Catalyst for ethylene oxide polymerization, method for producing the same, and method for producing monomer using the same

Abstract

To provide a catalyst for ethylene oxide polymerization composed of particles containing a primary amino group, a method for producing the catalyst for ethylene oxide polymerization, and a method for producing various monomers using the catalyst for ethylene oxide polymerization.SOLUTION: The present invention provides a catalyst (α) for ethylene oxide polymerization composed of particles containing a primary amino group, and / or, a catalyst (α) for ethylene oxide polymerization composed of particles containing a primary amino group, which is a reaction product of components including a polymer (α1) having at least one protected isocyanate group and at least one silicon alkoxide group as side chains of the polyethylene main chain.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to catalysts that can be used in the polymerization of ethylene oxide. [Background technology]

[0002] In conventional ethylene oxide polymerization, ethylene oxide gas is blown into the polymer in the presence of an alkaline catalyst such as ethylenediamine, and heated under pressure to carry out ring-opening addition polymerization, thereby introducing flexible ethylene oxide chains into various monomers. Summary of the Invention [Problem to be solved by the invention]

[0003] However, in conventional methods, after the introduction of the ethylene oxide chain, it is necessary to remove the alkaline catalyst such as ethylenediamine by a relatively costly method such as distillation.In addition, the monomer produced by the conventional polymerization method requires a process such as activated carbon treatment to remove coloration caused by impurities derived from the remaining amine, which also increases the production cost.

[0004] The problem to be solved by the present disclosure is to provide an ethylene oxide polymerization catalyst that is a particle containing a primary amino group, a method for producing the same, and a method for producing various monomers using the same. [Means for solving the problem]

[0005] As a result of extensive research, the present inventors have found that the above-mentioned problems can be solved by using a specific ethylene oxide polymerization catalyst, a method for producing the same, and a method for producing various monomers using the same.

[0006] The present disclosure provides the following: (Item 1) Ethylene oxide polymerization catalyst (α) is a particle containing primary amino groups. (Item 2) A polymer (α1) containing at least one protected isocyanate group and at least one protected silicon alkoxide group as a side chain of a polyethylene main chain, Ethylene oxide polymerization catalyst (α) is a particle containing primary amino groups. (Item 3) The component (α1) comprises the general formula (1), Item 2. A catalyst (α) for ethylene oxide polymerization, which is a particle containing a primary amino group. General formula (1): ZYX (In general formula (1), X is a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, or a halogen atom; Y is a polyethylene main chain containing a structure derived from a compound (A) having a radical polymerizable group and a protected isocyanate group, and a structure derived from a compound (B) having a radical polymerizable group and a silicon alkoxide group, Z is a structure derived from the polymerization initiator (C). (Item 4) Item 3. The ethylene oxide polymerization catalyst (α), which is a particle containing a primary amino group, according to Item 3, wherein the compound (A) having a radical polymerizable group and a protected isocyanate group has a structure derived from one or more compounds selected from compounds represented by structural formula (1). Structural formula (1): [ka] (Item 5) Item 4. The ethylene oxide polymerization catalyst (α), which is a particle containing a primary amino group, according to Item 3, wherein the compound (B) having a radical polymerizable group and a silicon alkoxide group is one or more compounds selected from compounds represented by structural formula (2). Structural formula (2): [ka] (Item 6) Step [1] Polymerizing a compound (A) having a radical polymerizable group and a protected isocyanate group, and a compound (B) having a radical polymerizable group and a silicon alkoxide group by atom transfer radical polymerization (ATRP); Step [2] A step of hydrolyzing the polymer obtained in step [1] in the presence of an alkaline catalyst, and dealcoholizing and condensing the silicon alkoxide, or hydrolyzing and condensing the polymer obtained in step [1] in the presence of inorganic particles and under acidic conditions to obtain particles having protected isocyanate groups; Step [3] A step of dehydrating and condensing the particles obtained in step [2] by heat treatment at 100°C or higher and 200°C or lower, and deprotecting the protected isocyanate groups to regenerate the isocyanate groups; Step [4] A step of converting the isocyanate groups of the particles having isocyanate groups obtained in step [3] into primary amines via a carbamic acid-derived structure; Including, A method for producing a catalyst for ethylene oxide polymerization, which is a particle containing primary amino groups. (Item 7) A step of addition-polymerizing ethylene oxide in the presence of an ethylene oxide polymerization catalyst (α) that is a particle containing a primary amino group according to Item 1 or 2. A method for producing a monomer of general formula (2), comprising: General formula (2): [ka] (In general formula (2), m is an integer between 1 and 30, n is an integer between 1 and 30. [Effects of the Invention]

[0007] The ethylene oxide polymerization catalyst, which is a particle containing a primary amino group, provided by the present disclosure, its production method, and the production method for various monomers using the same can achieve at least one of the desired effects explicitly or implicitly set forth in the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0008] Throughout this disclosure, the range of values ​​for each physical property, content, etc. may be set as appropriate (for example, by selecting from the upper and lower limit values ​​described in each item below). Specifically, for the value φ, if the lower limit of the value φ is exemplified as A1, A2, A3, etc., and the upper limit of the value φ is exemplified as B1, B2, B3, etc., the range of the value φ is exemplified as A1 or more, A2 or more, A3 or more, B1 or less, B2 or less, B3 or less, A1 to B1, A1 to B2, A1 to B3, A2 to B1, A2 to B2, A2 to B3, A3 to B1, A3 to B2, A3 to B3, etc. In addition, in this disclosure, the symbol "to" is used to mean that the values ​​before and after it are included as the lower and upper limits. Below, the components and manufacturing methods of this disclosure will be described in detail.

[0009] <Ethylene oxide polymerization catalyst (α) that is a particle containing a primary amino group> Examples of the ethylene oxide polymerization catalyst (α) (also referred to as "component (α)" in the present disclosure) that is a particle containing a primary amino group include those in which a primary amino group is introduced onto the surface of the particle.

[0010] An example of a method for introducing primary amino groups onto the particle surface is to react a component containing a polymer (α1) containing at least one protected isocyanate group and at least one silicon alkoxide group as side chains of a polyethylene main chain, and more specifically, a method that involves the following steps [1] to [4]. Step [1] Polymerizing a compound (A) having a radical polymerizable group and a protected isocyanate group, and a compound (B) having a radical polymerizable group and a silicon alkoxide group by atom transfer radical polymerization (ATRP); Step [2] A step of hydrolyzing the polymer obtained in step [1] in the presence of an alkaline catalyst, and dealcoholizing and condensing the silicon alkoxide, or hydrolyzing and condensing the polymer obtained in step [1] in the presence of inorganic particles and under acidic conditions to obtain particles having protected isocyanate groups; Step [3] A step of dehydrating and condensing the particles obtained in step [2] by heat treatment at 100°C or higher and 200°C or lower, and deprotecting the protected isocyanate groups to regenerate the isocyanate groups; Step [4] A step of converting the isocyanate groups of the particles having isocyanate groups obtained in step [3] into primary amines via a carbamic acid-derived structure.

[0011] The particles containing primary amino groups obtained through steps [1] to [4] have primary amino groups introduced onto the particle surface via sigma bonds. When examined using an atomic force microscope, it was found that the primary amino groups were introduced onto the particle surface via sigma bonds in a radial pattern around the particle. Radial introduction of primary amino groups onto the particle surface via sigma bonds is preferable because it ensures the reactivity of the primary amino groups while allowing them to be easily removed by filtration, centrifugation, or other methods after the reaction is complete. Furthermore, when particles containing tertiary amino groups were used as a catalyst in the polymerization of ethylene oxide as a substitute for component (α), the reaction did not proceed, or proceeded poorly.

[0012] An example of the first step in a specific method for obtaining component (α) is a process for obtaining a block copolymer of components (A) and (B) (also referred to as an "AB block copolymer" in the present disclosure). Examples of processes for obtaining an AB block copolymer include a process including steps 1-1-1) and 1-1-2), or a process including steps 1-2-1) and 1-2-2). 1-1-1) A step of polymerizing component (A) by atom transfer radical polymerization. 1-1-2) A step of polymerizing the polymer obtained in 1-1-1) with component (B). 1-2-1) A step of polymerizing component (B) by atom transfer radical polymerization. 1-2-2) A step of polymerizing the polymer obtained in 1-2-1) with component (A).

[0013] The second step of the specific method for obtaining the component (α) is, for example, a step of treating the AB block copolymer obtained in the first step with 2-1) or 2-2). 2-1) A process in which the AB block copolymer is hydrolyzed in the presence of an alkaline catalyst, and the silicon alkoxide is dealcoholized and condensed to form spherical silicon dioxide. 2-2) A process in which the AB block copolymer is hydrolyzed and condensed in the presence of inorganic particles and under acidic conditions to introduce protected isocyanate groups onto the inorganic particle surface.

[0014] As a specific example of the third step of the method for obtaining the component (α), the particles obtained in the second step are treated in 3). 3) A process in which the particles obtained in the second step are heat-treated at 100°C or higher and 200°C or lower to complete the dehydration condensation of the silicon dioxide silanol groups and deprotect the protected isocyanate groups, thereby regenerating the isocyanate groups.

[0015] A specific fourth step of the method for obtaining component (α) is, for example, the step of treating the particles obtained in the third step with 4). 4) A process of converting the deprotected regenerated isocyanate group into a primary amine via a carbamic acid-derived structure. For example, reacting an isocyanate group with water results in a structure called -NHCOOH (a structure derived from carbamic acid), and then releasing CO2 results in a structure called -NH2.

[0016] Through the above-mentioned steps 1 to 4, it is possible to produce ethylene oxide addition polymerization catalyst particles, which are component (α), in which primary amino groups are radially introduced onto the particle surface via sigma bonds.

[0017] The upper limit of the particle size (arithmetic mean diameter) of the (α) component is 100 μm, 90 μm, 80 μm, 70 μm, 60 μm, 50 μm, 40 μm, 30 μm, 20 μm, 10 μm, 5 μm, 1 μm, 900 nm, 800 nm, 700 nm, 600 nm, 500 nm, 400 nm, 300 nm, 200 nm, 100 nm, 90 nm, 80 nm, 70 nm, 60 nm, 50 nm, 40 nm, 30 nm, 20 nm, etc. are exemplified, with the lower limit being 90 μm, 80 μm, 70 μm, 60 μm, 50 μm, 40 μm, 30 μm, 20 μm, 10 μm, 5 μm, 1 μm, 900 nm, 800 nm, 700 nm, 600 nm, 500 nm, 400 nm, 300 nm, 200 nm, 100 nm, 90 nm, 80 nm, 70 nm, 60 nm, 50 nm, 40 nm, 30 nm, 20 nm, 10 nm, etc. In one embodiment, the particle size (arithmetic mean diameter) of component (α) is preferably 10 nm to 100 μm, and more preferably 100 nm to 100 μm. The arithmetic mean diameter in the present disclosure refers to the average (arithmetic mean) obtained by capturing images using an optical microscope, an electron microscope, or the like (for example, Winroof is an example of image processing software that can be used here), measuring the maximum diameters of 500 particles, and performing statistical processing on the measured diameters.

[0018] <Polymer (α1) containing at least one protected isocyanate group and at least one protected silicon alkoxide group as a side chain of a polyethylene main chain> The method for introducing primary amino groups into particles described above involves "polymerizing a compound containing a compound (A) having a radical polymerizable group and a protected isocyanate group, and a compound (B) having a radical polymerizable group and a silicon alkoxide group by atom transfer radical polymerization (ATRP)," which results in a polymer (α1) (also referred to in the present disclosure as "component (α1)") containing at least one protected isocyanate group and at least one silicon alkoxide group as side chains on a polyethylene main chain.

[0019] The component (α1) is a polymer obtained by reacting a compound (A) having a radical polymerizable group and a protected isocyanate group, a compound (B) having a radical polymerizable group and a silicon alkoxide group, a polymerization initiator (C), and, if necessary, a compound (D) having a radical polymerizable group.

[0020] The method for obtaining the (α1) component is as follows: a method of polymerizing the components (A) and (C) and then polymerizing the resulting polymer with the component (B); or a method of polymerizing the components (B) and (C) and then polymerizing the resulting polymer with the component (A); Examples include:

[0021] The structure of the (α1) component can be one or more selected from a block copolymer, a random copolymer, and an alternating copolymer. The (α1) component of the present disclosure is preferably a so-called block copolymer in which the (A) component and the (B) component each have a long, continuous structure. This structure can satisfactorily achieve the desired effects of the present disclosure.

[0022] The polymerization conditions for obtaining component (α1) include, for example, adding the necessary components and then reacting them at 20°C to 100°C for 30 minutes to 10 hours. The type of polymerization includes, for example, atom transfer radical polymerization (ATRP). Polymerization by atom transfer radical polymerization makes it easy to control the polymerization, and the atom transfer radical polymerization reagent is stable, so the reaction can easily proceed even in the presence of water, etc.

[0023] An example of the (α1) component is the general formula (1). General formula (1): ZYX (In general formula (1), X is a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, or a halogen atom; Y is a polyethylene main chain containing a structure derived from a compound (A) having a radical polymerizable group and a protected isocyanate group, and a structure derived from a compound (B) having a radical polymerizable group and a silicon alkoxide group, Z is a structure derived from the polymerization initiator (C).

[0024] When X in general formula (1) is a halogen atom, it is one or more selected from Cl, Br, and I.

[0025] When X in general formula (1) is a hydrocarbon group, the upper limit of the number of carbon atoms is, for example, 4, 3, or 2, and the lower limit is, for example, 3, 2, or 1. In one embodiment, when X in general formula (1) is a hydrocarbon group, the number of carbon atoms is 1 or more and 4 or less.

[0026] The upper limit of the number average molecular weight of the general formula (1) is 1,000,000, 900,000, 800,000, 700,000, 600,000, 500,000, 400,000, 300,000, 200,000, 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, 40,000, 30,000, 20,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, 1,000, 900, 800, 700, 600, 500, 400, 300, Examples of the lower limit include 900,000, 800,000, 700,000, 600,000, 500,000, 400,000, 300,000, 200,000, 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, 40,000, 30,000, 20,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, 1,000, 900, 800, 700, 600, 500, 400, 300, 200, and 100. In one embodiment, the number average molecular weight of the general formula (1) is preferably 500 or more and 1,000,000 or less, and more preferably 1,000 or more and 5,000 or less.

[0027] The upper limit of the weight average molecular weight of the general formula (1) is 1,000,000, 900,000, 800,000, 700,000, 600,000, 500,000, 400,000, 300,000, 200,000, 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, 40,000, 30,000, 20,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, 1,000, 900, 800, 700, 600, 500, 400, 300, Examples of the lower limit include 900,000, 800,000, 700,000, 600,000, 500,000, 400,000, 300,000, 200,000, 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, 40,000, 30,000, 20,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, 1,000, 900, 800, 700, 600, 500, 400, 300, 200, and 100. In one embodiment, the weight average molecular weight of the general formula (1) is preferably 500 or more and 1,000,000 or less, and more preferably 1,000 or more and 5,000 or less.

[0028] Examples of upper limits of the molecular weight distribution (Mw / Mn) of general formula (1) are 1.8, 1.7, 1.6, 1.5, 1.4, 1.3, 1.2, 1.1, etc., and examples of lower limits are 1.7, 1.6, 1.5, 1.4, 1.3, 1.2, 1.1, 1.0, etc. In one embodiment, the molecular weight distribution (Mw / Mn) of general formula (1) is preferably 1.0 to 1.8.

[0029] The number average molecular weight, weight average molecular weight, and molecular weight distribution can be measured under the following conditions. Measuring equipment: Product name: "Nexera GPC System" (Shimadzu Corporation) Columns: Styragel HR 0.5 (Waters), Styragel HR 1 (Waters), Styragel HR 2 (Waters), Styragel HR 3 (Waters), Styragel HR 4 (Waters) ·Eluent:THF Column temperature: 40℃ Calibration curve: Standard polystyrene ·Measurement concentration: 0.10% by mass

[0030] Specific examples of the general formula (1) include the following compounds.

[0031] [ka]

[0032] [ka]

[0033] [ka]

[0034] [ka]

[0035] [ka]

[0036] [ka]

[0037] <Compound (A) Having a Radically Polymerizable Group and a Protected Isocyanate Group> The compound (A) having a radically polymerizable group and a protected isocyanate group (also referred to as "component (A)" in this disclosure) may be any compound as long as it has a radically polymerizable group and a protected isocyanate group. Component (A) is used as a component constituting component (α1). When 2-isocyanatoethyl methacrylate or the like is used as an alternative to component (A), radical polymerization with a peroxide such as benzoyl peroxide does not yield a sufficient polymer. This is because isocyanate groups form dimers such as uretdione groups in the presence of free radicals, preventing efficient radical polymerization and resulting in a polymer with the desired degree of polymerization. Component (A), which has a terminal protected isocyanate group, is stable against radicals, making it possible to synthesize a polymer having a polyethylene main chain of the desired molecular weight as the basic skeleton and at least one isocyanate group and silicon alkoxide group in the side chain. In the diagrams of specific examples of the general formula (1) that are the (α1) component (such as the above [Chemical Formula 7] to [Chemical Formula 12]), the letter "a" attached to the structure derived from the component (A) indicates the number of times the component (A) exists in the general formula (1). "a" is an integer of 1 or more and 1,000 or less.

[0038] An example of component (A) is a compound represented by general formula (3).

[0039] General formula (3): [ka] (In general formula (3), R 1 is a hydrocarbon group having 1 to 10 carbon atoms and having -NH-C(=O)-, which may have -C(=O)-O-, R 2 and R 3 or R 2 and R 3 represents one carbon atom and forms a double bond with N, R 2 and R 3 represents a hydrocarbon group having 1 to 10 carbon atoms which may contain a nitrogen atom, R4 is a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.

[0040] R in general formula (3) 1 Preferably, R in the general formula (3) has -C(=O)-O-. 1 -C(=O)-O- is R represented by general formula (3) 4 The group —C(═CH)— (i.e., R 1 Preferably, the bond is directly to the group (the group above the group).

[0041] R in general formula (3) 1 has -NH-C(=O)-. 1 The --NH--C(.dbd.O)-- in the formula (3) preferably bonds directly to the N atom or indirectly via the O atom.

[0042] R in general formula (3) 1 The upper limit of the number of carbon atoms in the hydrocarbon group is, for example, 10, 9, 8, 7, 6, 5, 4, 3, or 2, and the lower limit is, for example, 9, 8, 7, 6, 5, 4, 3, 2, or 1. 1 The hydrocarbon group has preferably 1 or more and 10 or less carbon atoms, more preferably 1 or more and 5 or less carbon atoms, and even more preferably 1 or more and 3 or less carbon atoms.

[0043] R in general formula (3) 2 and R 3 The upper limit of the total number of double bonds in the general formula (3) is 3, 2, etc., and the lower limit is 2, 1, etc. 2 and R 3 The total number of double bonds is preferably 1 to 3.

[0044] R in general formula (3) 2 and R 3The upper limit of the total number of N atoms in the general formula (3) is 3, 2, etc., and the lower limit is 2, 1, etc. 2 and R 3 The total number of N atoms having both of the above is preferably 1 or more and 3 or less.

[0045] R in general formula (3) 2 and R 3 The upper limit of the number of carbon atoms in the hydrocarbon group having both of these groups in total is, for example, 10, 9, 8, 7, 6, 5, 4, 3, or 2, and the lower limit is, for example, 9, 8, 7, 6, 5, 4, 3, 2, or 1. 2 and R 3 The number of carbon atoms in the hydrocarbon group having both of the above in total is preferably 1 or more and 10 or less, and more preferably 1 or more and 5 or less.

[0046] R in general formula (3) 4 The upper limit of the number of carbon atoms in the hydrocarbon group is, for example, 3 or 2, and the lower limit is, for example, 2 or 1. In one embodiment, R 4 The hydrocarbon group preferably has 1 or more and 3 or less carbon atoms.

[0047] An example of the structure obtained when the component (A) is incorporated into the component (α1) is a structure such as that shown in general formula (4).

[0048] General formula (4): [ka] (In general formula (4), R 1 is a hydrocarbon group having 1 to 10 carbon atoms and having -NH-C(=O)-, which may have -C(=O)-O-, R 2 and R 3 or R 2 and R 3 represents one carbon atom and forms a double bond with N, R 2and R 3 represents a hydrocarbon group having 1 to 10 carbon atoms which may contain a nitrogen atom, R 4 is a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, R 1 ~R 4 may each independently be the same or different for each repeating unit, a is an integer between 1 and 1,000.

[0049] R in general formula (4) 1 ~R 4 is R in general formula (3) 1 ~R 4 It refers to the same content as

[0050] a in general formula (4) represents the number of general formula (4) present in the polymer when the compound of general formula (3) is polymerized, and examples of the upper limit include 1,000, 900, 800, 700, 600, 500, 400, 300, 200, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10, 5, 2, etc., and examples of the lower limit include 900, 800, 700, 600, 500, 400, 300, 200, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10, 5, 2, 1, etc. In one embodiment, a in general formula (4) is preferably 1 to 1,000.

[0051] Examples of component (A) include one or more compounds selected from 2-[0-(1'-methylpropylideneamino)carboxyamino]ethyl (meth)acrylate and 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl (meth)acrylate. Specific examples of component (A) include one or more compounds selected from compounds of structural formula (1).

[0052] Structural formula (1): [ka]

[0053] Commercially available products may be used as component (A), such as 2-[0-(1'-methylpropylideneamino)carboxyamino]ethyl methacrylate (product name "Karenz MOI-BM", manufactured by Resonac Co., Ltd.) and 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (product name "Karenz MOI-BP", manufactured by Resonac Co., Ltd.).

[0054] Component (A) may be obtained by protecting the isocyanate group of a commercially available compound having a radical polymerizable group and an isocyanate group by a known method. Examples of commercial products of compounds having a radical polymerizable group and an isocyanate group include 2-isocyanatoethyl methacrylate (product name "Karenz MOI", manufactured by Resonac Co., Ltd.), 2-isocyanatoethyl acrylate (product name "Karenz AOI", manufactured by Resonac Co., Ltd.), and 2-(2-methacryloyloxyethyloxy)ethyl isocyanate (product name "Karenz MOI-EG", manufactured by Resonac Co., Ltd.).

[0055] Examples of upper limits of the molecular weight of component (A) include 1,000, 950, 900, 850, 800, 750, 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, 200, 150, and 100, and examples of lower limits include 950, 900, 850, 800, 750, 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, 200, 150, 100, and 50. In one embodiment, the molecular weight of component (A) is preferably 50 to 1,000. In the present disclosure, the term "molecular weight" simply refers to a numerical value calculated based on atomic weight.

[0056] It is also possible to use a polymer obtained by reacting radically polymerizable groups of the component (A) together as the component (A). In this case, the upper limit of the number average molecular weight is 1,000,000, 900,000, 800,000, 700,000, 600,000, 500,000, 400,000, 300,000, 200,000, 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, 40,000, 30,000, 20,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, 1,000, 900, 800, 700, 600, 500, 400, 300, 2 Examples of the lower limit include 900,000, 800,000, 700,000, 600,000, 500,000, 400,000, 300,000, 200,000, 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, 40,000, 30,000, 20,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, 1,000, 900, 800, 700, 600, 500, 400, 300, 200, 100, and the like. In one embodiment, the number average molecular weight of the polymer obtained by reacting the radically polymerizable groups of the component (A) is preferably 500 or more and 1,000,000 or less, and more preferably 1,000 or more and 5,000 or less.

[0057] The upper limit of the weight average molecular weight of the polymer obtained by reacting the radical polymerizable groups of component (A) with each other is 1,000,000, 900,000, 800,000, 700,000, 600,000, 500,000, 400,000, 300,000, 200,000, 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, 40,000, 30,000, 20,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, 1,000, 900, 800, 700, 600, 50 Examples include 0, 400, 300, and 200, and the lower limit is 900,000, 800,000, 700,000, 600,000, 500,000, 400,000, 300,000, 200,000, 100,000, 90,000, 80,000, 70,000, 60,000, 50, Examples of such molecular weights include 1,000, 40,000, 30,000, 20,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, 1,000, 900, 800, 700, 600, 500, 400, 300, 200, and 100. In one embodiment, the weight average molecular weight of the polymer obtained by reacting the radically polymerizable groups of the component (A) together is preferably 500 or more and 1,000,000 or less, and more preferably 1,000 or more and 5,000 or less.

[0058] The upper limit of the number of radically polymerizable groups in component (A) is, for example, 20, 15, 10, 8, 6, 4, or 2, and the lower limit is, for example, 15, 10, 8, 6, 4, 2, or 1. In one embodiment, the number of radically polymerizable groups in component (A) is preferably 1 to 20, and more preferably 1.

[0059] The upper limit of the number of protected isocyanate groups in component (A) can be 20, 15, 10, 8, 6, 4, or 2, and the lower limit can be 15, 10, 8, 6, 4, 2, or 1. In one embodiment, the number of protected isocyanate groups in component (A) is preferably 1 to 20, and more preferably 1.

[0060] The upper limit of the amount of component (A) (based on solid content) relative to 100% by mass (based on solid content) of component (α1) is 99, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, or 5% by mass, and the lower limit is 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, or 1% by mass. In one embodiment, the amount of component (A) (based on solid content) relative to 100% by mass (based on solid content) of component (α1) is preferably 1 to 99% by mass.

[0061] The upper limit of the amount of component (A) (based on solid content) relative to 100 mol % (based on solid content) of component (α1) is 99, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, or 5 mol %, and the lower limit is 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, or 1 mol %. In one embodiment, the amount of component (A) (based on solid content) relative to 100 mol % (based on solid content) of component (α1) is preferably 1 to 99 mol %.

[0062] <Compound (B) Having a Radical Polymerizable Group and a Silicon Alkoxide Group> The compound (B) having a radical polymerizable group and a silicon alkoxide group (also referred to as "component (B)" in the present disclosure) may have a radical polymerizable group (e.g., a (meth)acryloyl group, etc.) and a silicon alkoxide group (a group in which a hydrocarbon group is bonded to a silicon atom via an oxygen atom). Component (B) is used as a component constituting component (α1). In the diagrams of specific examples of general formula (1) that are component (α1) (e.g., [Chemical Formula 7] to [Chemical Formula 12] above), the "b" attached to the structure derived from component (B) indicates the number of times component (B) is present in general formula (1). b is an integer of 1 or more and 1,000 or less.

[0063] An example of component (B) is the compound represented by general formula (5).

[0064] General formula (5): [ka] (In general formula (5), R 5 is a hydrocarbon group having 1 to 10 carbon atoms, which may have -C(=O)-O-; R 6 ~R 8 are each independently a hydrocarbon group having 1 to 10 carbon atoms which may have -O-; R 6 ~R 8 at least one of which has -O-; R 9 is a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.

[0065] R in general formula (5) 5 Preferably, R in the general formula (5) has —C(═O)—O—. 5 -C(=O)-O- is R represented by general formula (5) 9 The group —C(═CH)— (i.e., R 5 Preferably, the bond is directly to the group (the group above the group).

[0066] R in general formula (5) 5 The upper limit of the number of carbon atoms in the hydrocarbon group is, for example, 10, 9, 8, 7, 6, 5, 4, 3, or 2, and the lower limit is, for example, 9, 8, 7, 6, 5, 4, 3, 2, or 1. 5 The hydrocarbon group has preferably 1 or more and 10 or less carbon atoms, more preferably 1 or more and 5 or less carbon atoms, and even more preferably 1 or more and 3 or less carbon atoms.

[0067] R in general formula (5) 6 ~R 8 The upper limit of the number of -O- is 3, 2, etc., and the lower limit is 2, 1, etc. In one embodiment, R 6 ~R8 The number of -O- groups in the general formula (5) is preferably 1 or more and 3 or less. 6 ~R 8 The -O- in the formula (5) represents an -O- directly bonded to Si. 6 ~R 8 If the number of -O- is 3, R 6 ~R 8 Each of R in the general formula (5) has —O—. 6 ~R 8 If there are two -O- atoms in R 6 ~R 8 and R in general formula (5) 6 ~R 8 If there is one -O- in R 6 ~R 8 It means that one selected from the group consisting of:

[0068] R in general formula (5) 6 ~R 8 The upper limit of the number of carbon atoms in the hydrocarbon group is, for example, 10, 9, 8, 7, 6, 5, 4, 3, or 2, and the lower limit is, for example, 9, 8, 7, 6, 5, 4, 3, 2, or 1. 6 ~R 8 The hydrocarbon group has preferably 1 or more and 10 or less carbon atoms, more preferably 1 or more and 5 or less carbon atoms, and even more preferably 1 or more and 3 or less carbon atoms.

[0069] R in general formula (5) 9 The upper limit of the number of carbon atoms in the hydrocarbon group is, for example, 3 or 2, and the lower limit is, for example, 2 or 1. In one embodiment, R 9 The hydrocarbon group has 1 or more and 3 or less carbon atoms.

[0070] An example of the structure obtained when the component (B) is incorporated into the component (α1) is a structure such as that shown in general formula (6).

[0071] General formula (6): [ka] (In general formula (6), R 5 is a hydrocarbon group having 1 to 10 carbon atoms, which may have -C(=O)-O-; R 6 ~R 8 are each independently a hydrocarbon group having 1 to 10 carbon atoms which may have -O-; R 6 ~R 8 at least one of which has -O-; R 9 is a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, R 5 ~R 9 may each independently be the same or different for each repeating unit, b is an integer between 1 and 1,000.

[0072] R in general formula (6) 5 ~R 9 is R in general formula (5) 5 ~R 9 It refers to the same content as

[0073] b in general formula (6) represents the number of general formula (6) present in the polymer when the compound of general formula (5) is polymerized, and examples of the upper limit include 1,000, 900, 800, 700, 600, 500, 400, 300, 200, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10, 5, 2, etc., and examples of the lower limit include 900, 800, 700, 600, 500, 400, 300, 200, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10, 5, 2, 1, etc. In one embodiment, b in general formula (6) is preferably 1 to 1,000.

[0074] Specific examples of the component (B) include one or more compounds selected from compounds of structural formula (2).

[0075] Structural formula (2): [ka]

[0076] Commercially available products may be used as component (B), such as 3-methacryloxypropylmethyldimethoxysilane (product name "KBM-502", manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyltrimethoxysilane (product name "KBM-503", manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropylmethyldiethoxysilane (product name "KBE-502", manufactured by Shin-Etsu Chemical Co., Ltd.), and 3-methacryloxypropyltriethoxysilane (product name "KBE-503", manufactured by Shin-Etsu Chemical Co., Ltd.).

[0077] Examples of upper limits for the molecular weight of component (B) include 1,000, 950, 900, 850, 800, 750, 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, 200, 150, and 100, and examples of lower limits include 950, 900, 850, 800, 750, 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, 200, 150, 100, and 50. In one embodiment, the molecular weight of component (B) is preferably 50 to 1,000.

[0078] It is also possible to use a polymer obtained by reacting radically polymerizable groups of the component (B) with each other as the component (B). In this case, the upper limit of the number average molecular weight is 1,000,000, 900,000, 800,000, 700,000, 600,000, 500,000, 400,000, 300,000, 200,000, 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, 40,000, 30,000, 20,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, 1,000, 900, 800, 700, 600, 500, 400, 300, 2 Examples of the lower limit include 900,000, 800,000, 700,000, 600,000, 500,000, 400,000, 300,000, 200,000, 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, 40,000, 30,000, 20,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, 1,000, 900, 800, 700, 600, 500, 400, 300, 200, 100, and the like. In one embodiment, the number average molecular weight of the polymer obtained by reacting the radically polymerizable groups of the component (B) is preferably 500 or more and 1,000,000 or less, and more preferably 1,000 or more and 5,000 or less.

[0079] The upper limit of the weight average molecular weight of the polymer obtained by reacting the radical polymerizable groups of component (B) with each other is 1,000,000, 900,000, 800,000, 700,000, 600,000, 500,000, 400,000, 300,000, 200,000, 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, 40,000, 30,000, 20,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, 1,000, 900, 800, 700, 600, 50 Examples include 0, 400, 300, and 200, and the lower limit is 900,000, 800,000, 700,000, 600,000, 500,000, 400,000, 300,000, 200,000, 100,000, 90,000, 80,000, 70,000, 60,000, 50, Examples of such molecular weights include 1,000, 40,000, 30,000, 20,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, 1,000, 900, 800, 700, 600, 500, 400, 300, 200, and 100. In one embodiment, the weight average molecular weight of the polymer obtained by reacting the radically polymerizable groups of component (B) together is preferably 500 or more and 1,000,000 or less, and more preferably 1,000 or more and 5,000 or less.

[0080] The upper limit of the number of radically polymerizable groups in component (B) is, for example, 20, 15, 10, 8, 6, 4, or 2, and the lower limit is, for example, 15, 10, 8, 6, 4, 2, or 1. In one embodiment, the number of radically polymerizable groups in component (B) is preferably 1 to 20, and more preferably 1.

[0081] The upper limit of the number of silicon alkoxide groups in component (B) can be 20, 15, 10, 8, 6, 4, or 2, while the lower limit can be 15, 10, 8, 6, 4, 2, or 1. In one embodiment, the number of silicon alkoxide groups in component (B) is preferably 1 to 20, and more preferably 1.

[0082] The upper limit of the content ratio of component (A) to component (B) (mass ratio, solid content equivalent, [component (A) / component (B)]) is 99 / 1, 95 / 5, 90 / 10, 85 / 15, 80 / 20, 75 / 25, 70 / 30, 65 / 35, 60 / 40, 55 / 45, 50 / 50, 45 / 55, 40 / 60, 35 / 65, 30 / 70, 25 / 75, 20 / 80, 15 Examples of the lower limit include 95 / 5, 90 / 10, 85 / 15, 80 / 20, 75 / 25, 70 / 30, 65 / 35, 60 / 40, 55 / 45, 50 / 50, 45 / 55, 40 / 60, 35 / 65, 30 / 70, 25 / 75, 20 / 80, 15 / 85, 10 / 90, 5 / 95, 1 / 99, etc. In one embodiment, the content ratio of component (A) to component (B) (mass ratio, solid content equivalent, [component (A) / component (B)]) is preferably 1 / 99 to 99 / 1.

[0083] The upper limit of the content ratio of component (A) to component (B) (molar ratio, solid content equivalent, [component (A) / component (B)]) is 99 / 1, 95 / 5, 90 / 10, 85 / 15, 80 / 20, 75 / 25, 70 / 30, 65 / 35, 60 / 40, 55 / 45, 50 / 50, 45 / 55, 40 / 60, 35 / 65, 30 / 70, 25 / 75, 20 / 80, 15 Examples of the lower limit include 95 / 5, 90 / 10, 85 / 15, 80 / 20, 75 / 25, 70 / 30, 65 / 35, 60 / 40, 55 / 45, 50 / 50, 45 / 55, 40 / 60, 35 / 65, 30 / 70, 25 / 75, 20 / 80, 15 / 85, 10 / 90, 5 / 95, 1 / 99, etc. In one embodiment, the content ratio of component (A) to component (B) (molar ratio, calculated as solid content, [component (A) / component (B)]) is preferably 1 / 99 to 99 / 1.

[0084] The upper limit of the amount of component (B) (based on solid content) relative to 100% by mass (based on solid content) of component (α1) is 99, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, or 5% by mass, and the lower limit is 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, or 1% by mass. In one embodiment, the amount of component (B) (based on solid content) relative to 100% by mass (based on solid content) of component (α1) is preferably 1 to 99% by mass.

[0085] The upper limit of the amount of component (B) (based on solid content) relative to 100 mol % (based on solid content) of component (α1) is 99, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, or 5 mol %, and the lower limit is 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, or 1 mol %. In one embodiment, the amount of component (B) (based on solid content) relative to 100 mol % (based on solid content) of component (α1) is preferably 1 to 99 mol %.

[0086] <Polymerization initiator (C)> The polymerization initiator (C) (also referred to as "component (C)" in the present disclosure) is used as a component constituting the component (α1).

[0087] Examples of the component (C) include one or more selected from photopolymerization initiators, thermal polymerization initiators, and atom transfer radical polymerization reagents.

[0088] Examples of the photopolymerization initiator include one or more selected from alkylphenone-type photopolymerization initiators, acylphosphine oxide-type photopolymerization initiators, hydrogen abstraction-type photopolymerization initiators, and oxime ester-type photopolymerization initiators.

[0089] Examples of alkylphenone-type photopolymerization initiators include benzyl dimethyl ketals such as 2,2-dimethoxy-1,2-diphenylethan-1-one, α-hydroxyalkylphenones such as 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and α-aminoalkylphenones such as 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one.

[0090] Examples of the acylphosphine oxide type photopolymerization initiator include one or more selected from 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0091] Examples of hydrogen abstraction type photopolymerization initiators include phenylglyoxylic acid methyl ester.

[0092] Examples of the oxime ester type photopolymerization initiator include one or more selected from 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], and ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime).

[0093] Examples of the thermal polymerization initiator include one or more selected from organic peroxides and azo compounds. Examples of the organic peroxide include one or more selected from 1,1-bis(t-butylperoxy)2-methylcyclohexane, 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, and 1,1-bis(t-butylperoxy)cyclohexane. Examples of the azo compound include one or more selected from 1,1'-azobis(cyclohexane-1-carbonitrile), 2-(carbamoylazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, azodi-t-octane, and azodi-t-butane.

[0094] Atom transfer radical polymerization reagents include ethyl bromoacetate, methyl bromoacetate, 2-bromoisobutyric acid, ethyl 2-bromoisobutyrate, 2-bromoisobutyric bromide, allyl bromide, ethyl 2-bromopropionate, methyl 2-bromopropionate, t-butyl 2-bromoisobutyrate, [11-[(2-bromo-2-methylpropanoyl)oxy]undecyl]phosphoric acid, methyl chloroacetate, Chloroacetonitrile, methyl (R)-(+)-2-chloropropionate, methyl (S)-(-)-2-chloropropionate, 2-chloropropanenitrile, diethyl 2-bromo-2-methylmalonate, ethyl 2-chloro-2-phenylacetate, ethyl 2-bromo-2-phenylacetate, methyl α-bromophenylacetate, bromoacetonitrile, t-butyl 2-bromopropionate, (1-chloroethyl)benzene, ethyl 2-chloropropane pionate, 2,2-dichloroacetophenone, ethyl 2-iodopropionate, 2-hydroxyethyl 2-bromo-2-methylpropanoate, 3-(trimethoxysilyl)propyl 2-bromo-2-methylpropanoate, (1-bromoethyl)benzene, 2-[(2-bromo-2-methylpropanoyl)oxy]ethyl (meth)acrylate, methyl 2-chloropropionate, 2-[(2-hydroxyethyl)disulfanyl]ethyl 2-bromo-2 1-methylpropionate, 11-mercaptoundecyl 2-bromo-2-methylpropanoate, pentaerythritol tetrakis(2-bromoisobutyrate), 2-propyn-1-yl 2-bromo-2-methylpropanoate, 3-(trichlorosilyl)propyl 2-bromo-2-methylpropanoate, 3-(triethoxysilyl)propyl 2-bromo-2-methylpropanoate, and diethyl bromomalonate.

[0095] The atom transfer radical polymerization reagent is preferably one or more compounds selected from the compounds shown in Figure 1. The bonded halogen atom may be any of Br, Cl, and I, and the halogen atom derived from the polymerization catalyst may be substituted with a halogen-free atom or functional group using a halogen scavenger such as allyltributyltin.

[0096] Figure 1: [ka] (In Figure 1, L is an integer between 1 and 1,000.

[0097] L in Figure 1 indicates the number of repetitions of the structure in parentheses, with upper limits such as 1,000, 900, 800, 700, 600, 500, 400, 300, 200, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10, 5, 2, etc., and lower limits such as 900, 800, 700, 600, 500, 400, 300, 200, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10, 5, 2, 1, etc. In one embodiment, L in Figure 1 is preferably 1 to 1,000.

[0098] Component (C) is preferably an atom transfer radical polymerization reagent. Atom transfer radical polymerization reagents are preferred because they are easy to control the polymerization and the reaction proceeds without inactivation even if water is generated as the reaction progresses. On the other hand, initiators used in anionic and cationic polymerization are relatively prone to loss of activity due to water, and dehydration and degassing are necessary. By including an atom transfer radical polymerization reagent in component (α1), it becomes possible to precisely control the polymerization reaction, enabling the production of AB block copolymers.

[0099] Examples of upper limits for the molecular weight of component (C) include 1,000, 950, 900, 850, 800, 750, 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, 200, 150, and 100, and examples of lower limits include 950, 900, 850, 800, 750, 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, 200, 150, 100, and 50. In one embodiment, the molecular weight of component (C) is preferably 50 to 1,000.

[0100] The upper limit of the number of halogen atoms in component (C) can be 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1, and the lower limit can be 9, 8, 7, 6, 5, 4, 3, 2, 1, or 0. In one embodiment, the number of halogen atoms in component (C) is preferably 0 to 10, and more preferably 1 to 5.

[0101] The upper limit of the content ratio of component (A) to component (C) (mass ratio, solid content equivalent, [component (A) / component (C)]) is 99.99 / 0.01, 99.95 / 0.05, 99.9 / 0.1, 99.5 / 0.5, 99 / 1, 95 / 5, 90 / 10, 85 / 15, 80 / 20, 75 / 25, 70 / 30, 65 / 35, 60 / 40, 55 / 45, 50 / 50, 45 / 55, 40 / 60, 35 / 65, 30 / 70, 25 / 75, 20 / 80, 15 / 85, 10 / 90, 5 / 95, 1 / 99, 0.5 / 99.5, 0.1 / 9 Examples of the lower limit include 99.95 / 0.05, 99.9 / 0.1, 99.5 / 0.5, 99 / 1, 95 / 5, 90 / 10, 85 / 15, 80 / 20, 75 / 25, 70 / 30, 65 / 35, 60 / 40, 55 / 45, 50 / 50, 45 / 55, 40 / 60, 35 / 65, 30 / 70, 25 / 75, 20 / 80, 15 / 85, 10 / 90, 5 / 95, 1 / 99, 0.5 / 99.5, 0.1 / 99.9, 0.05 / 99.95, and 0.01 / 99.99. In one embodiment, the content ratio of the component (A) to the component (C) (mass ratio, solid content equivalent, [component (A) / component (C)]) is preferably 0.01 / 99.99 to 99.99 / 0.01.

[0102] The upper limit of the content ratio of component (B) to component (C) (mass ratio, solid content equivalent, [component (B) / component (C)]) is 99.99 / 0.01, 99.95 / 0.05, 99.9 / 0.1, 99.5 / 0.5, 99 / 1, 95 / 5, 90 / 10, 85 / 15, 80 / 20, 75 / 25, 70 / 30, 65 / 35, 60 / 40, 55 / 45, 50 / 50, 45 / 55, 40 / 60, 35 / 65, 30 / 70, 25 / 75, 20 / 80, 15 / 85, 10 / 90, 5 / 95, 1 / 99, 0.5 / 99.5, 0.1 / 9 Examples of the lower limit include 99.95 / 0.05, 99.9 / 0.1, 99.5 / 0.5, 99 / 1, 95 / 5, 90 / 10, 85 / 15, 80 / 20, 75 / 25, 70 / 30, 65 / 35, 60 / 40, 55 / 45, 50 / 50, 45 / 55, 40 / 60, 35 / 65, 30 / 70, 25 / 75, 20 / 80, 15 / 85, 10 / 90, 5 / 95, 1 / 99, 0.5 / 99.5, 0.1 / 99.9, 0.05 / 99.95, and 0.01 / 99.99. In one embodiment, the content ratio of the component (B) to the component (C) (mass ratio, solid content equivalent, [component (B) / component (C)]) is preferably 0.01 / 99.99 to 99.99 / 0.01.

[0103] The upper limit of the content ratio of component (A) to component (C) (molar ratio, solid content equivalent, [component (A) / component (C)]) is 99.99 / 0.01, 99.95 / 0.05, 99.9 / 0.1, 99.5 / 0.5, 99 / 1, 95 / 5, 90 / 10, 85 / 15, 80 / 20, 75 / 25, 70 / 30, 65 / 35, 60 / 40, 55 / 45, 50 / 50, 45 / 55, 40 / 60, 35 / 65, 30 / 70, 25 / 75, 20 / 80, 15 / 85, 10 / 90, 5 / 95, 1 / 99, 0.5 / 99.5, 0.1 / 9 Examples of the lower limit include 99.95 / 0.05, 99.9 / 0.1, 99.5 / 0.5, 99 / 1, 95 / 5, 90 / 10, 85 / 15, 80 / 20, 75 / 25, 70 / 30, 65 / 35, 60 / 40, 55 / 45, 50 / 50, 45 / 55, 40 / 60, 35 / 65, 30 / 70, 25 / 75, 20 / 80, 15 / 85, 10 / 90, 5 / 95, 1 / 99, 0.5 / 99.5, 0.1 / 99.9, 0.05 / 99.95, and 0.01 / 99.99. In one embodiment, the content ratio of the component (A) to the component (C) (molar ratio, calculated as solid content, [component (A) / component (C)]) is preferably 0.01 / 99.99 to 99.99 / 0.01.

[0104] The upper limit of the content ratio of component (B) to component (C) (molar ratio, solid content equivalent, [component (B) / component (C)]) is 99.99 / 0.01, 99.95 / 0.05, 99.9 / 0.1, 99.5 / 0.5, 99 / 1, 95 / 5, 90 / 10, 85 / 15, 80 / 20, 75 / 25, 70 / 30, 65 / 35, 60 / 40, 55 / 45, 50 / 50, 45 / 55, 40 / 60, 35 / 65, 30 / 70, 25 / 75, 20 / 80, 15 / 85, 10 / 90, 5 / 95, 1 / 99, 0.5 / 99.5, 0.1 / 9 Examples of the lower limit include 99.95 / 0.05, 99.9 / 0.1, 99.5 / 0.5, 99 / 1, 95 / 5, 90 / 10, 85 / 15, 80 / 20, 75 / 25, 70 / 30, 65 / 35, 60 / 40, 55 / 45, 50 / 50, 45 / 55, 40 / 60, 35 / 65, 30 / 70, 25 / 75, 20 / 80, 15 / 85, 10 / 90, 5 / 95, 1 / 99, 0.5 / 99.5, 0.1 / 99.9, 0.05 / 99.95, and 0.01 / 99.99. In one embodiment, the content ratio of the component (B) to the component (C) (molar ratio, calculated as solid content, [component (B) / component (C)]) is preferably 0.01 / 99.99 to 99.99 / 0.01.

[0105] Examples of upper limits for the amount of component (C) (in terms of solid content) relative to a total of 100% by mass (in terms of solid content) of component (α1) include 99, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1, 0.5, 0.1, and 0.05% by mass, and examples of lower limits include 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1, 0.5, 0.1, 0.05, and 0.01% by mass. In one embodiment, the content (in terms of solid content) of the component (C) relative to a total of 100% by mass (in terms of solid content) of the component (α1) is preferably 0.01 to 99% by mass.

[0106] Examples of upper limits for the amount of component (C) (in terms of solid content) relative to a total of 100 mol % (in terms of solid content) of component (α1) include 99, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1, 0.5, 0.1, and 0.05 mol %, and examples of lower limits include 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1, 0.5, 0.1, 0.05, and 0.01 mol %. In one embodiment, the content (in terms of solid content) of the component (C) relative to a total of 100 mol % (in terms of solid content) of the component (α1) is preferably 0.01 to 99 mol %.

[0107] <Compound (D) Having a Radically Polymerizable Group> Component (α1) may contain a compound (D) having a radical polymerizable group (also referred to as "component (D)" in the present disclosure). Component (D) refers to a compound having a radical polymerizable group other than components (A) and (B).

[0108] Specific examples of the component (D) include linear alkyl group-containing mono(meth)acrylates, branched alkyl group-containing mono(meth)acrylates, and alicyclic structure-containing mono(meth)acrylates.

[0109] Examples of linear alkyl group-containing mono(meth)acrylates include one or more selected from n-butyl(meth)acrylate, pentyl(meth)acrylate, hexyl(meth)acrylate, heptyl(meth)acrylate, n-octyl(meth)acrylate, nonyl(meth)acrylate, decyl(meth)acrylate, hexadecyl(meth)acrylate, lauryl(meth)acrylate, and stearyl(meth)acrylate.

[0110] Examples of the branched alkyl group-containing mono(meth)acrylate include one or more selected from isoamyl(meth)acrylate, isooctyl(meth)acrylate, isononyl(meth)acrylate, isodecyl(meth)acrylate, isostearyl(meth)acrylate, and 2-ethylhexyl(meth)acrylate.

[0111] Examples of the alicyclic structure-containing mono(meth)acrylate include one or more selected from cyclohexyl(meth)acrylate, 3,3,5-trimethylcyclohexyl(meth)acrylate, 4-t-butylcyclohexyl(meth)acrylate, isobornyl(meth)acrylate, dicyclopentanyl(meth)acrylate, and dicyclopentenyl(meth)acrylate.

[0112] The upper limit of the amount of component (D) (based on solid content) relative to 100% by mass (based on solid content) of component (α1) is 99, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, or 5% by mass, and the lower limit is 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, or 1% by mass. In one embodiment, the amount of component (D) (based on solid content) relative to 100% by mass (based on solid content) of component (α1) is preferably 1 to 99% by mass.

[0113] The upper limit of the amount of component (D) (based on solid content) relative to 100 mol % (based on solid content) of component (α1) is 99, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, or 5 mol %, and the lower limit is 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, or 1 mol %. In one embodiment, the amount of component (D) (based on solid content) relative to 100 mol % (based on solid content) of component (α1) is preferably 1 to 99 mol %.

[0114] <Additives> In the step of reacting components (A) to (C), and optionally component (D), additives such as those used in other inventions when polymerizing a monomer having a radically polymerizable group may be used.

[0115] <Particles having a protected isocyanate group> As a method for obtaining particles having a protected isocyanate group, A method of hydrolyzing the (α1) component in the presence of an alkali catalyst and dealcoholizing and condensing the silicon alkoxide of the (α1) component; A method of hydrolyzing and condensing the (α1) component in the presence of inorganic particles and under acidic conditions Examples include:

[0116] One method for hydrolyzing the component (α1) is to carry out the reaction at 15 to 50°C.

[0117] Examples of alkaline catalysts used in the hydrolysis of component (α1) include ammonia, amines (e.g., one or more selected from ethanolamine, diethanolamine, and triethanolamine), quaternary ammonium compounds, amine coupling agents, potassium carbonate, sodium carbonate, sodium hydroxide, and one or more selected from potassium hydroxide.

[0118] Examples of inorganic particles used in the hydrolysis of component (α1) include one or more selected from zinc oxide particles, silica particles, alumina particles, cerium oxide particles, iron oxide particles, titanium oxide particles, zirconium oxide particles, and cuprous oxide particles. The inorganic particles are preferably silica particles.

[0119] The inorganic particles may be spherical, rod-like, plate-like, fibrous, or irregular in shape, and are preferably spherical or irregular in shape.

[0120] The upper limit of the particle size (arithmetic mean diameter) of inorganic particles is 100 μm, 90 μm, 80 μm, 70 μm, 60 μm, 50 μm, 40 μm, 30 μm, 20 μm, 10 μm, 5 μm, 1 μm, 900 nm, 800 nm, 700 nm, 600 nm, 500 nm, 400 nm, 300 nm, 200 nm, 100 nm, 90 nm, 80 nm, 70 nm, 60 nm, 50 nm, 40 nm, 30 nm, 20 nm Examples of the upper limit include 90 μm, 80 μm, 70 μm, 60 μm, 50 μm, 40 μm, 30 μm, 20 μm, 10 μm, 5 μm, 1 μm, 900 nm, 800 nm, 700 nm, 600 nm, 500 nm, 400 nm, 300 nm, 200 nm, 100 nm, 90 nm, 80 nm, 70 nm, 60 nm, 50 nm, 40 nm, 30 nm, 20 nm, 10 nm, etc. In one embodiment, the particle diameter (arithmetic mean diameter) of the inorganic particles is preferably 10 nm to 100 μm, and more preferably 100 nm to 100 μm. The arithmetic mean diameter in the present disclosure refers to the average (arithmetic mean) obtained by capturing images using an optical microscope, an electron microscope, or the like (for example, Winroof is an example of image processing software that can be used here), measuring the maximum diameters of 500 particles, and performing statistical processing on the measured diameters.

[0121] In the process of obtaining particles having a blocked isocyanate group, additives such as those used in other inventions may be used in producing particles.

[0122] <Compound with regenerated isocyanate groups> As a method for obtaining a compound with regenerated isocyanate groups, An example of such a method is to subject particles having protected isocyanate groups to a heat treatment at 100°C or higher and 200°C or lower to dehydration condensation, and then deprotect the protected isocyanate groups to regenerate the isocyanate groups.

[0123] Examples of upper limits of the temperature when particles having a protected isocyanate group are heat-treated include 200, 190, 180, 170, 160, 150, 140, 130, 120, and 110° C., and examples of lower limits of the temperature are 190, 180, 170, 160, 150, 140, 130, 120, 110, and 100° C. In one embodiment, the temperature when particles having a protected isocyanate group are heat-treated is 100° C. or higher and 200° C. or lower.

[0124] Examples of compounds with regenerated isocyanate groups include the following compounds:

[0125] [ka]

[0126] [ka]

[0127] [ka]

[0128] <Particles containing primary amino groups> Because the generated isocyanate group is highly reactive, it can react with water to generate a primary amine via a carbamic acid-derived structure, thereby obtaining particles containing primary amino groups. In other words, it is possible to synthesize a polymer having a polyethylene main chain as the basic skeleton and at least one primary amino group and silicon alkoxide group in the side chain. This also makes it possible to synthesize a polymer silane coupling agent containing primary amino groups. Polymerization of 2-aminoethyl methacrylate, etc., using atom transfer radical polymerization is difficult due to the influence of its active hydrogen. Therefore, the disclosed synthesis and production method is very useful for synthesizing polymers having a polyethylene main chain as the basic skeleton and at least one primary amino group and silicon alkoxide group in the side chain. The polymer synthesized in this manner can be subjected to ethylene oxide addition polymerization using the disclosed method using ethylene oxide addition polymerization catalyst particles, which are the (α1) component in which primary amino groups are radially introduced onto the particle surface via sigma bonds. That is, it becomes possible to carry out ethylene oxide addition polymerization in a heterogeneous catalyst system, and a step of removing a basic catalyst such as ethylenediamine by a relatively cost-intensive method such as distillation becomes unnecessary. Furthermore, a step of treating with activated carbon to remove coloration due to impurities derived from the remaining amine catalyst becomes unnecessary.

[0129] The upper limit of the content ratio of compounds with regenerated isocyanate groups to water (mass ratio, solid content equivalent, [compounds with regenerated isocyanate groups / water]) is 99.99 / 0.01, 99.95 / 0.05, 99.9 / 0.1, 99.5 / 0.5, 99 / 1, 95 / 5, 90 / 10, 85 / 15, 80 / 20, 75 / 25, 70 / 30, 65 / 35, 60 / 40, 55 / 45, 50 / 50, 45 / 55, 40 / 60, 35 / 65, 30 / 70, 25 / 7 Examples of the lower limit include 99.95 / 0.05, 99.9 / 0.1, 99.5 / 0.5, 99 / 1, 95 / 5, 90 / 10, 85 / 15, 80 / 20, 75 / 25, 70 / 30, 65 / 35, 60 / 40, 55 / 45, 50 / 50, 45 / 55, 40 / 60, 35 / 65, 30 / 70, 25 / 75, 20 / 80, 15 / 85, 10 / 90, 5 / 95, 1 / 99, etc. In one embodiment, the content ratio of the compound with regenerated isocyanate groups to water (mass ratio, solid content equivalent, [compound with regenerated isocyanate groups / water]) is preferably 1 / 99 to 99.99 / 0.01.

[0130] The upper limit of the content ratio of compounds with regenerated isocyanate groups to water (molar ratio, solid content equivalent, [compounds with regenerated isocyanate groups / water]) is 99.99 / 0.01, 99.95 / 0.05, 99.9 / 0.1, 99.5 / 0.5, 99 / 1, 95 / 5, 90 / 10, 85 / 15, 80 / 20, 75 / 25, 70 / 30, 65 / 35, 60 / 40, 55 / 45, 50 / 50, 45 / 55, 40 / 60, 35 / 65, 30 / 70, 25 / 7 Examples of the lower limit include 99.95 / 0.05, 99.9 / 0.1, 99.5 / 0.5, 99 / 1, 95 / 5, 90 / 10, 85 / 15, 80 / 20, 75 / 25, 70 / 30, 65 / 35, 60 / 40, 55 / 45, 50 / 50, 45 / 55, 40 / 60, 35 / 65, 30 / 70, 25 / 75, 20 / 80, 15 / 85, 10 / 90, 5 / 95, 1 / 99, etc. In one embodiment, the content ratio of the compound with regenerated isocyanate groups to water (molar ratio, solid content equivalent, [compound with regenerated isocyanate groups / water]) is preferably 1 / 99 to 99.99 / 0.01.

[0131] Examples of polymer silane coupling agents having a primary amino group include the following compounds.

[0132] [ka]

[0133] [ka]

[0134] [ka]

[0135] When removing particles containing primary amino groups from a system, filtration and / or centrifugation are used. When filtering, the upper limit of the pore size of the filter paper is 100 μm, 90 μm, 80 μm, 70 μm, 60 μm, 50 μm, 40 μm, 30 μm, 20 μm, 10 μm, 5 μm, 1 μm, 900 nm, 800 nm, 700 nm, 600 nm, 500 nm, 400 nm, 300 nm, 200 nm, 100 nm, 90 nm, 80 nm, 70 nm, 60 nm, 50 nm, 40 nm, 30 nm, and 20 nm. Examples of the diameter include the following: 90 μm, 80 μm, 70 μm, 60 μm, 50 μm, 40 μm, 30 μm, 20 μm, 10 μm, 5 μm, 1 μm, 900 nm, 800 nm, 700 nm, 600 nm, 500 nm, 400 nm, 300 nm, 200 nm, 100 nm, 90 nm, 80 nm, 70 nm, 60 nm, 50 nm, 40 nm, 30 nm, 20 nm, 10 nm, etc. In one embodiment, the pore size of the filter paper is preferably 10 nm to 100 μm. The pore size of the filter paper may be selected according to the particle size of the component (α). When centrifuging, separation can be performed using a centrifugal separator (for example, model number "CR21G", manufactured by Koki Holdings Co., Ltd.) at a specific relative centrifugal acceleration. Examples of upper limits of the relative centrifugal acceleration include 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,500, 2,000, 1,500, 1,000, 500, and 300 G, and examples of lower limits include 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,500, 2,000, 1,500, 1,000, 500, 300, and 100 G. In one embodiment, the relative centrifugal acceleration is preferably 100 to 10,000 G. The relative centrifugal acceleration may be selected in accordance with the (α) component.

[0136] <Use of component (α)> Component (α) can be used as a catalyst for the polymerization of ethylene oxide. For example, a compound having an octahydro-1H-4,7-methanoindene skeleton can be introduced into a flexible ethylene oxide chain by blowing ethylene oxide gas into the presence of component (α) and heating the compound to carry out ring-opening addition polymerization. Furthermore, a radically polymerizable group can be introduced by esterification into the terminal hydroxy group of a reaction product obtained with an acid chloride (e.g., one or more selected from acrylic acid chloride and methacrylic acid chloride) or an acid anhydride (e.g., one or more selected from acrylic acid anhydride and methacrylic acid anhydride). Examples of compounds obtained in this manner include those represented by general formula (2).

[0137] General formula (2): [ka] (In general formula (2), m is an integer between 1 and 30, n is an integer between 1 and 30.

[0138] That is, the process for obtaining the compound of general formula (2) is as follows: Step [1] (α) A step of ring-opening addition polymerization of ethylene oxide with a compound having an octahydro-1H-4,7-methanoindene skeleton in the presence of the component; Step [2] (α) removing the component by centrifugation and / or filtration; Step [3]: A step of reacting the compound obtained in Step [2] with one or more compounds selected from acid chlorides and acid anhydrides; is exemplified.

[0139] Examples of upper limits of m in general formula (2) include 30, 25, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, and 2, and examples of lower limits include 25, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, and 1. In one embodiment, m in general formula (2) is preferably 1 or more and 30 or less, more preferably 1 or more and 10 or less, and even more preferably 1 or more and 7 or less.

[0140] Examples of upper limits of n in general formula (2) include 30, 25, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, and 2, and examples of lower limits include 25, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, and 1. In one embodiment, n in general formula (2) is preferably 1 or more and 30 or less, more preferably 1 or more and 10 or less, and even more preferably 1 or more and 7 or less.

[0141] Examples of compounds having an octahydro-1H-4,7-methanoindene skeleton include one or more selected from (octahydro-1H-4,7-methanoindene-1,6-diyl)dimethanol, (octahydro-1H-4,7-methanoindene-1,5-diyl)dimethanol, and (octahydro-1H-4,7-methanoindene-2,5-diyl)dimethanol.

[0142] The reaction conditions for polymerizing ethylene oxide include, for example, a method in which the polymerization reaction is carried out by heating at 30 to 100° C. for 30 minutes to 24 hours.

[0143] The upper limit of the content ratio of compounds having an octahydro-1H-4,7-methanoindene skeleton to ethylene oxide (mass ratio, solid content equivalent, [compounds having an octahydro-1H-4,7-methanoindene skeleton / ethylene oxide]) is 99.99 / 0.01, 99.95 / 0.05, 99.9 / 0.1, 99.5 / 0.5, 99 / 1, 95 / 5, 90 / 10, 85 / 15, 80 / 20, 75 / 25, 70 / 30, 65 / 35, 60 / 40, 55 / 45, 50 / 50, 45 / 55, 40 / 60, 35 / 65, 30 / 70, 25 / 75, 20 / 80, 15 / 85, 1 Examples include 0 / 90, 5 / 95, 1 / 99, 0.5 / 99.5, 0.1 / 99.9, and 0.05 / 99.95, with the lower limit being 99.95 / 0.05, 99.9 / 0.1, 99.5 / 0.5, 99 / 1, 95 / 5, 90 / 10, 85 / 15, 80 / 20, 75 / 25, 70 / 30, and 65. Examples of such ratios include 0.01 / 99.99 to 99.99 / 0.01, 0.01 / 99.99, 0.05 / 99.95, 0.01 / 99.99, 0.05 / 99.95, 0.01 / 99.99, and 0.01 / 99.99. In one embodiment, the content ratio of the compound having an octahydro-1H-4,7-methanoindene skeleton to ethylene oxide (mass ratio, solid content equivalent, [compound having an octahydro-1H-4,7-methanoindene skeleton / ethylene oxide]) is preferably 0.01 / 99.99 to 99.99 / 0.01.

[0144] The upper limit of the content ratio of compounds having an octahydro-1H-4,7-methanoindene skeleton to ethylene oxide (molar ratio, solid content equivalent, [compounds having an octahydro-1H-4,7-methanoindene skeleton / ethylene oxide]) is 99.99 / 0.01, 99.95 / 0.05, 99.9 / 0.1, 99.5 / 0.5, 99 / 1, 95 / 5, 90 / 10, 85 / 15, 80 / 20, 75 / 25, 70 / 30, 65 / 35, 60 / 40, 55 / 45, 50 / 50, 45 / 55, 40 / 60, 35 / 65, 30 / 70, 25 / 75, 20 / 80, 15 / 85, 1 Examples include 0 / 90, 5 / 95, 1 / 99, 0.5 / 99.5, 0.1 / 99.9, and 0.05 / 99.95, with the lower limit being 99.95 / 0.05, 99.9 / 0.1, 99.5 / 0.5, 99 / 1, 95 / 5, 90 / 10, 85 / 15, 80 / 20, 75 / 25, 70 / 30, and 65. Examples include 0.01 / 99.99 to 99.99 / 0.01, 0.01 / 99.99, 0.05 / 99.95, 0.01 / 99.99, 0.05 / 99.95, 0.01 / 99.99, etc. In one embodiment, the content ratio of the compound having an octahydro-1H-4,7-methanoindene skeleton to ethylene oxide (molar ratio, calculated as solid content, [compound having an octahydro-1H-4,7-methanoindene skeleton / ethylene oxide]) is preferably 0.01 / 99.99 to 99.99 / 0.01.

[0145] The upper limit of the content ratio of the reaction product of a compound having an octahydro-1H-4,7-methanoindene skeleton and ethylene oxide to one or more selected from acid chlorides and acid anhydrides (mass ratio, solid content equivalent, [reaction product of a compound having an octahydro-1H-4,7-methanoindene skeleton and ethylene oxide / one or more selected from acid chlorides and acid anhydrides]) is 99.99 / 0.01, 99.95 / 0.05, 99.9 / 0.1, 99.5 / 0.5, 99 / 1, 95 / 5, 90 / 10, 85 / 15, 80 / 20, 75 / 25, 70 / 30, 65 / 35, 60 / 40, 55 / 45, 50 / 50, 45 / 55, 40 / 60, 35 Examples include 65 / 65, 30 / 70, 25 / 75, 20 / 80, 15 / 85, 10 / 90, 5 / 95, 1 / 99, 0.5 / 99.5, 0.1 / 99.9, and 0.05 / 99.95, with the lower limit being 99.95 / 0.05, 99.9 / 0.1, 99.5 / 0.5, 99 / 1, 95 / 5, 90 / 10, 85 / 15, and 80 / 20. Examples of the ratio include 75 / 25, 70 / 30, 65 / 35, 60 / 40, 55 / 45, 50 / 50, 45 / 55, 40 / 60, 35 / 65, 30 / 70, 25 / 75, 20 / 80, 15 / 85, 10 / 90, 5 / 95, 1 / 99, 0.5 / 99.5, 0.1 / 99.9, 0.05 / 99.95, and 0.01 / 99.99. In one embodiment, the ratio of the content of the compound having the isocyanate group regenerated and water (mass ratio, solid content equivalent, [reaction product of a compound having an octahydro-1H-4,7-methanoindene skeleton and ethylene oxide / one or more selected from acid chlorides and acid anhydrides]) is preferably 0.01 / 99.99 to 99.99 / 0.01.

[0146] The upper limit of the content ratio of the reaction product of a compound having an octahydro-1H-4,7-methanoindene skeleton and ethylene oxide to one or more selected from acid chlorides and acid anhydrides (molar ratio, solid content equivalent, [reaction product of a compound having an octahydro-1H-4,7-methanoindene skeleton and ethylene oxide / one or more selected from acid chlorides and acid anhydrides]) is 99.99 / 0.01, 99.95 / 0.05, 99.9 / 0.1, 99.5 / 0.5, 99 / 1, 95 / 5, 90 / 10, 85 / 15, 80 / 20, 75 / 25, 70 / 30, 65 / 35, 60 / 40, 55 / 45, 50 / 50, 45 / 55, 40 / 60, 35 Examples include 65 / 65, 30 / 70, 25 / 75, 20 / 80, 15 / 85, 10 / 90, 5 / 95, 1 / 99, 0.5 / 99.5, 0.1 / 99.9, and 0.05 / 99.95, with the lower limit being 99.95 / 0.05, 99.9 / 0.1, 99.5 / 0.5, 99 / 1, 95 / 5, 90 / 10, 85 / 15, and 80 / 20. Examples of the ratio include 75 / 25, 70 / 30, 65 / 35, 60 / 40, 55 / 45, 50 / 50, 45 / 55, 40 / 60, 35 / 65, 30 / 70, 25 / 75, 20 / 80, 15 / 85, 10 / 90, 5 / 95, 1 / 99, 0.5 / 99.5, 0.1 / 99.9, 0.05 / 99.95, and 0.01 / 99.99. In one embodiment, the content ratio of the compound having the isocyanate group regenerated and water (molar ratio, solid content equivalent, [reaction product of a compound having an octahydro-1H-4,7-methanoindene skeleton and ethylene oxide / one or more selected from acid chlorides and acid anhydrides]) is preferably 0.01 / 99.99 to 99.99 / 0.01.

[0147] Examples of upper limits for the content (in terms of solid content) of component (α) relative to 100% by mass (in terms of solid content) of the total of compounds having an octahydro-1H-4,7-methanoindene skeleton include 99, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1, 0.5, 0.1, and 0.05% by mass, and examples of lower limits include 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1, 0.5, 0.1, 0.05, and 0.01% by mass. In one embodiment, the content (in terms of solid content) of the component (α) relative to a total of 100% by mass (in terms of solid content) of the compounds having an octahydro-1H-4,7-methanoindene skeleton is preferably 0.01 to 99% by mass.

[0148] Examples of upper limits for the content (in terms of solid content) of the component (α) relative to a total of 100 mol % (in terms of solid content) of compounds having an octahydro-1H-4,7-methanoindene skeleton include 99, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1, 0.5, 0.1, and 0.05 mol %, and examples of lower limits include 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1, 0.5, 0.1, 0.05, and 0.01 mol %. In one embodiment, the content (in terms of solid content) of the component (α) relative to a total of 100 mol % (in terms of solid content) of compounds having an octahydro-1H-4,7-methanoindene skeleton is preferably 0.01 to 99 mol %.

[0149] The monomer of general formula (2) can be used in medical and dental hardenable compositions. Adhesives and composite resins used in the medical and dental fields generally use (meth)acrylic acid derivative monomers such as methyl (meth)acrylate, triethylene glycol di(meth)acrylate, and urethane di(meth)acrylate. These monomers undergo free radical polymerization (also referred to as "radical polymerization" in this disclosure) to cleave carbon-carbon double bonds and convert them into single bonds, forming polymers that harden. The commonly used (meth)acrylic acid derivative monomers, such as methyl (meth)acrylate, triethylene glycol di(meth)acrylate, and urethane di(meth)acrylate, undergo a change from a liquid to a solid state upon hardening, resulting in polymerization shrinkage of several percent. On the other hand, monomers of general formula (2) exhibit low polymerization shrinkage upon hardening and can be used as so-called low polymerization shrinkage monomers. When a low-polymerization-shrinkage monomer of general formula (2) is obtained by, for example, in the presence of a basic catalyst such as ethylenediamine, by injecting ethylene oxide gas and heating under pressure to perform ring-opening addition polymerization to introduce a flexible ethylene oxide chain, the basic catalyst such as ethylenediamine must be removed by a relatively costly method such as distillation after the ethylene oxide chain is introduced. Furthermore, when the low-polymerization-shrinkage monomer of general formula (2) is used in a medical or dental curable composition, a step such as activated carbon treatment is essential to remove coloration caused by remaining amine-derived impurities, which also increases production costs. On the other hand, when a low-polymerization-shrinkage monomer of general formula (2) is obtained by the method of the present disclosure, the component (α) is particulate, so it can be easily removed by filtration or centrifugation. Therefore, production costs can be reduced, and a high-purity product can be obtained because there are no amine-derived impurities.

[0150] In addition, it is also conceivable that the monomer of general formula (2) of the present disclosure may be used in various applications in which the effects thereof can be exerted.

[0151] Additives such as those used in other inventions may be used in the preparation of medical and dental hardenable compositions for the monomer of general formula (2). [Example]

[0152] Specific examples of the present disclosure will be described below using examples, but the present disclosure is not limited to these examples. In the examples, parts and percentages are all by mass unless otherwise specified.

[0153] <Synthesis Example 1-1: Synthesis of (α1)-1 Component> In a pre-baked 100 mL Schlenk polymerization tube equipped with a three-way stopcock, 134 mg (0.932 mmol) of Cu(I)Br was precisely weighed, and 30 mL of dehydrated and degassed anisole, 0.1 mL of nonane (internal standard for monitoring the polymerization reaction), 92.7 mg (0.5 mmol) of n-tributylamine (polymerization cocatalyst), and 146 mg (156 mmol) of 2,2'-bipyridine were injected in this order via syringe under argon flow. The Schlenk polymerization tube was heated to 70 °C with magnetic stirring to completely dissolve the catalyst ligands. Next, 50.0 mmol of a radically polymerizable monomer bearing a silicon alkoxide group (Table 1) was added, and after thorough stirring and homogenization, 181 mg (1.00 mmol) of methyl 2-bromo-2-methylpropanoate (polymerization initiator) was added to initiate the polymerization. Samples were withdrawn at regular intervals under an argon stream, and the monomer conversion was measured by gas chromatography. When the monomer conversion reached 95%, 12.1 g (50 mmol) of (E)-2-(((butan-2-ylideneamino)oxy)carbonyl)amino)ethyl methacrylate was added all at once. Again, samples were withdrawn at regular intervals under an argon stream, and the monomer conversion was measured by gas chromatography. When the monomer conversion reached 95%, the heating was stopped, a small amount of oxygen was bubbled in to terminate the polymerization reaction, and the remaining monomer / anisole was distilled off using an evaporator. These reaction steps yielded the desired silane coupling agent: an AB block copolymer with a polyethylene main chain as the basic skeleton and protected isocyanate and silicon alkoxide groups on the side chains. GPC analysis revealed that the molecular weight distribution (Mw / Mn) of the resulting AB block copolymer was 1.03.

[0154] <Synthesis Examples 1-2 to 1-12: Synthesis of (α1)-2 to (α1)-12 Components> Synthesis Examples 1-2 to 1-6 were carried out in the same manner as Synthesis Example 1-1, except that component (B) was changed as shown in Table 1, to obtain component (α1)-2 (Synthesis Example 1-2) to component (α1)-6 (Synthesis Example 1-6). Synthesis Examples 1-7 to 1-12 were carried out in the same manner as Synthesis Example 1, except that component (A) was changed to 12.6 g (50 mmol) of 2-(3,5-dimethyl-1H-pyrazole-1-carboxyamido)ethyl methacrylate and component (B) was changed as shown in Table 1, to obtain component (α1)-7 (Synthesis Example 1-7) to component (α1)-12 (Synthesis Example 1-12). Although the mass of component (B) differed, the molar amount was the same: 50.0 mmol.

[0155] [Table 1]

[0156] <Synthesis Examples 2-1 to 2-12: Synthesis of (α)-1 to (α)-12 Components> 1.0 g of each of (α1)-1 to (α1)-12 was dissolved in 5.0 mL of a tetrahydrofuran / distilled water (80 vol% / 20 vol%) mixed solvent. 0.1 mL of 1N sodium hydroxide solution was added while stirring with a magnetic stirrer to hydrolyze the silicon alkoxide groups, synthesizing spherical particles with a diameter of approximately 100 nm. The solution was centrifuged, washed with ion-exchanged water, and then freeze-dried to obtain white spherical particles. The resulting spherical particles were transferred to 5.0 mL cryovials and heated in air at 150 °C for 12 hours to dehydrate and condense the silanol groups. Next, 10 mg of dibutyltin dilaurate and 3.0 mL of dehydrated anisole were added to the 5.0 mL cryovials, and the air was replaced with argon bubbling to degas the ampoules. The ampoules were then heat-sealed using an acetylene-oxygen gas burner. They were then heated in a block heater at 150 °C for 3 hours. The ampoules were sealed using an acetylene-oxygen gas burner. They were then heated for 3 hours in a block heater at 150°C. After heating, the ampoules were returned to room temperature, and gas chromatography confirmed the presence of 3,5-dimethyl-1H-pyrazole and (E)-butan-2-one oxime, which had been released from the protected isocyanate groups. The release rates were confirmed to be over 99%. After confirming the release of the protecting groups, the ampoules were centrifuged, washed with acetone, and vacuum-dried. All particles were white and spherical. Furthermore, FT-IR spectroscopy using the KBr powder pellet method revealed a sharp absorption spectrum derived from primary amines in both white spherical particles.

[0157] <Examples 1-1 to 1-12: Ethylene Oxide Addition Polymerization to Compounds Having Octahydro-1H-4,7-methanoinden Skeleton> 100 mg of each of the (α)-1 to (α)-12 components was weighed into a 5.0 mL cryovial. The Synthesis Example numbers correspond to the Example numbers. In parallel, an equimolar mixture of (octahydro-1H-4,7-methanoindene-1,6-diyl)dimethanol, (octahydro-1H-4,7-methanoindene-1,5-diyl)dimethanol, and (octahydro-1H-4,7-methanoindene-2,5-diyl)dimethanol was dissolved in tetrahydrofuran to a concentration of 5 wt %. 1.0 mL of this solution was pipetted into a 5.0 mL cryovial containing 100 mg of the (α)-1 to (α)-12 components (white spherical particles). Next, 3.0 mL of a 1 mol / L ethylene oxide / tetrahydrofuran solution was added to the 5.0 mL cryovial. The 5.0 mL cryovial was heat-sealed using an acetylene-oxygen gas burner and reacted with stirring and heating for 12 hours in a shaking block heater heated to 50°C. After the reaction was completed, the ethylene oxide addition polymerization catalyst particles were removed by vacuum filtration, and a very small amount was subjected to molecular weight measurement by gel permeation chromatography. The results showed that 1 to 5 moles of ethylene oxide had been addition polymerized in all examples. Furthermore, the Hazen color number of the solution after removal of the ethylene oxide addition polymerization catalyst particles was APHA 5 or less, and no coloration was observed.

[0158] <Examples 2-1 to 2-12: Synthesis of Low Polymerization Shrinkage Monomers for Medical and Dental Use> Two equivalent moles of acrylic acid chloride and pyridine were added to the solution from which the ethylene oxide addition polymerization catalyst particles had been removed in Examples 1-1 to 1-12 in an ice bath. After 3 hours of reaction, the pyridine hydrochloride was removed by vacuum filtration, and the solvent was removed using an evaporator. FT-IR and 1H-NMR analyses confirmed that a compound corresponding to general formula (2) had been synthesized. Furthermore, the Hazen color index was APHA5 or less, and no coloration was observed.

[0159] <Comparative Examples 1-1 to 1-3: Ethylene Oxide Addition Polymerization to Compounds Having Octahydro-1H-4,7-methanoinden Skeleton> 100 mg (Comparative Example 1-1), 200 mg (Comparative Example 1-2), and 300 mg (Comparative Example 1-3) of ethylenediamine were weighed into 5.0 mL cryovials. The Synthesis Example numbers correspond to the amounts of ethylenediamine in each case. In parallel, an equimolar mixture of (octahydro-1H-4,7-methanoindene-1,6-diyl)dimethanol, (octahydro-1H-4,7-methanoindene-1,5-diyl)dimethanol, and (octahydro-1H-4,7-methanoindene-2,5-diyl)dimethanol was dissolved in tetrahydrofuran to a concentration of 5 wt%. 1.0 mL of this solution was pipetted into a 5.0 mL cryovial containing ethylenediamine. Next, 3.0 mL of a 1 mol / L ethylene oxide / tetrahydrofuran solution was added to the 5.0 mL cryovial. The 5.0 mL cryovial was heat-sealed using an acetylene-oxygen gas burner and stirred and heated for 12 hours in a shaking block heater heated to 50°C. After the reaction was completed, molecular weight was measured by gel permeation chromatography. The results showed that 1 to 5 moles of ethylene oxide had been added and polymerized in all comparative examples. However, the Hazen color number of the solution was yellow in proportion to the amount of ethylenediamine, and was APHA 300 or higher.

[0160] <Comparative Examples 2-1 to 2-3: Synthesis of Low Polymerization Shrinkage Monomers for Medical and Dental Use> Two equivalent moles of acrylic acid chloride and pyridine were added to the solutions synthesized in Comparative Examples 1-1 to 1-3 in an ice bath. After 3 hours of reaction, pyridine hydrochloride was removed by vacuum filtration, and the solvent and ethylenediamine were removed by evaporator and vacuum distillation. FT-IR and 1H-NMR analyses confirmed that a compound corresponding to general formula (2) had been synthesized. However, the Hazen color index was APHA300 or higher, and the compound was a very deep yellow. Industrial Applicability

[0161] Conventional synthesis methods for low-polymerization-shrinkage monomers used in medical and dental curable compositions involve introducing flexible ethylene oxide chains by blowing ethylene oxide gas into the mixture in the presence of a basic catalyst such as ethylenediamine, heating under pressure, and conducting ring-opening addition polymerization. However, this conventional method requires the removal of the basic catalyst, such as ethylenediamine, after the ethylene oxide chain has been introduced using a relatively costly method such as distillation. Furthermore, when using low-polymerization-shrinkage monomers with the structural formula 2-((3-((2-(buta-1,3-dien-2-yloxy)ethoxy)methyl)octahydro-1H-4,7-methanoinden-5-yl)methoxy)ethyl acrylate, produced by conventional synthesis methods, in medical and dental curable compositions, a process such as activated carbon treatment is essential to remove coloration caused by remaining amine-derived impurities, which also increases production costs. However, the present inventors discovered that the use of the heterogeneous catalyst of the present invention in ethylene oxide addition polymerization eliminates the need for a relatively costly process for removing a basic catalyst such as ethylenediamine by distillation, and further eliminates the need for a process such as activated carbon treatment to remove coloration due to impurities derived from the remaining amine catalyst, leading to the completion of the present invention. Therefore, the present invention can be said to have great potential for industrial applicability.

Claims

1. a polymer (α1) containing at least one protected isocyanate group and at least one protected silicon alkoxide group as a side chain of a polyethylene main chain; An ethylene oxide polymerization catalyst (α) which is a particle containing a primary amino group.

2. The component (α1) contains the general formula (1), 2. An ethylene oxide polymerization catalyst (α) comprising particles containing primary amino groups according to claim 1. General formula (1): ZYX (In general formula (1), X is a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, or a halogen atom; Y is a polyethylene main chain containing a structure derived from a compound (A) having a radical polymerizable group and a protected isocyanate group, and a structure derived from a compound (B) having a radical polymerizable group and a silicon alkoxide group, Z is a structure derived from the polymerization initiator (C).

3. The ethylene oxide polymerization catalyst (α), which is a particle containing a primary amino group according to claim 2, wherein the compound (A) having a radical polymerizable group and a protected isocyanate group has a structure derived from one or more compounds selected from compounds represented by structural formula (1). Structural formula (1): [Chemical Formula 1]

4. The ethylene oxide polymerization catalyst (α), which is a particle containing a primary amino group according to claim 2, wherein the compound (B) having a radical polymerizable group and a silicon alkoxide group is one or more compounds selected from compounds represented by structural formula (2): Structural formula (2): 【Chemistry 2】

5. Step [1] Polymerizing a compound containing a compound (A) having a radical polymerizable group and a protected isocyanate group, and a compound (B) having a radical polymerizable group and a silicon alkoxide group by atom transfer radical polymerization (ATRP); Step [2] A step of hydrolyzing the polymer obtained in step [1] in the presence of an alkali catalyst, and dealcoholizing and condensing the silicon alkoxide, or hydrolyzing and condensing the polymer obtained in step [1] in the presence of inorganic particles and under acidic conditions to obtain particles having protected isocyanate groups; Step [3] A step of dehydrating and condensing the particles obtained in step [2] by heat treatment at 100°C or higher and 200°C or lower, and deprotecting the protected isocyanate groups to regenerate the isocyanate groups; Step [4]: ​​A step of converting the isocyanate groups of the particles having isocyanate groups obtained in step [3] into primary amines via a carbamic acid-derived structure; Including, A method for producing an ethylene oxide polymerization catalyst, which is a particle containing a primary amino group.

6. A step of addition-polymerizing ethylene oxide in the presence of the ethylene oxide polymerization catalyst (α) which is the particle containing a primary amino group according to claim 1. A method for producing a monomer of general formula (2), comprising: General formula (2): 【Chemistry 3】 (In general formula (2), m is an integer of 1 to 30, n is an integer of 1 or more and 30 or less.

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