersion of the obtained polyrotaxane crosslinked polymer (C′-6) was 980 nm.
Next, the aqueous dispersion of the polymer (C′-6) was coagulated, washed with water and dried using a 5 mass% sulfuric acid aqueous solution to obtain a polymer (C′-6).

  For the polyrotaxane crosslinked polymers (C-1) to (C-26) and the polymers (C′-1) to (C′-6), the gel content, the mobility of the cyclic molecules, and the volume were determined according to the evaluation methods described above. Table 1 shows the results of measurement and evaluation of the average particle size, the stability of the aqueous dispersion, and the production stability (the amount of coagulum).

Moreover, the measurement chart of the storage elastic modulus E 'of a polyrotaxane crosslinked polymer (C-1) and a polymer (C'-4) is shown in FIG. 1, FIG. 2, respectively.
As shown in FIG. 1, in the measurement chart of the storage elastic modulus E ′ of the polyrotaxane crosslinked polymer (C-1), while a transition associated with the movement of the cyclic molecule on the linear molecule is seen, In the measurement chart of the storage elastic modulus E ′ of the polymer (C′-4) that does not use the modified polyrotaxane in FIG. 2 for the cross-linking, there is no transition associated with the movement of the cyclic molecule on the linear molecule. From the viscoelasticity measurement results, it can be seen that the mobility of the cyclic molecule can be evaluated.

  As shown in Examples 1 to 26, according to the present invention, the modified polyrotaxane (A) and the monomer (B) are copolymerized in a mini-emulsion, resulting in polyrotaxane crosslinking, that is, mobility of cyclic molecules. It can be seen that cross-linked polymers having various particle diameters and highly stable aqueous dispersions can be obtained while maintaining the function, and that the amount of coagulum produced at that time is small and the production stability is excellent.

On the other hand, in Comparative Example 1, since copolymerization is not performed in the miniemulsion, the amount of coagulum is larger than that in Example 1, and the production stability is inferior.
In Comparative Examples 2 to 4, since the modified polyrotaxane (A) is not used, a function derived from the mobility of the cyclic molecule cannot be obtained.
As shown in Comparative Example 5, a polyrotaxane crosslinked polymer (C) having a function derived from the mobility of cyclic molecules even when a polyrotaxane and a polymer of a monomer having a hydroxyl group or the like are crosslinked with a crosslinking agent such as diisocyanate. No water dispersion is obtained.
Moreover, since the monomer (B) is not used in Comparative Example 6, a stable aqueous dispersion of the polyrotaxane crosslinked polymer (C) cannot be obtained.

Claims (11)

A method for producing a polyrotaxane crosslinked polymer (C) by copolymerizing a modified polyrotaxane (A) and a monomer (B) having a radically polymerizable carbon-carbon double bond,
The modified polyrotaxane (A) has a functional monomer on the cyclic molecule of the polyrotaxane (a) having a linear molecule penetrating through the opening of the cyclic molecule and having blocking groups at both ends of the linear molecule. (B) has a reacted structure;
A method for producing a polyrotaxane crosslinked polymer (C), wherein the modified polyrotaxane (A) and a part or all of the monomer (B) are formed into a miniemulsion in an aqueous solvent and then copolymerized.   In Claim 1, a shear is added to the mixture of the modified polyrotaxane (A), a part or all of the monomer (B), an emulsifier, an aqueous solvent, and a hydrophobic stabilizer using a high shear device. Production of a polyrotaxane crosslinked polymer (C), comprising: a miniemulsion step for forming a miniemulsion and a copolymerization step for carrying out polymerization in the presence of a radical initiator in the obtained miniemulsion Method.   3. The polyrotaxane according to claim 2, wherein the high shear device is any one of a pressure type homogenizer, a high pressure pump and an interaction chamber, an emulsifying device for applying ultrasonic energy, and an emulsifying device for applying high frequency. A method for producing a crosslinked polymer (C).   The functional monomer (b) according to any one of claims 1 to 3, wherein the functional monomer (b) is selected from a carbon-carbon double bond, an isocyanate group, an isothiocyanate group, an epoxy group, and a dicarboxylic anhydride group. A method for producing a crosslinked polyrotaxane polymer (C), which is a compound having a functional group.   5. The group according to claim 4, wherein the functional monomer (b) is 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, glycidyl acrylate, glycidyl methacrylate, allyl isocyanate, allyl isothiocyanate, and maleic anhydride. A method for producing a polyrotaxane crosslinked polymer (C), which is one or more selected from the group consisting of:   In any 1 item | term of Claim 1 thru | or 5, the said modified | denatured polyrotaxane (A) is this functional monomer (A) with respect to a total of 100 mass parts of the said polyrotaxane (a) and a functional monomer (b). b) A method for producing a crosslinked polyrotaxane polymer (C), characterized by reacting at a ratio of 0.1 to 99.9 parts by mass.   In any 1 item | term of the Claims 1 thru | or 6, the said modified | denatured polyrotaxane (A) is the said functional monomer in the solution which dissolved the said polyrotaxane (a) in at least one part of the said monomer (B). A process for producing a polyrotaxane crosslinked polymer (C), which is obtained by reacting the body (b).   The monomer (B) according to any one of claims 1 to 7, wherein the monomer (B) is one or more selected from the group consisting of conjugated dienes and (meth) acrylic acid esters. A process for producing a crosslinked polyrotaxane polymer (C).   The amount of the monomer (B) copolymerized with the modified polyrotaxane (A) according to any one of claims 1 to 8 is a total of 100 of the modified polyrotaxane (A) and the monomer (B). The method for producing a crosslinked polyrotaxane polymer (C), wherein the content is 50 to 99.9% by mass with respect to mass%.   The method for producing a crosslinked polyrotaxane polymer (C) according to any one of claims 1 to 9, wherein the polyrotaxane crosslinked polymer (C) obtained has a gel content of 30 to 100% by mass.   The method for producing a polyrotaxane crosslinked polymer (C) according to any one of claims 1 to 10, wherein the polyrotaxane crosslinked polymer (C) to be obtained has a volume average particle diameter of 5 to 3000 nm.

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