Polymers, copolymers, inks, ink containers, image forming methods, image forming apparatuses, and solar cell backsheets.

Abstract

To provide a polymer or a copolymer with which a colorant dispersion excellent in storage stability, an ink excellent in storage stability and redispersibility, and a solar cell back sheet excellent in weather resistance can be produced.SOLUTION: The polymer has a structural unit represented by general formula (1). (R1 represents hydrogen or a methyl group; L1 represents -COO-, -CONH- or a bond; X represents a C2-10 hydrocarbon group or an oxygen-containing C2-10 hydrocarbon group; L2 represents -O- or -NH-; Y represents a C2-12 hydrocarbon group; L3 represents -NH-C2H4-R2, -O-Ph-CH2CH(R2)2 or -O-Np-CH2CH(R2)2; Ph represents a phenylene group; Np represents a naphthylene group; and R2 represents a phosphonic acid group.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to polymers, copolymers, inks, ink containers, image forming methods, image forming apparatuses, and solar cell backsheets. [Background technology]

[0002] Inkjet printers are widely used as printing machines for paper media. When printing on media other than paper (for example, transparent or colored plastic film or colored fabric), in addition to black, yellow, magenta, and cyan inks, a highly opaque white ink is required.

[0003] For example, rutile-type titanium dioxide with a high refractive index is used as a pigment for white ink with high opacity. Furthermore, as a dispersant for the titanium dioxide, an AB block type carboxyl group-containing AB block copolymer has been proposed, comprising methacrylate containing at least six or more aliphatic cyclic alkyl groups and methacrylic acid as constituent components (see, for example, Patent Document 1). [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] The present invention aims to provide polymers or copolymers capable of producing colorant dispersions with excellent storage stability, inks with excellent storage stability and redispersibility, and solar cell backsheets with excellent weather resistance. [Means for solving the problem]

[0005] The polymer of the present invention, as a means for solving the aforementioned problems, is characterized by being a polymer having a structural unit represented by the following general formula (1).

[0006] [ka] (In general formula (1), R1 is hydrogen or a methyl group, L1 is -COO-, -CONH-, or a bond, X is a hydrocarbon group having 2 to 10 carbon atoms, or a hydrocarbon group having 2 to 10 carbon atoms containing oxygen, L2 is -O- or -NH-, Y is a hydrocarbon group having 2 to 12 carbon atoms, L3 is -NH-C2H4-R2, -O-Ph-CH2CH(R2)2, or -O-Np-CH2CH(R2)2, where Ph is a phenylene group, Np is a naphthylene group, and R2 is a phosphonic acid group.) [Effects of the Invention]

[0007] According to the present invention, it is possible to provide polymers or copolymers that can be used to produce colorant dispersions with excellent storage stability, inks with excellent storage stability and redispersibility, and solar cell backsheets with excellent weather resistance. [Brief explanation of the drawing]

[0008] [Figure 1] This is a schematic diagram showing an example of an image forming apparatus. [Figure 2] This is a schematic diagram showing an example of an ink cartridge. [Modes for carrying out the invention]

[0009] (polymer) The polymer of the present invention is characterized by having a structural unit represented by the following general formula (1).

[0010] [ka] (In general formula (1), R1 is hydrogen or a methyl group, L1 is -COO-, -CONH-, or a bond, X is a hydrocarbon group having 2 to 10 carbon atoms, or a hydrocarbon group having 2 to 10 carbon atoms containing oxygen, L2 is -O- or -NH-, Y is a hydrocarbon group having 2 to 12 carbon atoms, L3 is -NH-C2H4-R2, -O-Ph-CH2CH(R2)2, or -O-Np-CH2CH(R2)2, where Ph is a phenylene group, Np is a naphthylene group, and R2 is a phosphonic acid group.)

[0011] Rutile-type titanium dioxide, which has been conventionally used in highly opaque white inks, has a specific gravity of 4.17 g / mL. Therefore, it is known that titanium dioxide precipitates in inks or colorant dispersions over time, and eventually separation occurs. When using an ink or colorant dispersion, there is no problem in use if the original dispersed state can be restored by stirring or shaking. However, there has been a problem that titanium dioxide deposited in the lower layer of the ink or colorant dispersion aggregates, and the dispersed state cannot be restored. In addition, due to the failure to restore the dispersed state of the ink or colorant dispersion, there have also been problems such as an increase in the viscosity of the ink or colorant dispersion, a decrease in white opacifying power, and ejection failure.

[0012] The conventional dispersant described in Patent Document 1 does not provide sufficient storage stability of ink and redispersibility of colorant, and further improvement has been demanded.

[0013] As a result of intensive studies by the present inventors, they have found that by using a polymer having a structural unit represented by the above general formula (1), a colorant dispersion excellent in storage stability and an ink excellent in storage stability and redispersibility can be obtained. Furthermore, it has been found that by using a polymer having a structural unit represented by the above general formula (1), a film in which a colorant such as titanium dioxide is uniformly dispersed without aggregation can be obtained, and by applying the obtained film as a protective layer to a solar cell back sheet, a solar cell back sheet excellent in weather resistance can also be obtained.

[0014] Therefore, in the present invention, by using a polymer having a structural unit represented by the above general formula (1), a colorant dispersion excellent in storage stability, an ink excellent in storage stability and redispersibility, and a polymer or copolymer capable of producing a solar cell back sheet excellent in weather resistance can be obtained.

[0015] <Polymer having a structural unit represented by general formula (1)> The polymer of the present invention has a structural unit represented by the following general formula (1), and may optionally contain other polymerizable monomers.

[0016]

Chem.

[0017] In the polymer having the structural unit represented by general formula (1), the phosphonic acid group present at the terminal improves the adsorption force to the surfaces of particles such as titanium oxide, titanium oxide surface-treated with alumina, and barium sulfate. Further, the "-NH-CO-NH- group" or "-NH-COO- group" bonded to the linking group X and the linking group Y in general formula (1) imparts water solubility to the polymer. Therefore, by using the polymer of the present invention when preparing a colorant dispersion in which a colorant described below is dispersed in water, a colorant dispersion having high dispersibility and long-term stability can be prepared.

[0018] From the viewpoint of storage stability of dispersions and inks, the number average molecular weight (Mn) and weight average molecular weight (Mw) of the polymer of the present invention, in terms of polystyrene, are preferably 2,000 to 20,000 and 5,000 to 50,000, respectively, and more preferably 5,000 to 15,000 and 15,000 to 40,000, respectively.

[0019] There are no particular limitations on the method for synthesizing the polymer of the present invention, and it can be appropriately selected depending on the purpose. For example, the methods shown in (1) to (5) below are examples.

[0020] (1) Diethyl 2-aminoethylphosphonic acid (A1) is reacted with a diamine or amino alcohol (A2) to obtain a phosphonic acid diester derivative (A3).

[0021] [ka]

[0022] (2) React with an isocyanate compound having a polymerizable group (A4) to obtain a phosphonic acid diester derivative (A5).

[0023] [ka]

[0024] (3) The phosphonic acid diester derivative (A5) is reacted with trimethylsilyl bromide to form trimethylsilyl ester (A6), which is then hydrolyzed to obtain polymerizable phosphonic acid monomer (A7).

[0025] [ka]

[0026] [ka]

[0027] (4) Finally, it is obtained by polymerizing monomer (A7) in the presence of a radical polymerization initiator.

[0028] [ka]

[0029] (copolymer) <Structural unit represented by general formula (2)> The copolymer of the present invention has a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2) below, and may optionally have other polymerizable monomers.

[0030] [ka] (In general formula (2), R3 is hydrogen, or a methyl group, X + (This is a proton or a positive ion.) In this specification, the "structural unit represented by general formula (2)" may be referred to as the "second monomer." In this specification, a copolymer having a structural unit represented by general formula (1) and a structural unit represented by general formula (2) may be referred to as a copolymer.

[0031] In the general formula (2) above, the proton or cation induces electrostatic repulsion between copolymer molecules. Therefore, by using the copolymer of the present invention when preparing a colorant dispersion in which the colorant described later is dispersed in water, the dispersibility, redispersibility, and storage stability of the colorant dispersion can be improved.

[0032] The aforementioned proton or cation is not particularly limited and can be appropriately selected depending on the purpose. For example, sodium ion, potassium ion, lithium ion, tetramethylammonium ion, tetraethylammonium ion, tetrapropylammonium ion, tetrabutylammonium ion, tetrapentylammonium ion, tetrahexylammonium ion, triethylmethylammonium ion, tributylmethylammonium ion, trioctylmethylammonium ion, 2-hydroxyethyltrimethylammonium ion, tris(2-hydroxyethyl)methylammonium ion, propyltrimethylammonium ion, hexyltrimethylammonium ion, octyltrimethylammonium ion, nonyltrimethylammonium ion, decyltrimethylammonium ion, dodecyltrimethylammonium ion, tetradecyltrimethylammonium ion, hexadecyltrimethylammonium ion, octadecyltrimethylammonium ion. Examples include diammonium ions, didodecyldimethylammonium ions, ditetradecyldimethylammonium ions, dihexadecyldimethylammonium ions, dioctadecyldimethylammonium ions, ethylhexadecyldimethylammonium ions, ammonium ions, dimethylammonium ions, trimethylammonium ions, monoethylammonium ions, diethylammonium ions, triethylammonium ions, monoethanolammonium ions, diethanolammonium ions, triethanolammonium ions, methylethanolammonium ions, methyldiethanolammonium ions, dimethylethanolammonium ions, monopropanolammonium ions, dipropanolammonium ions, trippropanolammonium ions, isopropanolammonium ions, morpholinium ions, N-methylmorpholinium ions, N-methyl-2-pyrrolidonium ions, and 2-pyrrolidonium ions.

[0033] In the copolymer of the present invention, the number-average molecular weight (Mn) and weight-average molecular weight (Mw), in terms of polystyrene, are preferably 2,000 to 20,000 and 5,000 to 50,000, respectively, and more preferably 5,000 to 15,000 and 15,000 to 40,000.

[0034] The structure of the copolymer of the present invention is not particularly limited and can be appropriately selected depending on the purpose. Examples include random copolymers, graft copolymers, and block copolymers.

[0035] There are no particular limitations on the synthesis method of the copolymer of the present invention, and it can be appropriately selected depending on the purpose. For example, it can be obtained by copolymerizing the polymerizable phosphonic acid monomer (A7) described in the above (polymer) synthesis method with (meth)acrylic acid.

[0036] <Other polymerizable monomers> The polymer or copolymer of the present invention may have other polymerizable monomers in addition to the structural unit represented by general formula (1) and the structural unit represented by general formula (2). The aforementioned other polymerizable monomers are not particularly limited and can be appropriately selected depending on the purpose. Examples include polymerizable hydrophobic monomers, polymerizable hydrophilic monomers, and polymerizable surfactants. In this specification, "other polymerizable monomers" may be referred to as "third monomers."

[0037] <<Polymerizable hydrophobic monomers>> The polymerizable hydrophobic monomer is not particularly limited and can be appropriately selected depending on the purpose. Examples include unsaturated ethylene monomers having aromatic rings such as α-methylstyrene, 4-t-butylstyrene, and 4-chloromethylstyrene; methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, dimethyl maleate, dimethyl itaconate, dimethyl fumarate, lauryl (meth)acrylate (C12), tridecyl (meth)acrylate (C13), tetradecyl (meth)acrylate (C14), pentadecyl (meth)acrylate (C15), hexadecyl (meth)acrylate (C16), heptadecyl (meth)acrylate (C17), nonadecyl (meth)acrylate (C19), and eicosyl (meth)acrylate (C20). Examples include alkyl (meth)acrylates such as henicosyl (meth)acrylate (C21) and docosyl (meth)acrylate (C22); and unsaturated ethylene monomers having alkyl groups such as 1-heptene, 3,3-dimethyl-1-pentene, 4,4-dimethyl-1-pentene, 3-methyl-1-hexene, 4-methyl-1-hexene, 5-methyl-1-hexene, 1-octene, 3,3-dimethyl-1-hexene, 3,4-dimethyl-1-hexene, 4,4-dimethyl-1-hexene, 1-nonene, 3,5,5-trimethyl-1-hexene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, and 1-docosene. These can be used individually or in combination of two or more.

[0038] <<Polymerizable hydrophilic monomers>> The polymerizable hydrophilic monomer is not particularly limited and can be appropriately selected depending on the purpose. Examples include anionic unsaturated ethylene monomers such as maleic acid or its salts, monomethyl maleate, itaconic acid, monomethyl itaconic acid, fumaric acid, 4-styrene sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, or unsaturated ethylene monomers containing phosphoric acid, phosphonic acid, alendronic acid, or etidronic acid; and nonionic unsaturated ethylene monomers such as (meth)acrylate-2-hydroxyethyl, diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, tetraethylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, (meth)acrylamide, N-methylol(meth)acrylamide, N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, acrylamide, N,N-dimethylacrylamide, Nt-butylacrylamide, N-octylacrylamide, and Nt-octylacrylamide.

[0039] There are no particular restrictions on the content of the polymerizable hydrophobic monomer and the polymerizable hydrophilic monomer, and they can be appropriately selected depending on the purpose. For example, they can be used in an amount of 5 to 100% by mass relative to the total amount of monomers that form a polymer having the structural unit represented by general formula (1), or a copolymer having the structural unit represented by general formula (1) and the structural unit represented by general formula (2).

[0040] <<Polymerizable surfactant>> The polymerizable surfactant is a surfactant having at least one unsaturated double bond group capable of radical polymerization within its molecule, and examples include anionic surfactants and nonionic surfactants.

[0041] -Anionic surfactant- The anionic surfactant is not particularly limited and can be appropriately selected depending on the purpose, for example, ammonium sulfate base (-SO3-NH4 +) and hydrocarbon compounds having an allyl group (-CH2-CH=CH2), such as sulfate bases (-SO3-NH4 + A hydrocarbon compound having a sulfate base such as (-CO-C(CH3)=CH2) and a methacrylic group (-SO3-NH4), or an ammonium sulfate base (-SO3-NH4 + Examples include aromatic hydrocarbon compounds having a sulfate base such as ) and a 1-propenyl group (-CH=CH2CH3). Specific examples of the aforementioned anionic surfactants include Eleminor JS-20 and RS-300 (both manufactured by Sanyo Chemical Industries), Aqualon KH-10, Aqualon KH-1025, Aqualon KH-05, Aqualon HS-10, Aqualon HS-1025, Aqualon BC-0515, Aqualon BC-10, Aqualon BC-1025, Aqualon BC-20, and Aqualon BC-2020 (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).

[0042] -Nonionic surfactant- The nonionic surfactant is not particularly limited and can be appropriately selected depending on the purpose. Examples include hydrocarbon compounds or aromatic hydrocarbon compounds having a 1-propenyl group (-CH=CH2CH3) and a polyoxyethylene group (-(C2H4O)nH). Specific examples of the aforementioned nonionic surfactants include Aqualon RN-20, Aqualon RN-2025, Aqualon RN-30, and Aqualon RN-50 (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and Latemul PD-104, Latemul PD-420, Latemul PD-430, and Latemul PD-450 (all manufactured by Kao Corporation).

[0043] There are no particular restrictions on the content of the polymerizable surfactant, and it can be appropriately selected depending on the purpose. For example, it can be used in an amount of 0.1 to 10% by mass relative to the total amount of monomers that form a polymer having the structural unit represented by general formula (1), or a copolymer having the structural unit represented by general formula (1) and the structural unit represented by general formula (2).

[0044] In the process of forming the polymers and copolymers of the present invention, a radical polymerization initiator may be used. The radical polymerization initiator is not particularly limited and can be appropriately selected depending on the purpose. Examples include peroxyketals, hydroperoxides, dialkylperoxides, diacylperoxides, peroxydicarbonates, peroxyesters, cyano-based azobisisobutyronitrile, azobis(2-methylbutyronitrile), azobis(2,2'-isovaleronitrile), and non-cyano-based dimethyl-2,2'-azobisisobutyrate. Among these, organic peroxides and azo compounds are preferred, and azo compounds are more preferred, due to their ease of molecular weight control and low decomposition temperature. There are no particular restrictions on the content of the radical polymerization initiator, and it can be appropriately selected depending on the purpose, but it is preferably 1 to 10% by mass relative to the total amount of polymerizable monomers. The polymerizable monomers refer to monomers that form polymers having the structural unit represented by the general formula (1), monomers that form copolymers having the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2), and all other polymerizable monomers.

[0045] A chain transfer agent may be added to adjust the molecular weight of the polymers and copolymers of the present invention. The chain transfer agent is not particularly limited and can be appropriately selected depending on the purpose. Examples include mercaptoacetic acid, mercaptopropionic acid, 2-propanethol, 2-mercaptoethanol, thiophenol, dodecyl mercaptan, 1-dodecanethiol, and thioglycerol.

[0046] The polymerization temperature for forming the polymers and copolymers of the present invention is not particularly limited and can be appropriately selected depending on the purpose, but 50°C to 150°C is preferred, and 60°C to 100°C is more preferred. The polymerization time for forming the polymers and copolymers of the present invention is not particularly limited and can be appropriately selected depending on the purpose, but 3 to 48 hours is preferred.

[0047] (ink) The ink of the present invention comprises water, a colorant, and a resin, and may optionally contain other components.

[0048] <Water> There are no particular restrictions on the water contained in the ink of the present invention, and it can be appropriately selected depending on the purpose. The water content in the ink of the present invention is not particularly limited and can be appropriately selected depending on the purpose, but from the viewpoint of ink drying properties and ejection reliability, it is preferably 10% to 90% by mass and more preferably 20% to 60% by mass relative to the total amount of ink.

[0049] <Colorants> There are no particular limitations on the colorants included in the ink of the present invention, and they can be appropriately selected depending on the purpose. For example, pigments, dyes, etc., can be used. Mixed crystals may also be used.

[0050] <<Pigment>> There are no particular restrictions on the aforementioned pigments, and they can be appropriately selected according to the purpose. For example, black pigments, yellow pigments, magenta pigments, cyan pigments, white pigments, green pigments, orange pigments, glossy pigments such as gold and silver, and metallic pigments can be used.

[0051] Furthermore, inorganic pigments and organic pigments can be used as the aforementioned pigments. The inorganic pigments mentioned above are not particularly limited and can be appropriately selected depending on the purpose. Examples include titanium dioxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chromium yellow, and carbon black produced by known methods such as the contact method, furnace method, and thermal method. There are no particular restrictions on the organic pigments mentioned above, and they can be appropriately selected depending on the purpose. Examples include azo pigments, polycyclic pigments (e.g., phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments, etc.), dye chelates (e.g., basic dye type chelates, acid dye type chelates, etc.), nitro pigments, nitroso pigments, and aniline black. Of these pigments, those with good affinity for the solvent are preferably used. In addition, resin hollow particles or inorganic hollow particles can also be used.

[0052] Specific examples of the aforementioned pigments include the following: Examples of black pigments include carbon blacks (CI Pigment Black 7) such as furnace black, lamp black, acetylene black, and channel black, or metals such as copper, iron (CI Pigment Black 11), and titanium dioxide, and organic pigments such as aniline black (CI Pigment Black 1). As color pigments, CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 17, CI Pigment Yellow 24, CI Pigment Yellow 34, CI Pigment Yellow 35, CI Pigment Yellow 37, CI Pigment Yellow 42 (yellow iron oxide), CI Pigment Yellow 53, CI Pigment Yellow 55, CI Pigment Yellow 74, CI Pigment CI Pigment Yellow 81, CI Pigment Yellow 83, CI Pigment Yellow 95, CI Pigment Yellow 97, CI Pigment Yellow 98, CI Pigment Yellow 100, CI Pigment Yellow 101, CI Pigment Yellow 104, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 117, CI Pigment Yellow 120, CI Pigment Yellow 138, CI Pigment Yellow 150, CI P Pigment Yellow 153, CI Pigment Yellow 155, CI Pigment Yellow 180, CI Pigment Yellow 185, CI Pigment Yellow 213, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 36, CI Pigment Orange 43, CI Pigment Orange 51, CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 5, CI Pigment Red 17, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 31, CI Pigment Red 38, CI Pigment Red 48:2, CI Pigment Red 48:2 (Permanent Red 2B (Ca)), CI Pigment Red 48:3, CI Pigment Red 48:4, CI Pigment Red 49:1, CI Pigment Red 52:2, CI Pigment Red 53:1, CI Pigment Red 57:1 (Brilliant Carmine 6B), CIPigment Red 60:1, CI Pigment Red 63:1, CI Pigment Red 63:2, CI Pigment Red 64:1, CI Pigment Red 81, CI Pigment Red 83, CI Pigment Red 88, CI Pigment Red 101 (Bengara), CI Pigment Red 104, CI Pigment Red 105, CI Pigment Red 106, CI Pigment Red 108 (Cadmium Red), CI Pigment Red 112, CI Pigment Red 114, CI Pigment Red D122 (Quinacridone Magenta), CI Pigment Red 123, CI Pigment Red 146, CI Pigment Red 149, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 170, CI Pigment Red 172, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 184, CI Pigment Red 185, CI Pigment Red 190, CI Pigment Red 193, CI Pigment Red Red 202, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 213, CI Pigment Red 219, CI Pigment Red 224, CI Pigment Red 254, CI Pigment Red 264, CI Pigment Violet 1 (Rhodamine Lake), CI Pigment Violet 3, CI Pigment Violet 5:1, CI Pigment Violet 16, CI Pigment Violet 19, CI Pigment Violet 2 3, CI Pigment Violet 38, CI Pigment Blue 1, CI Pigment Blue 2, CI Pigment Blue 15 (Phthalocyanine Blue), CI Pigment Blue 15:1, CI Pigment Blue 15:2, CI Pigment Blue 15:3, CI Pigment Blue 15:4 (Phthalocyanine Blue), CI Pigment Blue 16, CI Pigment Blue 17:1, CI Pigment Blue 56, CI Pigment Blue 60, CI Pigment Blue 63, CI Pigment Green 1, CIExamples include Pigment Green 4, CI Pigment Green 7, CI Pigment Green 8, CI Pigment Green 10, CI Pigment Green 17, CI Pigment Green 18, and CI Pigment Green 36.

[0053] <<dye>> There are no particular restrictions on the dyes used, and they can be appropriately selected according to the purpose. For example, acid dyes, direct dyes, reactive dyes, and basic dyes can be used. These may be used individually or in combination of two or more.

[0054] Specific examples of the aforementioned dyes include CI Acid Yellow 17, CI Acid Yellow 23, CI Acid Yellow 42, CI Acid Yellow 44, CI Acid Yellow 79, CI Acid Yellow 142, CI Acid Red 52, CI Acid Red 80, CI Acid Red 82, CI Acid Red 249, CI Acid Red 254, CI Acid Red 289, CI Acid Blue 9, CI Acid Blue 45, CI Acid Blue 249, CI Acid Black 1, CI Acid Black 2, CI Acid Black 24, CI Acid Black 94, CI Food Black 1, CI Food Black 2, CI Direct Yellow 1, CI Direct Yellow 12, CI Direct Yellow 24, CI Direct Yellow 33, CI Direct Yellow 50, CI Direct Yellow 55, CI Direct Yellow 58, CI Direct Yellow 86, CI Direct Yellow 132, CI Direct Yellow 142, CI Direct Yellow 144, CI Dye Rect Yellow 173, CI Direct Red 1, CI Direct Red 4, CI Direct Red 9, CI Direct Red 80, CI Direct Red 81, CI Direct Red 225, CI Direct Red 227, CI Direct Blue 1, CI Direct Blue 2, CI Direct Blue 15, CI Direct Blue 71, CI Direct Blue 86, CI Direct Blue 87, CI Direct Blue 98, CI Direct Blue 165, CI Direct Blue 199, CI Direct Blue 202, CI Direct Black 19, CI Direct Black 38, CI Direct Black 51, CI Direct Black 71, CI Direct Black 154, CI Direct Black 168, CI Direct Black 171, CI Direct Black 195, CI Reactive Red 14, CI Reactive Red 32, CI Reactive Red 55, CI Reactive Red 79, CI Reactive Red 249, CI Reactive Black 3, CIExamples include Reactive Black 4 and CI Reactive Black 35.

[0055] As the coloring material of the present invention, pigments are preferred because they have excellent adsorption capacity to the polymer or copolymer of the present invention, as well as excellent water resistance and weather resistance. In particular, when a white pigment is used as the coloring material, titanium dioxide and barium sulfate are preferred from the viewpoint of opacity, and titanium dioxide is more preferred.

[0056] The amount of colorant contained in the ink of the present invention is not particularly limited and can be appropriately selected depending on the purpose. However, from the viewpoint of improving image density and obtaining good fixation and ejection stability, it is preferably 0.1% by mass or more and 15% by mass or less, and more preferably 10% by mass or more and 15% by mass or less, relative to the total amount of ink.

[0057] <Resin> The resin contained in the ink of the present invention includes a polymer having a structural unit represented by the general formula (1), or a copolymer having a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2), and may optionally contain other resins (A). The aforementioned other resin (A) is not particularly limited and can be appropriately selected depending on the purpose. Examples include urethane resin, polyester resin, acrylic resin, vinyl acetate resin, styrene resin, butadiene resin, styrene-butadiene resin, vinyl chloride resin, acrylic styrene resin, and acrylic silicone resin. These may be used individually or in combination of two or more.

[0058] Resin particles made of the aforementioned other resin (A) may be used as the other resin (A). The aforementioned resin particles may be synthesized as appropriate, or commercially available products may be used. There are no particular restrictions on the volume-average particle size of the resin particles, and they can be appropriately selected depending on the purpose. However, from the standpoint of obtaining good fixation and high image hardness, a particle size of 10 nm to 1000 nm is preferred, 10 nm to 200 nm is more preferred, and 10 nm to 100 nm is particularly preferred. The volume-average particle size of the resin particles can be measured, for example, using a particle size analyzer (NanoTrac Wave-UT151, manufactured by MicroTrac-Bell Co., Ltd.).

[0059] <Other ingredients> The aforementioned other components are not particularly limited and can be appropriately selected depending on the purpose, and examples include organic solvents and additives.

[0060] <<Organic solvent>> The ink of the present invention may contain an organic solvent. Since the polymer and copolymer of the present invention are water-soluble in the ink, they may be used in combination with a hydrophilic organic solvent. The organic solvent is not particularly limited and can be appropriately selected depending on the purpose. For example, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,3-butanediol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 2, Polyhydric alcohols such as 4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,3-hexanediol, 2,5-hexanediol, 1,5-hexanediol, glycerin, 1,2,6-hexanetriol, 2-ethyl-1,3-hexanediol, ethyl-1,2,4-butanetriol, 1,2,3-butanetriol, 2,2,4-trimethyl-1,3-pentanediol, petriol, etc.; ethylene glycol monoethyl ether, ethylene glycol Examples include polyhydric alcohol alkyl ethers such as monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and propylene glycol monoethyl ether; polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether; nitrogen-containing heterocyclic compounds such as 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, and γ-butyrolactone; amides such as formamide, N-methylformamide, N,N-dimethylformamide, 3-methoxy-N,N-dimethylpropionamide, and 3-butoxy-N,N-dimethylpropionamide; amines such as monoethanolamine, diethanolamine, and triethylamine; sulfur-containing compounds such as dimethyl sulfoxide, sulfolane, and thiodiethanol; and propylene carbonate.

[0061] Since the aforementioned organic solvent not only functions as a wetting agent but also provides good drying properties, it is preferable to use an organic solvent with a boiling point of 250°C or lower.

[0062] Furthermore, when paper is used as the recording medium, polyol compounds having 8 or more carbon atoms and glycol ether compounds can be suitably used as organic solvents to improve ink permeability. Specific examples of the polyol compounds having 8 or more carbon atoms include 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol. Specific examples of the glycol ether compounds include polyhydric alcohol alkyl ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and propylene glycol monoethyl ether; and polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether.

[0063] There are no particular restrictions on the content of the organic solvent, and it can be appropriately selected depending on the purpose. However, from the viewpoint of ink drying properties and ejection reliability, it is preferable that the content be 10% by mass or more and 60% by mass or less, and more preferably 20% by mass or more and 60% by mass or less, relative to the total amount of ink.

[0064] <<Additives>> There are no particular restrictions on the aforementioned additives, and they can be appropriately selected depending on the purpose. Examples of other components include surfactants, defoamers, preservatives and antifungal agents, rust inhibitors, and pH adjusters.

[0065] -Surfactants used as other ingredients- There are no particular restrictions on the surfactants used as other components, and they can be appropriately selected depending on the purpose. Examples include silicone-based surfactants, fluorine-based surfactants, amphoteric surfactants, nonionic surfactants, and anionic surfactants. In this specification, when "surfactants used as other components" is mentioned, it refers to surfactants included as other components in the ink of the present invention, and does not fall under the category of "other polymerizable monomers" mentioned above.

[0066] --Silicone-based surfactants-- There are no particular restrictions on the silicone-based surfactant, and it can be appropriately selected depending on the purpose, but it is preferable that it does not decompose even at high pH (pH 11-14). Specific examples of silicone-based surfactants that do not decompose even at high pH (pH 11-14) include side-chain modified polydimethylsiloxane, both-end modified polydimethylsiloxane, one-end modified polydimethylsiloxane, and both-end modified polydimethylsiloxane. Among these, polyether-modified silicone-based surfactants having a polyoxyethylene group or a polyoxyethylene-polyoxypropylene group as a modifying group are more preferred from the viewpoint of improving hydrophilicity and increasing solubility in water. These may be used individually or in combination of two or more.

[0067] There are no particular limitations on the polyether-modified silicone surfactant, and it can be appropriately selected depending on the purpose. For example, a polyalkylene oxide structure represented by the general formula (S-1) can be introduced into the Si side chain of dimethylpolysiloxane.

[0068] [ka] General formula (S-1) (However, in general formula (S-1), m, n, a, and b each independently represent integers, R represents an alkylene group, and R' represents an alkyl group.)

[0069] As the polyether-modified silicone surfactant, a suitably synthesized one may be used, or a commercially available product may be used. Examples of commercially available polyether-modified silicone surfactants include KF-618, KF-642, KF-643 (all manufactured by Shin-Etsu Chemical Co., Ltd.), EMALEX-SS-5602, EMALEX-SS-1906EX (both manufactured by Nippon Emulsion Co., Ltd.), FZ-2105, FZ-2118, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ-2164 (all manufactured by Toray Dow Corning Silicone Co., Ltd.), BYK-33, BYK-387 (both manufactured by Big Chemie Co., Ltd.), and TSF4440, TSF4452, TSF4453 (all manufactured by Toshiba Silicone Co., Ltd.).

[0070] As the aforementioned silicone-based surfactant, a suitably synthesized one may be used, or a commercially available product may be used. Commercially available silicone-based surfactants can be obtained from companies such as BIC Chemie Inc., Shin-Etsu Chemical Co., Ltd., Toray Dow Corning Silicone Co., Ltd., Nippon Emulsion Co., Ltd., and Kyoeisha Chemical Co., Ltd.

[0071] --Fluorine-based surfactants-- There are no particular restrictions on the fluorinated surfactant, and it can be appropriately selected depending on the purpose, but compounds with 2 to 16 carbon atoms substituted with fluorine are preferred, and compounds with 4 to 16 carbon atoms substituted with fluorine are more preferred. Furthermore, there are no particular restrictions on the fluorine-based surfactant, and it can be appropriately selected depending on the purpose. However, from the viewpoint of low foaming ability, perfluoroalkyl sulfonic acid compounds, perfluoroalkyl carboxylic acid compounds, perfluoroalkyl phosphate ester compounds, perfluoroalkyl ethylene oxide adducts, and polyoxyalkylene ether polymer compounds having perfluoroalkyl ether groups in their side chains are preferred. Examples of the perfluoroalkyl sulfonic acid compound include perfluoroalkyl sulfonic acid, perfluoroalkyl sulfonate, and the like. Examples of the perfluoroalkyl carboxylic acid compound include perfluoroalkyl carboxylic acid, perfluoroalkyl carboxylate, and the like. Examples of the polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in a side chain thereof include sulfate ester salts of polyoxyalkylene ether polymers having a perfluoroalkyl ether group in a side chain, salts of polyoxyalkylene ether polymers having a perfluoroalkyl ether group in a side chain, and the like.

[0072] Further, fluorine-based surfactants represented by the following general formula (F-1) and general formula (F-2) are more preferable.

[0073]

Chemical Formula

[0074] C n F 2n+1 -CH2CH(OH)CH2-O-(CH2CH2O) a -Y General formula (F-2) In the compound represented by the general formula (F-2), Y is H or C m F 2m+1 , wherein m is an integer of 1 to 6; or CH2CH(OH)CH2-C m F 2m+1 , wherein m is an integer of 4 to 6; or C p H 2p+1 , wherein p is an integer of 1 to 19. n is an integer of 1 to 6. a is an integer of 4 to 14.

[0075] Examples of counterions for the salts of these fluorinated surfactants include Li, Na, K, NH4, NH3CH2CH2OH, NH2(CH2CH2OH)2, and NH(CH2CH2OH)3.

[0076] As the fluorine-based surfactant, a suitably synthesized one may be used, or a commercially available product may be used. Examples of commercially available fluorine-based surfactants include Surflon S-111, Surflon S-112, Surflon S-113, Surflon S-121, Surflon S-131, Surflon S-132, Surflon S-141, Surflon S-145 (all manufactured by AGC Inc.), Flurad FC-93, Flurad FC-95, Flurad FC-98, Flurad FC-129, Flurad FC-135, Flurad FC-170C, Flurad FC-430, Flurad FC-431 (all manufactured by Sumitomo 3M Limited), Megafac F-470, Megafac F-1405, Megafac F-474 (all manufactured by DIC Corporation), Zonyl TBS, Examples include FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, UR, Capstone FS-30, Capstone FS-31, Capstone FS-3100, Capstone FS-34, Capstone FS-35 (all manufactured by Chemors), FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW (all manufactured by Neos Corporation), Polyfox PF-136A, Polyfox PF-156A, Polyfox PF-151N, Polyfox PF-154, Polyfox PF-159 (all manufactured by Omnova), and Unidyne DSN-403N (manufactured by Daikin Industries, Ltd.). Among these, FS-3100, FS-34, FS-300 (all manufactured by Chemors), FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW (all manufactured by Neos Corporation), Polyfox PF-151N (all manufactured by Omnova), and Unidyne DSN-403N (all manufactured by Daikin Industries, Ltd.) are preferred because they offer excellent print quality, particularly significantly improved color development, penetration into paper, wettability, and uniform dyeing.

[0077] --Amphoteric surfactant-- The aforementioned amphoteric surfactant is not particularly limited and can be appropriately selected depending on the purpose. Examples include laurylaminopropionate, lauryldimethylbetaine, stearyldimethylbetaine, and lauryldihydroxyethylbetaine. These may be used individually or in combination of two or more.

[0078] --Nonionic surfactant-- The nonionic surfactant is not particularly limited and can be appropriately selected depending on the purpose. Examples include polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene alkylamines, polyoxyethylene alkylamides, polyoxyethylene propylene block polymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and ethylene oxide adducts of acetylene alcohol. These may be used individually or in combination of two or more.

[0079] --Anionic surfactant-- The anionic surfactant is not particularly limited and can be appropriately selected depending on the purpose. Examples include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, lauryl salt, and polyoxyethylene alkyl ether sulfate salts. These may be used individually or in combination of two or more.

[0080] There are no particular restrictions on the content of surfactants used as other components, and they can be appropriately selected depending on the purpose. However, from the viewpoint of excellent wettability and discharge stability, and improved image quality, a content of 0.001% to 5% by mass is preferred, and 0.05% to 5% by mass is more preferred.

[0081] -Antifoaming agent- Surfactants used as other components can be used as defoaming agents. There are no particular restrictions on the defoaming agent, and it can be appropriately selected depending on the purpose. Examples include silicone-based defoaming agents, polyether-based defoaming agents, and fatty acid ester-based defoaming agents. Among these, silicone-based defoaming agents are preferred because they have excellent foam-breaking effects. These may be used individually or in combination of two or more types.

[0082] -Preservative and fungicidal agent- There are no particular restrictions on the aforementioned preservative and antifungal agent, and it can be appropriately selected depending on the purpose. For example, 1,2-benzisothiazolin-3-one is one such example.

[0083] - pH adjuster - The pH adjusting agent is not particularly limited as long as it can adjust the pH to 7 or higher, and can be appropriately selected according to the purpose. Examples include amines such as diethanolamine and triethanolamine.

[0084] <Method for detecting contained substances> Qualitative and quantitative methods for organic solvents, resins, colorants, and other components contained in ink include, for example, gas chromatography-mass spectrometry (GC-MS). An example of a GC-MS measuring instrument is the GCMS-QP2020NX (manufactured by Shimadzu Corporation). Furthermore, water contained in ink can be measured by general methods such as quantitative analysis of volatile components by gas chromatography-mass spectrometry (GC-MS) or mass fluctuation analysis by simultaneous thermogravimetric and differential thermal analysis (TG-DTA).

[0085] <Ink properties> The physical properties of the ink of the present invention are not particularly limited and can be appropriately selected depending on the purpose. For example, it is preferable that the viscosity, surface tension, pH, etc., are within the following ranges. The viscosity of the ink of the present invention at 25°C is preferably 5 mPa·s to 30 mPa·s, and more preferably 5 mPa·s to 25 mPa·s, in order to improve print density and character quality, and to obtain good ejection performance. Here, the viscosity can be measured using, for example, a rotational viscometer (RE-80L manufactured by Toki Sangyo Co., Ltd.). The measurement conditions for the viscosity are 25°C, standard cone rotor (1°34' × R24), sample volume of 1.2 mL, rotation speed of 50 rpm, and measurement can be performed for 3 minutes. The surface tension of the ink of the present invention is preferably 35 mN / m or less, and more preferably 32 mN / m or less, at 25°C, in order to allow the ink to level nicely on the recording medium described later and shorten the ink drying time. From the viewpoint of preventing corrosion of metal components in contact with the ink, the pH of the ink of the present invention is preferably 7 to 12, and more preferably 8 to 11.

[0086] (ink container) The ink of the present invention can be used when contained in a container. In this specification, a container containing the ink of the present invention may be referred to as an "ink container". There are no particular restrictions on the ink storage container, and examples include well-known ink cartridges for inkjet printers. The aforementioned ink storage container is easy to store and transport, and offers excellent handling, so it can be detachably attached to ink cartridges, image forming apparatus, etc., and used for replenishing ink. The ink container is not particularly limited and can be appropriately selected from known containers, for example, one having a container body and a cap.

[0087] There are no particular restrictions on the shape of the ink container, and it can be appropriately selected according to the purpose, but it is preferably cylindrical. Furthermore, it is preferable that spiral-shaped irregularities are formed on the inner surface, allowing the ink contents to move towards the discharge port side by rotating it, and that some or all of the spiral-shaped irregularities have a bellows function. There are no particular restrictions on the material of the ink container, and it can be appropriately selected according to the purpose. However, from the viewpoint of good dimensional accuracy, resins such as polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, polyacrylic acid, polycarbonate resin component ABS resin, and polyacetal resin are preferred. There are no particular restrictions on the structure and size of the ink container, and they can be appropriately selected according to the purpose.

[0088] (Image forming apparatus and image forming method) The image forming apparatus of the present invention comprises an ink container for containing the ink of the present invention, and an ejection means for ejecting the ink contained in the ink container onto a recording medium, and may also have other means as needed. The image forming method of the present invention comprises the step of ejecting the ink of the present invention onto a recording medium to form an image, and may include other steps as needed.

[0089] <Discharge means and discharge process> The ejection means is a process of ejecting the ink contained in the ink container onto the recording medium. The ejection process is the process of ejecting the ink contained in the ink container onto the recording medium. The discharge step can be suitably carried out by the discharge means. There are no particular restrictions on the ejection means, and known ink ejection means can be used, such as an inkjet method.

[0090] <Other means and other processes> The aforementioned other means are not particularly limited and can be appropriately selected depending on the purpose. Examples include pre-processing means, post-processing means, heating means, drying means, and means related to feeding, transporting, and paper discharge of recording media. The aforementioned other processes are not particularly limited and can be appropriately selected depending on the purpose. Examples include pre-processing processes, post-processing processes, heating processes, drying processes, and processes related to the feeding, transporting, and discharge of recording media. The aforementioned other steps can be suitably carried out by the aforementioned other means.

[0091] -Pre-treatment means and pre-treatment process- The aforementioned pretreatment means is a means for applying a pretreatment solution to the recording medium before applying the ink. The aforementioned pretreatment step is a step of applying a pretreatment solution to the recording medium before applying the ink. The aforementioned pretreatment step can be suitably carried out by the aforementioned pretreatment means. One embodiment of a preprocessing apparatus equipped with the aforementioned preprocessing means is to add a liquid storage unit containing the preprocessing liquid and a liquid ejection head, similar to the case of inks such as black (K), cyan (C), magenta (M), yellow (Y), and white (W), and to eject the preprocessing liquid using an inkjet recording method. There are no particular limitations on the pretreatment means, and they can be appropriately selected depending on the purpose. Examples include a means of storing the pretreatment liquid in an ink storage means, similar to ordinary ink, and applying it to a recording medium using an inkjet method, as well as a blade coating method, a roll coating method, a spray coating method, etc.

[0092] The aforementioned pretreatment liquid contains a flocculant, an organic solvent, and water, and may optionally contain a surfactant, an antifoaming agent, a pH adjuster, a preservative and antifungal agent, a rust inhibitor, and the like. The organic solvent, surfactant, defoamer, pH adjuster, antiseptic and antifungal agent, and rust inhibitor can be the same materials used in inks, or other materials used in known processing solutions can be used. The type of flocculant is not particularly limited and can be appropriately selected depending on the purpose. Examples include water-soluble cationic polymers, acids, and polyvalent metal salts.

[0093] -Post-processing means and post-processing steps- The post-processing means is a means for applying a post-processing solution to the recording medium after applying the ink. The aforementioned pre-treatment step is a step of applying a post-treatment solution to the recording medium after applying the ink. The post-processing step can be suitably carried out by the post-processing means. One embodiment of a post-processing apparatus equipped with the aforementioned post-processing means is to add a liquid storage unit containing the post-processing liquid and a liquid ejection head, similar to the case of inks such as black (K), cyan (C), magenta (M), yellow (Y), and white (W), and to eject the post-processing liquid using an inkjet recording method. There are no particular limitations on the post-processing means, and they can be appropriately selected according to the purpose. Examples include a means of storing the post-processing liquid in an ink storage means, similar to ordinary ink, and applying it to a recording medium using an inkjet method, as well as a blade coating method, a roll coating method, a spray coating method, etc.

[0094] The post-treatment solution is not particularly limited as long as it can form a transparent layer. The post-treatment solution can be obtained by selecting and mixing organic solvents, water, resins, surfactants, defoamers, pH adjusters, anti-corrosion and anti-fungal agents, rust inhibitors, etc., as needed. The post-treatment solution may be applied to the entire recording area formed on the recording medium, or only to the area where the image is formed.

[0095] - Heating means and heating process, and drying means and drying process - The heating means includes, for example, means for heating the printed surface or the back surface of the recording medium. The heating step includes, for example, a step of heating the printed surface or the back surface of the recording medium. The heating step can be suitably carried out by the heating means. The drying means includes, for example, means for drying the printed surface or the back surface of the recording medium. The drying process includes, for example, drying the printed surface and the back surface of the recording medium. The drying process can be suitably carried out by the drying means. The heating means and drying means are not particularly limited, but for example, a hot air heater, an infrared heater, etc., can be used. Heating and drying can be performed before printing, during printing, or after printing.

[0096] The aforementioned image forming apparatus and image forming method are not limited to those that visualize meaningful images such as characters or figures using ink. For example, they also include those that form patterns such as geometric designs, and those that create three-dimensional images. Unless otherwise specified, the image forming apparatus includes both serial type apparatuses that move the ejection head and line type apparatuses that do not move the ejection head. The aforementioned image forming apparatus includes not only desktop models, but also wide-format recording devices capable of printing on A0-sized recording media, and continuous-feed printers that can use, for example, continuous paper wound in a roll as a recording medium.

[0097] <Recording medium> In this specification, "recording medium" refers to an object on which the ink of the present invention is recorded. Furthermore, the recording medium means an object to which the ink of the present invention or various processing solutions can be temporarily attached. There are no particular restrictions on the recording medium, and it can be appropriately selected according to the purpose. For example, plain paper, glossy paper, specialty paper, cloth, film, OHP sheets, general-purpose printing paper, and non-permeable substrates may be used. The aforementioned non-permeable substrate is a substrate having a surface with low water permeability and absorption, and includes materials that have numerous internal cavities but do not open to the outside. More quantitatively, in the Bristow method, from the start of contact to 30 msec 1 / 2 Up to 10 mL / m² of water absorption capacity 2 The following refers to the base material. Examples of the non-permeable substrate include plastic films such as polyvinyl chloride resin film, polyethylene terephthalate (PET) film, polypropylene, polyethylene, and polycarbonate film.

[0098] The recording medium is not limited to those commonly used as recording media; building materials such as wallpaper, flooring, and tiles, fabrics for clothing such as T-shirts, textiles, and leather can be used as appropriate. Furthermore, by adjusting the configuration of the transport path for the recording medium, ceramics, glass, and metal can also be used.

[0099] <Records> A recording medium having an image formed using the ink of the present invention can be used as a recording medium. The aforementioned recording can be obtained by recording using the image forming apparatus and image forming method.

[0100] Here, an example of the image forming apparatus of the present invention will be described with reference to Figures 1 and 2. Figure 1 is a perspective view of the apparatus. Figure 2 is a perspective view of the main tank. The image forming apparatus 400 is a serial type image forming apparatus. A mechanism 420 is provided inside the exterior 401 of the image forming apparatus 400. For example, each ink storage section 411 of the main tanks 410 (410k, 410c, 410m, 410y) for each color such as black (K), cyan (C), magenta (M), and yellow (Y) is formed from a packaging material such as aluminum laminate film. The ink storage section 411 is housed in a storage container case 414 made of plastic, for example. Thus, the main tanks 410 are used as ink cartridges for each color. Note that the ink colors are not limited to black (K), cyan (C), magenta (M), and yellow (Y), but may also be other colors such as white (W) or metallic ink. The same applies to the main tanks 410 and ink reservoirs 411 for each color. Meanwhile, a cartridge holder 404 is provided at the back of the opening when the cover 401c of the main body of the device is opened. The main tank 410 is detachably mounted on the cartridge holder 404. As a result, the ink outlets 413 of the main tank 410 and the ejection heads 434 for each color are connected via supply tubes 436 for each color, enabling ink to be ejected from the ejection heads 434 to the recording medium. Alternatively, the main tanks 410 for each color and each ink storage section 411 may be filled with a pre-treatment liquid or a post-treatment liquid instead of ink, and then ejected from the ejection head 434 to the recording medium.

[0101] <Application> The ink of the present invention can be suitably used in various recording devices using the inkjet recording method, such as printers, facsimile machines, copying machines, printer / fax / copier combination machines, and 3D modeling devices. Furthermore, there are no particular limitations on the applications of the ink of the present invention; it can be appropriately selected according to the purpose, and can be applied, for example, to printed materials, paints, coatings, and undercoats. In addition, it can be used not only to form two-dimensional characters and images, but also as a material for three-dimensional modeling to form three-dimensional objects. The aforementioned three-dimensional objects include three-dimensional objects obtained by applying multiple layers of ink. They also include molded products formed by processing a structure onto which ink has been applied, such as a recording medium. The three-dimensional modeling apparatus for creating the aforementioned three-dimensional object can be any known apparatus and is not particularly limited, but for example, one equipped with means for containing ink, supplying ink, dispensing ink, drying ink, etc., can be used. The aforementioned molded products are, for example, those obtained by subjecting sheet-like or film-like recordings or structures to molding processes such as heat stretching or die-cutting. They are suitably used in applications where the surface is decorated before molding, such as meters and control panels for automobiles, office automation equipment, electrical and electronic equipment, and cameras.

[0102] (Solar backsheet) A polymer having the structural unit represented by the general formula (1), or a copolymer having the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2), can also be used as a resin included in the protective layer of a solar cell backsheet. In other words, the solar cell backsheet of the present invention has a protective layer made of titanium dioxide and a resin, wherein the resin contained in the protective layer includes a polymer having a structural unit represented by the general formula (1), or a copolymer having a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2), and may optionally contain other resins (B). The solar cell backsheet of the present invention can improve the weather resistance of the solar cell module to light irradiation from both the light-receiving side and the back side by, for example, being provided on the back of the solar cell module.

[0103] The protective layer is preferably provided on a base film. There are no particular restrictions on the base film, and it can be appropriately selected depending on the purpose. However, from the viewpoint of excellent mechanical strength, dimensional stability, and thermal stability, polyester film is preferred, and polyester film mainly composed of polyethylene terephthalate or polyethylene naphthalate is more preferred. The aforementioned other resin (B) is not particularly limited and can be appropriately selected depending on the purpose, but from the viewpoint of excellent mechanical strength and heat resistance, acrylic resins are preferred, and acrylic resins that can be crosslinked with isocyanate are more preferred.

[0104] <Manufacturing method for solar cell backsheets> There are no particular limitations on the method for manufacturing the solar cell backsheet, and it can be appropriately selected depending on the purpose. For example, it can be manufactured by the following method (steps (1) to (4)). Step (1): Add the polymer or copolymer of the present invention to an organic solvent, stir and dissolve to prepare a solution, then gradually add the colorant to the solution while stirring, and stir again. Step (2): After dispersion using a dispersion device, the contents are filtered through a membrane filter. If necessary, an adjusted amount of organic solvent is added to prepare a protective layer forming solution. Step (3): The protective layer forming liquid is applied to the substrate surface using a wire bar and dried until the desired thickness is reached to create a protective layer. Step (4): By aging the protective layer, a solar cell backsheet is obtained.

[0105] There are no particular restrictions on the organic solvent used in step (1) above, and it can be appropriately selected depending on the purpose. For example, the organic solvents described in the (ink) section above, or hexamethylene diisocyanate can be suitably used. There are no particular restrictions on the colorant used in step (1) above, and it can be appropriately selected according to the purpose. For example, the colorants described in the (ink) section above can be suitably used. There are no particular restrictions on the dispersion device in step (2) above, and it can be appropriately selected according to the purpose. For example, the Big Rotor BR-2 (manufactured by AS ONE Corporation) can be used. There are no particular restrictions on the conditions for the dispersion process, and they can be appropriately selected according to the purpose. For example, the rotation speed can be set to 90 rpm and the processing time to 5 days. There are no particular restrictions on the substrate used in step (3) above, and it can be appropriately selected according to the purpose. For example, the recording media described in the above section (Image forming apparatus and image forming method) can be suitably used. In step (3) above, the "any film thickness" is not particularly limited and can be appropriately selected depending on the purpose; for example, it can be 2 μm. There are no particular restrictions on the drying conditions in step (3) above, and they can be appropriately selected according to the purpose. For example, the drying temperature can be set to 150°C and the drying time to 5 minutes. There are no particular restrictions on the aging conditions in step (4) above, and they can be appropriately selected according to the purpose. For example, the processing temperature can be set to 50°C and the processing time to 3 days.

[0106] In this specification, image formation, recording, printing, and the like are all synonymous. In this specification, recording media, media, and printed material are all synonymous. [Examples]

[0107] The following are examples of the present invention, but the scope of the present invention is not limited to these examples. In the following examples and comparative examples, "parts" and "%" refer to "parts by mass" and "% by mass" and respectively, unless otherwise specified.

[0108] The molecular weights of the polymers or copolymers obtained in the synthesis examples, examples, and comparative examples described later were measured by the following methods and conditions. (Measurement of molecular weight) Measurements were taken using GPC (Gel Permeation Chromatography) under the following conditions. • Equipment: GPC-8020 (manufactured by Tosoh Corporation) • Columns: TSK G2000HXL and G4000HXL (manufactured by Tosoh Corporation) ·Temperature: 40℃ • Solvent: THF (tetrahydrofuran) ·Flow rate: 1.0mL / min 1 mL of a polymer or copolymer at a concentration of 0.5% by mass was injected, and the number-average molecular weight (Mn) and weight-average molecular weight (Mw) of the polymer or copolymer were calculated from the molecular weight distribution of the polymer or copolymer measured under the above conditions using a molecular weight calibration curve prepared with monodisperse polystyrene standard samples.

[0109] (Synthesis of monomers) <Example of monomer synthesis 1> In a 100 mL four-necked flask, 4.81 g (80 mmol) of 1,2-ethylenediamine (Tokyo Chemical Co., Ltd.) was placed, and while stirring under a nitrogen stream, a solution of 3.92 g (16 mmol) of 2-bromoethylphosphonate diethyl ester (Tokyo Chemical Co., Ltd.) dissolved in 20 mL of ethanol (EtOH) (Kanto Chemical Co., Ltd.) was added dropwise over 30 minutes. After stirring at room temperature for 12 hours, the solvent was removed by distillation. 30 mL of ethyl acetate (Kanto Chemical Co., Ltd.) was added to the residue, and after stirring for 5 minutes, the precipitate was filtered off. The precipitate was purified by silica gel column chromatography using dichloromethane (MDC) / methanol (MeOH) (10 / 0~9 / 1 (v / v)) (Kanto Chemical Co., Ltd.) as the eluent to obtain 2.67 g of diethyl (2-N-(2-aminoethyl)aminoethyl)phosphonate diethyl ester (M1a). Next, 10 mL of tetrahydrofuran (THF) (manufactured by Kanto Chemical Co., Ltd.) and 2.25 g (10 mmol) of (M1a) were added to a 50 mL three-necked flask, and the mixture was cooled with ice water under a nitrogen stream. A solution of 2.02 g (10 mmol) of 3-isopropenyl-α,α-dimethylbenzyl isocyanate (manufactured by Tokyo Chemical Co., Ltd.) dissolved in 20 mL of THF was gradually added over 5 minutes, and the mixture was stirred at 0°C to room temperature for 15 hours. The solvent was removed by distillation, and the residue was purified by silica gel column chromatography using MDC / MeOH (8 / 2 (v / v)) (manufactured by Kanto Chemical Co., Ltd.) as the eluent to obtain 3.78 g of 2-(2-(3-(2-(3-prop-1-en-2-yl)phenyl)propan-2-yl)ureido)ethylamino)ethylphosphonic acid diethyl ester (M1b). Next, 2.13 g (5 mmol) of (M1b) was placed in a 100 mL round-bottom flask, and 10 mL of super-dehydrated MDC was added to dissolve it. A solution of 3.06 g (20 mmol) of trimethylsilyl bromide (manufactured by Tokyo Chemical Co., Ltd.) dissolved in 10 mL of super-dehydrated MDC was added under a nitrogen stream, and the mixture was stirred for 24 hours. Excess trimethylsilyl bromide was removed from the resulting solution under reduced pressure at room temperature to obtain 2.45 g of a white solid. 40 mL of MeOH was added under a nitrogen stream, and the mixture was stirred for 24 hours, after which the volatile components were removed by distillation under reduced pressure at room temperature. The resulting residue was washed twice with 30 mL of hexane (manufactured by Kanto Chemical Co., Ltd.), dried under reduced pressure at room temperature to obtain 1.69 g of 2-(2-(3-(2-(3-prop-1-en-2-yl)phenyl)propan-2-yl)ureido)ethylamino)ethylphosphonic acid (M1). The structural formula of the obtained monomer (M1) is shown below.

[0110] [ka]

[0111] <Example of monomer synthesis 2> In a 100 mL four-necked flask, 7.05 g (80 mmol) of 1,4-diaminobutane (Tokyo Chemical Industries, Ltd.) was placed, and while stirring under a nitrogen stream, a solution of 3.92 g (16 mmol) of 2-bromoethylphosphonate diethyl ester dissolved in 20 mL of EtOH was added dropwise over 30 minutes. After stirring at room temperature for 12 hours, the solvent was removed by distillation. 30 mL of ethyl acetate was added to the residue, and after stirring for 5 minutes, the precipitate was filtered off. The precipitate was purified by silica gel column chromatography using MDC / MeOH (10 / 0~9 / 1 (v / v)) as the eluent to obtain 3.07 g of diethyl(2-N-(4-aminobutyl)aminoethyl)phosphonate diethyl ester (M2a). Next, 10 mL of THF and 2.53 g (10 mmol) of (M2a) were added to a 50 mL three-necked flask and cooled with ice water under a nitrogen stream. A solution of 2.02 g (10 mmol) of 3-isopropenyl-α,α-dimethylbenzyl isocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 20 mL of THF was gradually added over 5 minutes, and the mixture was stirred at 0°C to room temperature for 15 hours. The solvent was removed by distillation, and the residue was purified by silica gel column chromatography using MDC / MeOH (8 / 2 (v / v)) as the eluent to obtain 3.86 g of 2-(4-(3-(2-(3-prop-1-en-2-yl)phenyl)propan-2-yl)ureido)butylamino)ethylphosphonic acid diethyl ester (M2b). Next, 2.27 g (5 mmol) of (M2b) was placed in a 100 mL round-bottom flask, and 10 mL of super-dehydrated MDC was added to dissolve it. A solution of 3.06 g (20 mmol) of trimethylsilyl bromide dissolved in 10 mL of super-dehydrated MDC was added under a nitrogen stream, and the mixture was stirred for 24 hours. Excess trimethylsilyl bromide was removed from the resulting solution under reduced pressure at room temperature to obtain 2.55 g of a white solid. 40 mL of MeOH was added under a nitrogen stream, and the mixture was stirred for 24 hours, after which the volatile components were removed under reduced pressure at room temperature. The resulting residue was washed twice with 30 mL of hexane and dried under reduced pressure at room temperature to obtain 1.77 g of 2-(4-(3-(2-(3-prop-1-en-2-yl)phenyl)propan-2-yl)ureido)butylamino)ethylphosphonic acid (M2). The structural formula of the obtained monomer (M2) is shown below.

[0112] [ka]

[0113] <Example of monomer synthesis 3> 20 mL of EtOH was placed in a 100 mL four-necked flask, and 11.54 g (80 mmol) of 1,8-diaminoocta (Tokyo Chemical Co., Ltd.) was added and dissolved. Under a nitrogen stream of stirring, a solution of 3.92 g (16 mmol) of 2-bromoethylphosphonate diethyl ester dissolved in 20 mL of EtOH was added dropwise over 30 minutes. After stirring at room temperature for 12 hours, the solvent was removed by distillation. 50 mL of ethyl acetate was added to the residue, and after stirring for 5 minutes, the precipitate was filtered off. The precipitate was purified by silica gel column chromatography using MDC / MeOH (10 / 0~9 / 1 (v / v)) as the eluent to obtain 5.56 g of diethyl(2-N-(8-aminooctyl)aminoethyl)phosphonate diethyl ester (M3a). Next, 10 mL of THF and 3.10 g (10 mmol) of (M3a) were added to a 50 mL three-necked flask and cooled with ice water under a nitrogen stream. A solution of 2.02 g (10 mmol) of 3-isopropenyl-α,α-dimethylbenzyl isocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 20 mL of THF was gradually added over 5 minutes, and the mixture was stirred at 0°C to room temperature for 15 hours. The solvent was removed by distillation, and the residue was purified by silica gel column chromatography using MDC / MeOH (8 / 2 (v / v)) as the eluent to obtain 4.43 g of 2-(8-(3-(2-(3-prop-1-en-2-yl)phenyl)propan-2-yl)ureido)octylamino)ethylphosphonic acid diethyl ester (M3b). Next, 2.55 g (5 mmol) of (M3b) was placed in a 100 mL round-bottom flask, and 10 mL of super-dehydrated MDC was added to dissolve it. A solution of 3.06 g (20 mmol) of trimethylsilyl bromide dissolved in 10 mL of super-dehydrated MDC was added under a nitrogen stream, and the mixture was stirred for 24 hours. Excess trimethylsilyl bromide was removed from the resulting solution under reduced pressure at room temperature to obtain 2.83 g of a white solid. 40 mL of MeOH was added under a nitrogen stream, and the mixture was stirred for 24 hours, after which the volatile components were removed by distillation under reduced pressure at room temperature. The resulting residue was washed twice with 30 mL of hexane and dried under reduced pressure at room temperature to obtain 2.02 g of 2-(8-(3-(2-(3-prop-1-en-2-yl)phenyl)propan-2-yl)ureido)octylamino)ethylphosphonic acid (M3). The structural formula of the obtained monomer (M3) is shown below.

[0114] [ka]

[0115] <Example of monomer synthesis 4> 20 mL of EtOH was placed in a 100 mL four-necked flask, and 16.03 g (80 mmol) of 1,12-diaminododecane (Tokyo Chemical Co., Ltd.) was added and dissolved. Under a nitrogen stream of stirring, a solution of 3.92 g (16 mmol) of 2-bromoethylphosphonate diethyl ester dissolved in 20 mL of EtOH was added dropwise over 30 minutes. After stirring at room temperature for 12 hours, the solvent was removed by distillation. 50 mL of ethyl acetate was added to the residue, and after stirring for 5 minutes, the precipitate was filtered off. The precipitate was purified by silica gel column chromatography using MDC / MeOH (10 / 0~9 / 1 (v / v)) as the eluent to obtain 6.55 g of diethyl(2-N-(12-aminododecyl)aminoethyl)phosphonate diethyl ester (M4a). Next, 10 mL of THF and 3.10 g (10 mmol) of (M4a) were added to a 50 mL three-necked flask and cooled with ice water under a nitrogen stream. A solution of 2.02 g (10 mmol) of 3-isopropenyl-α,α-dimethylbenzyl isocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 20 mL of THF was gradually added over 5 minutes, and the mixture was stirred at 0°C to room temperature for 15 hours. The solvent was removed by distillation, and the residue was purified by silica gel column chromatography using MDC / MeOH (8 / 2 (v / v)) as the eluent to obtain 4.48 g of 2-(12-(3-(2-(3-prop-1-en-2-yl)phenyl)propan-2-yl)ureido)dodecylamino)ethylphosphonic acid diethyl ester (M4b). Next, 2.83 g (5 mmol) of (M4b) was placed in a 100 mL round-bottom flask, and 10 mL of super-dehydrated MDC was added to dissolve it. A solution of 3.06 g (20 mmol) of trimethylsilyl bromide dissolved in 10 mL of super-dehydrated MDC was added under a nitrogen stream, and the mixture was stirred for 24 hours. Excess trimethylsilyl bromide was removed from the resulting solution under reduced pressure at room temperature to obtain 3.15 g of a white solid. 40 mL of MeOH was added under a nitrogen stream, and the mixture was stirred for 24 hours, after which the volatile components were removed under reduced pressure at room temperature. The resulting residue was washed twice with 30 mL of hexane and dried under reduced pressure at room temperature to obtain 2.35 g of 2-(12-(3-(2-(3-prop-1-en-2-yl)phenyl)propan-2-yl)ureido)dodecylamino)ethylphosphonic acid (M4). The structural formula of the obtained monomer (M4) is shown below.

[0116] [ka]

[0117] <Example 5 of monomer synthesis> 20 mL of EtOH was placed in a 100 mL four-necked flask, and 9.30 g (80 mmol) of 1,6-diaminohexane (Tokyo Chemical Industries, Ltd.) was added and dissolved. Under a nitrogen stream of stirring, a solution of 3.92 g (16 mmol) of 2-bromoethylphosphonate diethyl ester dissolved in 20 mL of EtOH was added dropwise over 30 minutes. After stirring at room temperature for 12 hours, the solvent was removed by distillation. 50 mL of ethyl acetate was added to the residue, and after stirring for 5 minutes, the precipitate was filtered off. The precipitate was purified by silica gel column chromatography using MDC / MeOH (10 / 0~9 / 1 (v / v)) as the eluent to obtain 6.55 g of diethyl(2-N-(6-aminohexyl)aminoethyl)phosphonate diethyl ester (M5a). Next, 10 mL of THF and 2.82 g (10 mmol) of (M5a) were added to a 50 mL three-necked flask and cooled with ice water under a nitrogen stream. A solution of 1.56 g (10 mmol) of 2-isocyanatoethyl methacrylate (Tokyo Chemical Co., Ltd.) dissolved in 20 mL of THF was gradually added over 5 minutes, and the mixture was stirred at 0°C to room temperature for 15 hours. The solvent was removed by distillation, and the residue was purified by silica gel column chromatography using MDC / MeOH (8 / 2 (v / v)) as the eluent to obtain 3.14 g of monomer precursor (M5b). Next, 2.18 g (5 mmol) of monomer precursor (M5b) was placed in a 100 mL round-bottom flask, and 10 mL of super-dehydrated MDC was added to dissolve it. A solution of 3.06 g (20 mmol) of trimethylsilyl bromide dissolved in 10 mL of super-dehydrated MDC was added under a nitrogen stream, and the mixture was stirred for 24 hours. Excess trimethylsilyl bromide was removed from the resulting solution under reduced pressure at room temperature to obtain 2.45 g of a white solid. 40 mL of MeOH was added under a nitrogen stream, and the mixture was stirred for 24 hours, after which the volatile components were removed by distillation under reduced pressure at room temperature. The resulting residue was washed twice with 30 mL of hexane and dried under reduced pressure at room temperature to obtain 1.68 g of monomer (M5). The structural formulas of the obtained monomer precursor (M5b) and monomer (M5) are shown below.

[0118] [ka]

[0119] <Example of monomer synthesis 6> 20 mL of EtOH was placed in a 100 mL four-necked flask, and 2.25 g (19 mmol) of 6-amino-1-hexanol (Tokyo Chemical Co., Ltd.) was added and dissolved. Under a nitrogen stream of stirring, a solution of 3.92 g (16 mmol) of 2-bromoethylphosphonic acid diethyl ester dissolved in 20 mL of EtOH was added dropwise over 30 minutes. After stirring at room temperature for 12 hours, the solvent was removed by distillation. The residue was purified by silica gel column chromatography using MDC / MeOH (10 / 0~9 / 1 (v / v)) as the eluent to obtain 3.36 g of diethyl(2-(6-hydroxyhexylamino)ethylphosphonic acid diethyl ester (M6a). Next, 10 mL of THF and 2.83 g (10 mmol) of (M6a) were added to a 50 mL three-necked flask and cooled with ice water under a nitrogen stream. A solution of 1.56 g (10 mmol) of 2-isocyanatoethyl methacrylate (Tokyo Chemical Co., Ltd.) dissolved in 20 mL of THF was gradually added over 5 minutes, and the mixture was stirred at 0°C to room temperature for 15 hours. The solvent was removed by distillation, and the residue was purified by silica gel column chromatography using MDC / MeOH (8 / 2 (v / v)) as the eluent to obtain 3.23 g of monomer precursor (M6b). Next, 2.18 g (5 mmol) of monomer precursor (M6b) was placed in a 100 mL round-bottom flask, and 10 mL of super-dehydrated MDC was added to dissolve it. A solution of 3.06 g (20 mmol) of trimethylsilyl bromide dissolved in 10 mL of super-dehydrated MDC was added under a nitrogen stream, and the mixture was stirred for 24 hours. Excess trimethylsilyl bromide was removed from the resulting solution under reduced pressure at room temperature to obtain 2.48 g of a white solid. 40 mL of MeOH was added under a nitrogen stream, and the mixture was stirred for 24 hours, after which volatile components were removed by distillation under reduced pressure at room temperature. The resulting residue was washed twice with 30 mL of hexane and dried under reduced pressure at room temperature to obtain 1.69 g of monomer (M6). The structural formulas of the obtained monomer precursor (M6b) and monomer (M6) are shown below.

[0120] [ka]

[0121] <Example 7 of monomer synthesis> In a 50 mL three-necked flask, 10 mL of THF and 2.80 g (10 mmol) of (M5a) were added and cooled with ice water under a nitrogen stream. A solution of 1.41 g (10 mmol) of 2-isocyanatoethyl acrylate (Tokyo Chemical Co., Ltd.) dissolved in 20 mL of THF was gradually added over 5 minutes, and the mixture was stirred at 0°C to room temperature for 15 hours. The solvent was removed by distillation, and the residue was purified by silica gel column chromatography using MDC / MeOH (8 / 2 (v / v)) as the eluent to obtain 3.15 g of monomer precursor (M7b). Next, 2.11 g (5 mmol) of monomer precursor (M7b) was placed in a 100 mL round-bottom flask, and 10 mL of super-dehydrated MDC was added to dissolve it. A solution of 3.06 g (20 mmol) of trimethylsilyl bromide dissolved in 10 mL of super-dehydrated MDC was added under a nitrogen stream, and the mixture was stirred for 24 hours. Excess trimethylsilyl bromide was removed from the resulting solution under reduced pressure at room temperature to obtain 2.39 g of a white solid. 40 mL of MeOH was added under a nitrogen stream, and the mixture was stirred for 24 hours, after which volatile components were removed by distillation under reduced pressure at room temperature. The resulting residue was washed twice with 30 mL of hexane and dried under reduced pressure at room temperature to obtain 1.66 g of monomer (M7). The structural formulas of the obtained monomer precursor (M7b) and monomer (M7) are shown below.

[0122] [ka]

[0123] <Example of monomer synthesis 8> In a 50 mL three-necked flask, 10 mL of THF and 2.81 g (10 mmol) of (M6a) were added and cooled with ice water under a nitrogen stream. A solution of 1.41 g (10 mmol) of 2-isocyanate ethyl acrylate (Tokyo Chemical Co., Ltd.) dissolved in 20 mL of THF was gradually added over 5 minutes, and the mixture was stirred at 0°C to room temperature for 15 hours. The solvent was removed by distillation, and the residue was purified by silica gel column chromatography using MDC / MeOH (8 / 2 (v / v)) as the eluent to obtain 3.23 g of monomer precursor (M8b). Next, 2.11 g (5 mmol) of monomer precursor (M8b) was placed in a 100 mL round-bottom flask, and 10 mL of super-dehydrated MDC was added to dissolve it. A solution of 3.06 g (20 mmol) of trimethylsilyl bromide dissolved in 10 mL of super-dehydrated MDC was added under a nitrogen stream, and the mixture was stirred for 24 hours. Excess trimethylsilyl bromide was removed from the resulting solution under reduced pressure at room temperature to obtain 2.41 g of a white solid. 40 mL of MeOH was added under a nitrogen stream, and the mixture was stirred for 24 hours, after which volatile components were removed by distillation under reduced pressure at room temperature. The resulting residue was washed twice with 30 mL of hexane and dried under reduced pressure at room temperature to obtain 1.68 g of monomer (M8). The structural formulas of the obtained monomer precursor (M8b) and monomer (M8) are shown below.

[0124] [ka]

[0125] <Example of monomer synthesis 9> In a 50 mL three-necked flask, 10 mL of THF and 2.80 g (10 mmol) of (M5a) were added and cooled with ice water under a nitrogen stream. A solution of 1.54 g (10 mmol) of N-(3-isocyanatetopropyl)acrylamide (Chemieliva Pharmaceutical) dissolved in 20 mL of THF was gradually added over 5 minutes, and the mixture was stirred at 0°C to room temperature for 15 hours. The solvent was removed by distillation, and the residue was purified by silica gel column chromatography using MDC / MeOH (8 / 2 (v / v)) as the eluent to obtain 3.15 g of monomer precursor (M9b). Next, 2.11 g (5 mmol) of monomer precursor (M9b) was placed in a 100 mL round-bottom flask, and 10 mL of super-dehydrated MDC was added to dissolve it. A solution of 3.06 g (20 mmol) of trimethylsilyl bromide dissolved in 10 mL of super-dehydrated MDC was added under a nitrogen stream, and the mixture was stirred for 24 hours. Excess trimethylsilyl bromide was removed from the resulting solution under reduced pressure at room temperature to obtain 2.39 g of a white solid. 40 mL of MeOH was added under a nitrogen stream, and the mixture was stirred for 24 hours, after which volatile components were removed by distillation under reduced pressure at room temperature. The resulting residue was washed twice with 30 mL of hexane and dried under reduced pressure at room temperature to obtain 1.66 g of monomer (M9). The structural formulas of the obtained monomer precursor (M9b) and monomer (M9) are shown below.

[0126] [ka]

[0127] <10 Examples of Monomer Synthesis> In a 50 mL three-necked flask, 10 mL of THF and 2.81 g (10 mmol) of (M6a) were added and cooled with ice water under a nitrogen stream. To this, a solution of 1.54 g (10 mmol) of N-(3-isocyanatetopropyl)acrylamide (Chemieliva Pharmaceutical) dissolved in 20 mL of THF was gradually added over 5 minutes, and the mixture was stirred at 0°C to room temperature for 15 hours. The solvent was removed by distillation, and the residue was purified by silica gel column chromatography using MDC / MeOH (8 / 2 (v / v)) as the eluent to obtain 3.23 g of monomer precursor (M10b). Next, 2.18 g (5 mmol) of monomer precursor (M10b) was placed in a 100 mL round-bottom flask, and 10 mL of super-dehydrated MDC was added to dissolve it. A solution of 3.06 g (20 mmol) of trimethylsilyl bromide dissolved in 10 mL of super-dehydrated MDC was added under a nitrogen stream, and the mixture was stirred for 24 hours. Excess trimethylsilyl bromide was removed from the resulting solution under reduced pressure at room temperature to obtain 2.47 g of a white solid. 40 mL of MeOH was added under a nitrogen stream, and the mixture was stirred for 24 hours, after which volatile components were removed by distillation under reduced pressure at room temperature. The resulting residue was washed twice with 30 mL of hexane and dried under reduced pressure at room temperature to obtain 1.66 g of monomer (M10). The structural formulas of the obtained monomer precursor (M10b) and monomer (M10) are shown below.

[0128] [ka]

[0129] <Monomer Synthesis Example 11> In a 50 mL three-necked flask, 10 mL of THF and 2.66 g (10 mmol) of (M5a) were added and cooled with ice water under a nitrogen stream. To this, a solution of 1.85 g (10 mmol) of 2-(2-isocyanate ethoxy)ethyl acrylate (FCH Group) dissolved in 20 mL of THF was gradually added over 5 minutes, and the mixture was stirred at 0°C to room temperature for 15 hours. The solvent was removed by distillation, and the residue was purified by silica gel column chromatography using MDC / MeOH (8 / 2 (v / v)) as the eluent to obtain 3.72 g of monomer precursor (M11b). Next, 2.33 g (5 mmol) of monomer precursor (M11b) was placed in a 100 mL round-bottom flask, and 10 mL of super-dehydrated MDC was added to dissolve it. A solution of 3.06 g (20 mmol) of trimethylsilyl bromide dissolved in 10 mL of super-dehydrated MDC was added under a nitrogen stream, and the mixture was stirred for 24 hours. Excess trimethylsilyl bromide was removed from the resulting solution under reduced pressure at room temperature to obtain 2.66 g of a white solid. 40 mL of MeOH was added under a nitrogen stream, and the mixture was stirred for 24 hours, after which volatile components were removed by distillation under reduced pressure at room temperature. The resulting residue was washed twice with 30 mL of hexane and dried under reduced pressure at room temperature to obtain 1.87 g of monomer (M11). The structural formulas of the obtained monomer precursor (M11b) and monomer (M11) are shown below.

[0130] [ka]

[0131] <Monomer Synthesis Example 12> In a 50 mL three-necked flask, 10 mL of THF and 2.67 g (10 mmol) of (M6a) were added and cooled with ice water under a nitrogen stream. To this, a solution of 1.85 g (10 mmol) of 2-(2-isocyanate ethoxy)ethyl acrylate (FCH Group) dissolved in 20 mL of THF was gradually added over 5 minutes, and the mixture was stirred at 0°C to room temperature for 15 hours. The solvent was removed by distillation, and the residue was purified by silica gel column chromatography using MDC / MeOH (8 / 2 (v / v)) as the eluent to obtain 3.65 g of monomer precursor (M12b). Next, 2.33 g (5 mmol) of monomer precursor (M12b) was placed in a 100 mL round-bottom flask, and 10 mL of super-dehydrated MDC was added to dissolve it. A solution of 3.06 g (20 mmol) of trimethylsilyl bromide dissolved in 10 mL of super-dehydrated MDC was added under a nitrogen stream, and the mixture was stirred for 24 hours. Excess trimethylsilyl bromide was removed from the resulting solution under reduced pressure at room temperature to obtain 2.61 g of a white solid. 40 mL of MeOH was added under a nitrogen stream, and the mixture was stirred for 24 hours, after which volatile components were removed by distillation under reduced pressure at room temperature. The resulting residue was washed twice with 30 mL of hexane and dried under reduced pressure at room temperature to obtain 1.89 g of monomer (M12). The structural formulas of the obtained monomer precursor (M12b) and monomer (M12) are shown below.

[0132] [ka]

[0133] <Monomer Synthesis Example 13> In a 100 mL flask, 6.00 g (20 mmol) of tetraethyl ethylene-1,1-diylbisphosphonate (Apollo Scientific Ltd.), 0.72 g (2 mmol) of copper(II) trifluoromethanesulfonate (Sigma-Aldrich), and 4.14 g (30 mmol) of 4-hydroxyphenylboronic acid (Tokyo Chemical Co., Ltd.) were added, and 50 mL of anhydrous toluene (Kanto Chemical Co., Ltd.) was added. The mixture was heated to 70 °C, stirred for 18 hours, cooled to room temperature, and diluted with 100 mL of dichloromethane (Kanto Chemical Co., Ltd.). The diluted solution was extracted using a saturated aqueous solution of saturated ethylenediaminetetraacetic acid (Tokyo Chemical Co., Ltd.), washed with water, and the organic phase was isolated. The solvent was removed from the organic phase by distillation, and the residue was purified by silica gel column chromatography using acetone / hexane (4 / 6~5 / 5 (v / v)) (manufactured by Kanto Chemical Co., Ltd.) as the eluent to obtain 5.66 g of monomer precursor (M13a). Next, 100 mL of methyl ethyl ketone (manufactured by Kanto Chemical Co., Ltd.) was placed in a 200 mL flask, and 3.94 g (10 mmol) of monomer precursor (M13a), 2.72 g (15 mmol) of 6-bromo-1-hexanol (manufactured by Tokyo Chemical Co., Ltd.), and 2.77 g (20 mmol) of potassium carbonate (manufactured by Kanto Chemical Co., Ltd.) were added, and the mixture was refluxed for 12 hours. After cooling to room temperature, the mixture was filtered through filter paper, and the filtrate was concentrated. The residue was purified by silica gel column chromatography using MDC / MeOH (98 / 2~90 / 10 (v / v)) as the eluent to obtain 3.22 g of monomer precursor (M13b). The structural formulas of the obtained monomer precursors (M13a) and (M13b) are shown below.

[0134] [ka] Next, 20 mL of super-dehydrated MDC was placed in a 100 mL flask, and 2.47 g (5 mmol) of monomer precursor (M13b) and 0.016 g (0.025 mmol) of dibutyltin dilaurate (Tokyo Chemical Co., Ltd.) were added. The mixture was then cooled with ice water under a nitrogen stream. 2.01 g (10 mmol) of 3-isopropenyl-α,α-dimethylbenzyl isocyanate (Tokyo Chemical Co., Ltd.) was added gradually over 10 minutes, and the mixture was stirred at 0°C to room temperature for 12 hours. The solvent was removed by distillation, and the residue was purified by silica gel column chromatography using MDC / MeOH (8 / 2 (v / v)) as the eluent to obtain 2.56 g of monomer precursor (M13c). Next, 1.39 g (2 mmol) of monomer precursor (M13c) was placed in a 100 mL round-bottom flask, and 20 mL of super-dehydrated MDC was added to dissolve it. 2.45 g (16 mmol) of trimethylsilyl bromide was added under a nitrogen stream, and the mixture was stirred for 24 hours. Excess trimethylsilyl bromide was removed from the resulting solution under reduced pressure at room temperature to obtain 1.71 g of a white solid. 40 mL of MeOH was added under a nitrogen stream, and the mixture was stirred for 24 hours, after which the volatile components were removed by distillation under reduced pressure at room temperature. The resulting residue was washed twice with 30 mL of hexane and dried under reduced pressure at room temperature to obtain 1.12 g of monomer (M13). The structural formulas of the obtained monomer precursor (M13c) and monomer (M13) are shown below.

[0135] [ka]

[0136] <Monomer Synthesis Example 14> 20 mL of ultra-dehydrated MDC was placed in a 100 mL flask, and 2.47 g (5 mmol) of monomer precursor (M13b) and 0.016 g (0.025 mmol) of dibutyltin dilaurate were added. The mixture was cooled with ice water under a nitrogen stream. 1.55 g (10 mmol) of 2-isocyanatoethyl methacrylate (Tokyo Chemical Co., Ltd.) was added gradually over 5 minutes, and the mixture was stirred at 0°C to room temperature for 12 hours. The solvent was removed by distillation, and the residue was purified by silica gel column chromatography using MDC / MeOH (8 / 2 (v / v)) as the eluent to obtain 2.55 g of monomer precursor (M14c). Next, 1.30 g (2 mmol) of monomer precursor (M14c) was placed in a 100 mL round-bottom flask, and 20 mL of super-dehydrated MDC was added to dissolve it. 2.45 g (16 mmol) of trimethylsilyl bromide was added under a nitrogen stream, and the mixture was stirred for 24 hours. Excess trimethylsilyl bromide was removed from the resulting solution under reduced pressure at room temperature to obtain 1.60 g of a white solid. 40 mL of MeOH was added under a nitrogen stream, and the mixture was stirred for 24 hours, after which the volatile components were removed by distillation under reduced pressure at room temperature. The resulting residue was washed twice with 30 mL of hexane and dried under reduced pressure at room temperature to obtain 1.01 g of monomer (M14). The structural formulas of the obtained monomer precursor (M14c) and monomer (M14) are shown below.

[0137] [ka]

[0138] <15 Examples of Monomer Synthesis> 20 mL of super-dehydrated MDC was placed in a 100 mL flask, and 2.47 g (5 mmol) of monomer precursor (M13b) and 0.016 g (0.025 mmol) of dibutyltin dilaurate were added. The mixture was cooled with ice water under a nitrogen stream. 1.41 g (10 mmol) of 2-isocyanatoethyl acrylate (Tokyo Chemical Co., Ltd.) was added gradually over 5 minutes, and the mixture was stirred at 0°C to room temperature for 12 hours. The solvent was removed by distillation, and the residue was purified by silica gel column chromatography using MDC / MeOH (8 / 2 (v / v)) as the eluent to obtain 2.44 g of monomer precursor (M15c). Next, 1.30 g (2 mmol) of monomer precursor (M15c) was placed in a 100 mL round-bottom flask, and 20 mL of super-dehydrated MDC was added to dissolve it. 2.45 g (16 mmol) of trimethylsilyl bromide was added under a nitrogen stream, and the mixture was stirred for 24 hours. Excess trimethylsilyl bromide was removed from the resulting solution under reduced pressure at room temperature to obtain 1.59 g of a white solid. 40 mL of MeOH was added under a nitrogen stream, and the mixture was stirred for 24 hours, after which the volatile components were removed by distillation under reduced pressure at room temperature. The resulting residue was washed twice with 30 mL of hexane and dried under reduced pressure at room temperature to obtain 1.00 g of monomer (M15). The structural formulas of the obtained monomer precursor (M15c) and monomer (M15) are shown below.

[0139] [ka]

[0140] <Monomer Synthesis Example 16> 20 mL of super-dehydrated MDC was placed in a 100 mL flask, and 2.47 g (5 mmol) of monomer precursor (M13b) and 0.016 g (0.025 mmol) of dibutyltin dilaurate were added. The mixture was cooled with ice water under a nitrogen stream. 1.54 g (10 mmol) of N-(3-isocyanatetopropyl)acrylamide (Chemieliva Pharmaceutical) was added gradually over 5 minutes, and the mixture was stirred at 0°C to room temperature for 12 hours. The solvent was removed by distillation, and the residue was purified by silica gel column chromatography using MDC / MeOH (8 / 2 (v / v)) as the eluent to obtain 2.41 g of monomer precursor (M16c). Next, 1.30 g (2 mmol) of monomer precursor (M16c) was placed in a 100 mL round-bottom flask, and 20 mL of super-dehydrated MDC was added to dissolve it. 2.45 g (16 mmol) of trimethylsilyl bromide was added under a nitrogen stream, and the mixture was stirred for 24 hours. Excess trimethylsilyl bromide was removed from the resulting solution under reduced pressure at room temperature to obtain 1.61 g of a white solid. 40 mL of MeOH was added under a nitrogen stream, and the mixture was stirred for 24 hours, after which the volatile components were removed by distillation under reduced pressure at room temperature. The resulting residue was washed twice with 30 mL of hexane and dried under reduced pressure at room temperature to obtain 1.02 g of monomer (M16). The structural formulas of the obtained monomer precursor (M16c) and monomer (M16) are shown below.

[0141] [ka]

[0142] <Monomer Synthesis Example 17> In a 100 mL flask, 6.00 g (20 mmol) of tetraethyl ethylene-1,1-diylbisphosphonate (Apollo Scientific Ltd.), 0.72 g (2 mmol) of copper(II) trifluoromethanesulfonate (Sigma-Aldrich), and 5.46 g (30 mmol) of 6-hydroxy-2-naphthaleneboronic acid (Tokyo Chemical Co., Ltd.) were added, and 50 mL of anhydrous toluene (Kanto Chemical Co., Ltd.) was added. The mixture was heated to 70 °C, stirred for 18 hours, cooled to room temperature, and diluted with 100 mL of dichloromethane (Kanto Chemical Co., Ltd.). The diluted solution was extracted using a saturated aqueous solution of saturated ethylenediaminetetraacetic acid (Tokyo Chemical Co., Ltd.), washed with water, and the organic phase was isolated. The solvent was removed from the organic phase by distillation, and the residue was purified by silica gel column chromatography using acetone / hexane (4 / 6~5 / 5 (v / v)) as the eluent to obtain 6.54 g of monomer precursor (M17a). Next, 100 mL of methyl ethyl ketone was placed in a 200 mL flask, and 4.45 g (10 mmol) of monomer precursor (M17a), 2.72 g (15 mmol) of 6-bromo-1-hexanol (Tokyo Chemical Industries, Ltd.), and 2.77 g (20 mmol) of potassium carbonate were added, and the mixture was refluxed for 12 hours. After cooling to room temperature, the mixture was filtered through filter paper, and the filtrate was concentrated. The residue was purified by silica gel column chromatography using MDC / MeOH (98 / 2~90 / 10 (v / v)) as the eluent to obtain 3.87 g of monomer precursor (M17b). The structural formulas of the obtained monomer precursor (M17a) and monomer (M17b) are shown below.

[0143] [ka] Next, 20 mL of super-dehydrated MDC was placed in a 100 mL flask, and 2.72 g (5 mmol) of monomer precursor (M17b) and 0.016 g (0.025 mmol) of dibutyltin dilaurate were added. The mixture was then cooled with ice water under a nitrogen stream. 2.01 g (10 mmol) of 3-isopropenyl-α,α-dimethylbenzyl isocyanate (manufactured by Tokyo Chemical Co., Ltd.) was added gradually over 10 minutes, and the mixture was stirred at 0°C to room temperature for 12 hours. The solvent was removed by distillation, and the residue was purified by silica gel column chromatography using MDC / MeOH (8 / 2 (v / v)) as the eluent to obtain 2.89 g of monomer precursor (M17c). Next, 1.49 g (2 mmol) of monomer precursor (M17c) was placed in a 100 mL round-bottom flask, and 20 mL of super-dehydrated MDC was added to dissolve it. 2.45 g (16 mmol) of trimethylsilyl bromide was added under a nitrogen stream, and the mixture was stirred for 24 hours. Excess trimethylsilyl bromide was removed from the resulting solution under reduced pressure at room temperature to obtain 1.81 g of a white solid. 40 mL of MeOH was added under a nitrogen stream, and the mixture was stirred for 24 hours, after which the volatile components were removed by distillation under reduced pressure at room temperature. The resulting residue was washed twice with 30 mL of hexane and dried under reduced pressure at room temperature to obtain 1.21 g of monomer (M17). The structural formulas of the obtained monomer precursor (M17c) and monomer (M17) are shown below.

[0144] [ka]

[0145] <Monomer Synthesis Example 18> 20 mL of ultra-dehydrated MDC was placed in a 100 mL flask, and 2.72 g (5 mmol) of monomer precursor (M17b) and 0.016 g (0.025 mmol) of dibutyltin dilaurate were added. The mixture was cooled with ice water under a nitrogen stream. 1.55 g (10 mmol) of 2-isocyanatoethyl methacrylate (Tokyo Chemical Co., Ltd.) was added gradually over 5 minutes, and the mixture was stirred at 0°C to room temperature for 12 hours. The solvent was removed by distillation, and the residue was purified by silica gel column chromatography using MDC / MeOH (8 / 2 (v / v)) as the eluent to obtain 2.73 g of monomer precursor (M18c). Next, 1.40 g (2 mmol) of monomer precursor (M18c) was placed in a 100 mL round-bottom flask, and 20 mL of super-dehydrated MDC was added to dissolve it. 2.45 g (16 mmol) of trimethylsilyl bromide was added under a nitrogen stream, and the mixture was stirred for 24 hours. Excess trimethylsilyl bromide was removed from the resulting solution under reduced pressure at room temperature to obtain 1.72 g of a white solid. 40 mL of MeOH was added under a nitrogen stream, and the mixture was stirred for 24 hours, after which the volatile components were removed by distillation under reduced pressure at room temperature. The resulting residue was washed twice with 30 mL of hexane and dried under reduced pressure at room temperature to obtain 1.10 g of monomer (M18). The structural formulas of the obtained monomer precursor (M18c) and monomer (M18) are shown below.

[0146] [ka]

[0147] <Monomer Synthesis Example 19> 20 mL of ultra-dehydrated MDC was placed in a 100 mL flask, and 2.72 g (5 mmol) of monomer precursor (M17b) and 0.016 g (0.025 mmol) of dibutyltin dilaurate were added. The mixture was cooled with ice water under a nitrogen stream. 1.41 g (10 mmol) of 2-isocyanatoethyl acrylate (Tokyo Chemical Co., Ltd.) was added gradually over 5 minutes, and the mixture was stirred at 0°C to room temperature for 12 hours. The solvent was removed by distillation, and the residue was purified by silica gel column chromatography using MDC / MeOH (8 / 2 (v / v)) as the eluent to obtain 2.58 g of monomer precursor (M19c). Next, 1.37 g (2 mmol) of monomer precursor (M19c) was placed in a 100 mL round-bottom flask, and 20 mL of super-dehydrated MDC was added to dissolve it. 2.45 g (16 mmol) of trimethylsilyl bromide was added under a nitrogen stream, and the mixture was stirred for 24 hours. Excess trimethylsilyl bromide was removed from the resulting solution under reduced pressure at room temperature to obtain 1.68 g of a white solid. 40 mL of MeOH was added under a nitrogen stream, and the mixture was stirred for 24 hours, after which the volatile components were removed by distillation under reduced pressure at room temperature. The resulting residue was washed twice with 30 mL of hexane and dried under reduced pressure at room temperature to obtain 1.09 g of monomer (M19). The structural formulas of the obtained monomer precursor (M19c) and monomer (M19) are shown below.

[0148] [ka]

[0149] <Example of monomer synthesis 20> 20 mL of ultra-dehydrated MDC was placed in a 100 mL flask, and 2.72 g (5 mmol) of monomer precursor (M17b) and 0.016 g (0.025 mmol) of dibutyltin dilaurate were added. The mixture was cooled with ice water under a nitrogen stream. 1.54 g (10 mmol) of N-(3-isocyanatetopropyl)acrylamide (Chemieliva Pharmaceutical) was added gradually over 5 minutes, and the mixture was stirred at 0°C to room temperature for 12 hours. The solvent was removed by distillation, and the residue was purified by silica gel column chromatography using MDC / MeOH (8 / 2 (v / v)) as the eluent to obtain 2.67 g of monomer precursor (M20c). Next, 1.40 g (2 mmol) of monomer precursor (M20c) was placed in a 100 mL round-bottom flask, and 20 mL of super-dehydrated MDC was added to dissolve it. 2.45 g (16 mmol) of trimethylsilyl bromide was added under a nitrogen stream, and the mixture was stirred for 24 hours. Excess trimethylsilyl bromide was removed from the resulting solution under reduced pressure at room temperature to obtain 1.72 g of a white solid. 40 mL of MeOH was added under a nitrogen stream, and the mixture was stirred for 24 hours, after which the volatile components were removed by distillation under reduced pressure at room temperature. The resulting residue was washed twice with 30 mL of hexane and dried under reduced pressure at room temperature to obtain 1.13 g of monomer (M20). The structural formulas of the obtained monomer precursor (M20c) and monomer (M20) are shown below.

[0150] [ka]

[0151] The structures of monomers (M1) to (M20) obtained in monomer synthesis examples 1 to 20 are summarized in Tables 1 and 2.

[0152] [Table 1]

[0153] [Table 2]

[0154] In Table 1, "-PhPrp-" represents the following structure.

[0155] [ka]

[0156] <Comparative synthesis example of monomers 1> 20 mL of super-dehydrated MDC, 4.86 g (48 mmol) of triethylamine (Kanto Chemical Co., Ltd.), and 6.16 g (40 mmol) of dimethyl 2-hydroxyethylphosphonate (Tokyo Chemical Co., Ltd.) were added to a 100 mL three-necked flask. The mixture was stirred at room temperature under a nitrogen stream, and then the flask was cooled with ice water. 3.62 g (4 mmol) of acrylate chloride (Tokyo Chemical Co., Ltd.) was added dropwise over 10 minutes, and the mixture was stirred at 0°C to room temperature for 15 hours. The resulting reaction solution was diluted with 20 mL of MDC, saturated aqueous solution of sodium bicarbonate was added, and after shaking, the separated organic phase was isolated and washed with water. The organic phase was dried over magnesium sulfate (Kanto Chemical Co., Ltd.), and the solvent was removed by distillation. The residue was purified by silica gel column chromatography using MDC / MeOH (10 / 1~8 / 2 (v / v)) as the eluent to obtain 5.88 g of monomer precursor (RM1a). Next, 2.08 g (10 mmol) of monomer precursor (RM1a) was placed in a 100 mL round-bottom flask, and 10 mL of super-dehydrated MDC was added to dissolve it. A solution of 6.12 g (40 mmol) of trimethylsilyl bromide dissolved in 15 mL of super-dehydrated MDC was added under a nitrogen stream, and the mixture was stirred for 24 hours. Excess trimethylsilyl bromide was removed from the resulting solution under reduced pressure at room temperature to obtain 3.07 g of oil. 50 mL of MeOH was added under a nitrogen stream, and the mixture was stirred for 24 hours, after which volatile components were removed by distillation under reduced pressure at room temperature. The resulting residue was washed twice with 30 mL of hexane and dried under reduced pressure at room temperature to obtain 1.62 g of comparative monomer (RM1). The structural formula of the obtained comparative monomer (RM1) is shown below.

[0157] [ka]

[0158] <Comparative Synthesis Example 2 of Monomer> 2.79 g (20 mmol) of 3-aminopropylphosphonic acid (manufactured by Merck KGaA) was placed into a 100 mL three-necked flask, 40 mL of 1N aqueous sodium hydroxide solution (manufactured by Kanto Chemical Co., Inc.) was added, and the mixture was stirred to dissolve. While cooling the flask with ice water, 3.11 g (20 mmol) of 2-isocyanate ethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 15 minutes under a nitrogen stream, followed by stirring at 0°C to room temperature for 3 hours. A small amount of precipitate was removed by filtration, and 1N hydrochloric acid (manufactured by Kanto Chemical Co., Inc.) was added until the pH of the filtrate reached 7. After stirring for 30 minutes, the precipitate was collected by filtration and dried to obtain 2.88 g of comparative monomer (RM2). Here, the structural formula of the obtained comparative monomer (RM2) is shown below.

[0159]

Chemical Formula

[0160] (Synthesis of Polymer and Copolymer) <Example 1> 20 mL of 1,4-dioxane was placed into a 100 mL three-necked flask, 3.70 g (10 mmol) of monomer (M1) was dissolved therein, and the mixture was heated to 70°C under a nitrogen stream. A solution prepared by dissolving 0.033 g (0.2 mmol) of 2,2'-azobis(isobutyronitrile) (AIBN) (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.011 g (0.1 mmol) of 3-mercaptopropionic acid (3MPA) (manufactured by Tokyo Chemical Industry Co., Ltd.) in 5 mL of 1,4-dioxane was added dropwise over 1 hour, followed by stirring at 70°C for 6 hours. After cooling to room temperature (25°C), the obtained reaction solution was poured into hexane. The precipitate was collected by filtration and dried under reduced pressure to obtain 3.55 g of polymer CP1 (number average molecular weight (Mn): 9,400, weight average molecular weight (Mw): 22,000).

[0161] <Example 2> A monomer solution was prepared by dissolving 3.96 g (10 mmol) of monomer (M1) and 0.58 g (5 mmol) of 2-hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) in 25 mL of 1,4-dioxane. 10% by mass of the prepared monomer solution was placed into a 100 mL three-neck flask, and heated to 70°C under a nitrogen stream. Then, a solution obtained by dissolving 0.049 g (0.3 mmol) of AIBN and 0.016 g (0.15 mmol) of 3MPA in the remaining monomer solution was added dropwise over 1 hour, followed by stirring at 70°C for 6 hours. After cooling to room temperature (25°C), the obtained reaction solution was poured into hexane. The precipitate was filtered off and dried under reduced pressure, to obtain 5.05 g of polymer CP2 (number-average molecular weight (Mn): 9,600, weight-average molecular weight (Mw): 23,400).

[0162] <Example 3> A monomer solution was prepared by dissolving 3.96 g (10 mmol) of monomer (M1) and 0.36 g (5 mmol) of acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) in 25 mL of 1,4-dioxane. 10% by mass of the prepared monomer solution was placed into a 100 mL three-neck flask, and heated to 70°C under a nitrogen stream. Then, a solution obtained by dissolving 0.049 g (0.3 mmol) of AIBN and 0.016 g (0.15 mmol) of 3MPA in the remaining monomer solution was added dropwise over 1 hour, followed by stirring at 70°C for 6 hours. After cooling to room temperature (25°C), the obtained reaction solution was poured into hexane. The precipitate was filtered off and dried under reduced pressure, to obtain 4.72 g of copolymer CP3 (number-average molecular weight (Mn): 9,900, weight-average molecular weight (Mw): 23,900).

[0163] <Example 4> 3.98 g (10 mmol) of monomer (M2) was dissolved in 20 mL of 1,4-dioxane in a 100 mL three-necked flask and heated to 70°C under a nitrogen stream. A solution of 0.033 g (0.2 mmol) of AIBN and 0.011 g (0.1 mmol) of 3 MPA dissolved in 5 mL of 1,4-dioxane was added dropwise over 1 hour, and the mixture was stirred at 70°C for 6 hours. After cooling to room temperature (25°C), the resulting reaction solution was added to hexane. The precipitate was filtered off and dried under reduced pressure to obtain 3.77 g of polymer CP4 (number average molecular weight (Mn): 10,100, weight average molecular weight (Mw): 22,000).

[0164] <Example 5> A monomer solution was prepared by dissolving 3.98 g (10 mmol) of monomer (M2) and 0.65 g (5 mmol) of 2-methoxyethyl acrylate (MTA) (manufactured by Tokyo Chemical Industry Co., Ltd.) in 25 mL of 1,4-dioxane. 10% by mass of the prepared monomer solution was placed in a 100 mL three-necked flask and heated to 70°C under a nitrogen stream. Then, a solution containing 0.049 g (0.3 mmol) of AIBN and 0.016 g (0.15 mmol) of 3MPA was added dropwise to the remaining monomer solution over 1 hour, and the mixture was stirred at 70°C for 6 hours. After cooling to room temperature (25°C), the resulting reaction solution was added to hexane. The precipitate was filtered off and dried under reduced pressure to obtain 5.05 g of polymer CP5 (number average molecular weight (Mn): 10,100, weight average molecular weight (Mw): 24,900).

[0165] <Example 6> A monomer solution was prepared by dissolving 3.98 g (10 mmol) of monomer (M2) and 0.36 g (5 mmol) of acrylic acid in 25 mL of 1,4-dioxane. 10% by mass of the prepared monomer solution was placed in a 100 mL three-necked flask and heated to 70°C under a nitrogen stream. Then, a solution containing 0.049 g (0.3 mmol) of AIBN and 0.016 g (0.15 mmol) of 3MPA was added dropwise to the remaining monomer solution over 1 hour, and the mixture was stirred at 70°C for 6 hours. After cooling to room temperature (25°C), the resulting reaction solution was added to hexane. The precipitate was filtered off and dried under reduced pressure to obtain 4.20 g of copolymer CP6 (number average molecular weight (Mn): 10,300, weight average molecular weight (Mw): 24,800).

[0166] <Example 7> A monomer solution was prepared by dissolving 4.54 g (10 mmol) of monomer (M3) and 0.72 g (5 mmol) of 2-ethoxyethyl acrylate (EEA) (manufactured by Tokyo Chemical Industry Co., Ltd.) in 25 mL of 1,4-dioxane. 10% by mass of the prepared monomer solution was placed in a 100 mL three-necked flask and heated to 70°C under a nitrogen stream. Then, a solution containing 0.049 g (0.3 mmol) of AIBN and 0.016 g (0.15 mmol) of 3MPA was added dropwise to the remaining monomer solution over 1 hour, and the mixture was stirred at 70°C for 6 hours. After cooling to room temperature (25°C), the resulting reaction solution was added to hexane. The precipitate was filtered off and dried under reduced pressure to obtain 5.05 g of polymer CP7 (number average molecular weight (Mn): 10,700, weight average molecular weight (Mw): 25,800).

[0167] <Example 8> A monomer solution was prepared by dissolving 4.54 g (10 mmol) of monomer (M3) and 0.36 g (5 mmol) of acrylic acid in 25 mL of 1,4-dioxane. 10% by mass of the prepared monomer solution was placed in a 100 mL three-necked flask and heated to 70°C under a nitrogen stream. Then, a solution containing 0.049 g (0.3 mmol) of AIBN and 0.016 g (0.15 mmol) of 3MPA was added dropwise to the remaining monomer solution over 1 hour, and the mixture was stirred at 70°C for 6 hours. After cooling to room temperature (25°C), the resulting reaction solution was added to hexane. The precipitate was filtered off and dried under reduced pressure to obtain 4.20 g of copolymer CP8 (number average molecular weight (Mn): 10,900, weight average molecular weight (Mw): 25,900).

[0168] <Example 9> A monomer solution was prepared by dissolving 4.54 g (10 mmol) of monomer (M4) and 0.58 g (5 mmol) of 2-hydroxyethyl acrylate (HEA) in 25 mL of 1,4-dioxane. 10% by mass of the prepared monomer solution was placed in a 100 mL three-necked flask and heated to 70°C under a nitrogen stream. Then, a solution containing 0.049 g (0.3 mmol) of AIBN and 0.016 g (0.15 mmol) of 3MPA was added dropwise to the remaining monomer solution over 1 hour, and the mixture was stirred at 70°C for 6 hours. After cooling to room temperature (25°C), the resulting reaction solution was added to hexane. The precipitate was filtered off and dried under reduced pressure to obtain 5.05 g of polymer CP9 (number average molecular weight (Mn): 10,700, weight average molecular weight (Mw): 25,800).

[0169] <Example 10> A monomer solution was prepared by dissolving 4.54 g (10 mmol) of monomer (M4) and 0.36 g (5 mmol) of acrylic acid in 25 mL of 1,4-dioxane. 10% by mass of the prepared monomer solution was placed in a 100 mL three-necked flask and heated to 70°C under a nitrogen stream. Then, a solution containing 0.049 g (0.3 mmol) of AIBN and 0.016 g (0.15 mmol) of 3MPA was added dropwise to the remaining monomer solution over 1 hour, and the mixture was stirred at 70°C for 6 hours. After cooling to room temperature (25°C), the resulting reaction solution was added to hexane. The precipitate was filtered off and dried under reduced pressure to obtain 4.20 g of copolymer CP10 (number average molecular weight (Mn): 10,900, weight average molecular weight (Mw): 25,900).

[0170] <Example 11> A monomer solution was prepared by dissolving 3.79 g (10 mmol) of monomer (M5) and 0.58 g (5 mmol) of 2-hydroxyethyl acrylate (HEA) in 25 mL of 1,4-dioxane. 10% by mass of the prepared monomer solution was placed in a 100 mL three-necked flask and heated to 70°C under a nitrogen stream. Then, a solution containing 0.049 g (0.3 mmol) of AIBN and 0.016 g (0.15 mmol) of 3MPA was added dropwise to the remaining monomer solution over 1 hour, and the mixture was stirred at 70°C for 6 hours. After cooling to room temperature (25°C), the resulting reaction solution was added to hexane. The precipitate was filtered off and dried under reduced pressure to obtain 4.33 g of polymer CP11 (number average molecular weight (Mn): 10,100, weight average molecular weight (Mw): 24,900).

[0171] <Example 12> A monomer solution was prepared by dissolving 3.79 g (10 mmol) of monomer (M5) and 0.43 g (5 mmol) of methacrylic acid in 25 mL of 1,4-dioxane. 10% by mass of the prepared monomer solution was placed in a 100 mL three-necked flask and heated to 70°C under a nitrogen stream. Then, a solution containing 0.049 g (0.3 mmol) of AIBN and 0.016 g (0.15 mmol) of 3MPA was added dropwise to the remaining monomer solution over 1 hour, and the mixture was stirred at 70°C for 6 hours. After cooling to room temperature (25°C), the resulting reaction solution was added to hexane. The precipitate was filtered off and dried under reduced pressure to obtain 3.98 g of copolymer CP12 (number average molecular weight (Mn): 10,600, weight average molecular weight (Mw): 25,000).

[0172] <Example 13> A monomer solution was prepared by dissolving 3.80 g (10 mmol) of monomer (M6) and 0.58 g (5 mmol) of 2-hydroxyethyl acrylate (HEA) in 25 mL of 1,4-dioxane. 10% by mass of the prepared monomer solution was placed in a 100 mL three-necked flask and heated to 70°C under a nitrogen stream. Then, a solution containing 0.049 g (0.3 mmol) of AIBN and 0.016 g (0.15 mmol) of 3MPA was added dropwise to the remaining monomer solution over 1 hour, and the mixture was stirred at 70°C for 6 hours. After cooling to room temperature (25°C), the resulting reaction solution was added to hexane. The precipitate was filtered off and dried under reduced pressure to obtain 4.13 g of polymer CP13 (number average molecular weight (Mn): 10,000, weight average molecular weight (Mw): 24,100).

[0173] <Example 14> A monomer solution was prepared by dissolving 3.80 g (10 mmol) of monomer (M6) and 0.43 g (5 mmol) of methacrylic acid in 25 mL of 1,4-dioxane. 10% by mass of the prepared monomer solution was placed in a 100 mL three-necked flask and heated to 70°C under a nitrogen stream. Then, a solution containing 0.049 g (0.3 mmol) of AIBN and 0.016 g (0.15 mmol) of 3MPA was added dropwise to the remaining monomer solution over 1 hour, and the mixture was stirred at 70°C for 6 hours. After cooling to room temperature (25°C), the resulting reaction solution was added to hexane. The precipitate was filtered off and dried under reduced pressure to obtain 4.06 g of copolymer CP14 (number average molecular weight (Mn): 10,300, weight average molecular weight (Mw): 24,300).

[0174] <Example 15> A monomer solution was prepared by dissolving 3.65 g (10 mmol) of monomer (M7) and 0.43 g (5 mmol) of methacrylic acid in 25 mL of 1,4-dioxane. 10% by mass of the prepared monomer solution was placed in a 100 mL three-necked flask and heated to 70°C under a nitrogen stream. Then, a solution containing 0.049 g (0.3 mmol) of AIBN and 0.016 g (0.15 mmol) of 3MPA was added dropwise to the remaining monomer solution over 1 hour, and the mixture was stirred at 70°C for 6 hours. After cooling to room temperature (25°C), the resulting reaction solution was added to hexane. The precipitate was filtered off and dried under reduced pressure to obtain 3.84 g of copolymer CP15 (number average molecular weight (Mn): 10,000, weight average molecular weight (Mw): 23,800).

[0175] <Example 16> A monomer solution was prepared by dissolving 3.66 g (10 mmol) of monomer (M8) and 0.43 g (5 mmol) of methacrylic acid in 25 mL of 1,4-dioxane. 10% by mass of the prepared monomer solution was placed in a 100 mL three-necked flask and heated to 70°C under a nitrogen stream. Then, a solution containing 0.049 g (0.3 mmol) of AIBN and 0.016 g (0.15 mmol) of 3MPA was added dropwise to the remaining monomer solution over 1 hour, and the mixture was stirred at 70°C for 6 hours. After cooling to room temperature (25°C), the resulting reaction solution was added to hexane. The precipitate was filtered off and dried under reduced pressure to obtain 3.76 g of copolymer CP16 (number average molecular weight (Mn): 10,500, weight average molecular weight (Mw): 23,900).

[0176] <Example 17> A monomer solution was prepared by dissolving 3.78 g (10 mmol) of monomer (M9) and 0.43 g (5 mmol) of methacrylic acid in 25 mL of 1,4-dioxane. 10% by mass of the prepared monomer solution was placed in a 100 mL three-necked flask and heated to 70°C under a nitrogen stream. Then, a solution containing 0.049 g (0.3 mmol) of AIBN and 0.016 g (0.15 mmol) of 3MPA was added dropwise to the remaining monomer solution over 1 hour, and the mixture was stirred at 70°C for 6 hours. After cooling to room temperature (25°C), the resulting reaction solution was added to hexane. The precipitate was filtered off and dried under reduced pressure to obtain 3.76 g of copolymer CP17 (number average molecular weight (Mn): 11,000, weight average molecular weight (Mw): 24,300).

[0177] <Example 18> A monomer solution was prepared by dissolving 3.79 g (10 mmol) of monomer (M10) and 0.43 g (5 mmol) of methacrylic acid in 25 mL of 1,4-dioxane. 10 mass% of the prepared monomer solution was placed into a 100 mL three-necked flask, heated to 70°C under a nitrogen stream, then a solution obtained by dissolving 0.049 g (0.3 mmol) of AIBN and 0.016 g (0.15 mmol) of 3MPA in the remaining monomer solution was added dropwise over 1 hour, followed by stirring at 70°C for 6 hours. After cooling to room temperature (25°C), the obtained reaction solution was poured into hexane. The precipitate was collected by filtration and dried under reduced pressure to obtain 3.99 g of copolymer CP18 (number average molecular weight (Mn): 11,300, weight average molecular weight (Mw): 25,100).

[0178] <Example 19> A monomer solution was prepared by dissolving 4.09 g (10 mmol) of monomer (M11) and 0.43 g (5 mmol) of methacrylic acid in 25 mL of 1,4-dioxane. 10 mass% of the prepared monomer solution was placed into a 100 mL three-necked flask, heated to 70°C under a nitrogen stream, then a solution obtained by dissolving 0.049 g (0.3 mmol) of AIBN and 0.016 g (0.15 mmol) of 3MPA in the remaining monomer solution was added dropwise over 1 hour, followed by stirring at 70°C for 6 hours. After cooling to room temperature (25°C), the obtained reaction solution was poured into hexane. The precipitate was collected by filtration and dried under reduced pressure to obtain 4.50 g of copolymer CP19 (number average molecular weight (Mn): 11,600, weight average molecular weight (Mw): 25,600).

[0179] <Example 20> A monomer solution was prepared by dissolving 4.10 g (10 mmol) of monomer (M12) and 0.43 g (5 mmol) of methacrylic acid in 25 mL of 1,4-dioxane. 10% by mass of the prepared monomer solution was placed in a 100 mL three-necked flask and heated to 70°C under a nitrogen stream. Then, a solution containing 0.049 g (0.3 mmol) of AIBN and 0.016 g (0.15 mmol) of 3MPA was added dropwise to the remaining monomer solution over 1 hour, and the mixture was stirred at 70°C for 6 hours. After cooling to room temperature (25°C), the resulting reaction solution was added to hexane. The precipitate was filtered off and dried under reduced pressure to obtain 4.44 g of copolymer CP20 (number average molecular weight (Mn): 11,000, weight average molecular weight (Mw): 25,100).

[0180] <Example 21> A monomer solution was prepared by dissolving 5.84 g (10 mmol) of monomer (M13) and 2.32 g (20 mmol) of 2-hydroxyethyl acrylate (HEA) in 40 mL of 1,4-dioxane. 10% by mass of the prepared monomer solution was placed in a 100 mL three-necked flask and heated to 70°C under a nitrogen stream. Then, a solution containing 0.099 g (0.6 mmol) of AIBN and 0.032 g (0.3 mmol) of 3MPA was added dropwise to the remaining monomer solution over 1 hour, and the mixture was stirred at 70°C for 6 hours. After cooling to room temperature (25°C), the resulting reaction solution was added to hexane. The precipitate was filtered off and dried under reduced pressure to obtain 7.18 g of polymer CP21 (number average molecular weight (Mn): 10,200, weight average molecular weight (Mw): 23,200).

[0181] <Example 22> A monomer solution was prepared by dissolving 5.84 g (10 mmol) of monomer (M13) and 1.72 g (20 mmol) of methacrylic acid in 40 mL of 1,4-dioxane. 10% by mass of the prepared monomer solution was placed in a 100 mL three-necked flask and heated to 70°C under a nitrogen stream. Then, a solution containing 0.099 g (0.6 mmol) of AIBN and 0.032 g (0.3 mmol) of 3MPA was added dropwise to the remaining monomer solution over 1 hour, and the mixture was stirred at 70°C for 6 hours. After cooling to room temperature (25°C), the resulting reaction solution was added to hexane. The precipitate was filtered off and dried under reduced pressure to obtain 6.72 g of copolymer CP22 (number average molecular weight (Mn): 10,900, weight average molecular weight (Mw): 25,400).

[0182] <Example 23> A monomer solution was prepared by dissolving 5.38 g (10 mmol) of monomer (M14) and 1.72 g (20 mmol) of methacrylic acid in 40 mL of 1,4-dioxane. 10% by mass of the prepared monomer solution was placed in a 100 mL three-necked flask and heated to 70°C under a nitrogen stream. Then, a solution containing 0.099 g (0.6 mmol) of AIBN and 0.032 g (0.3 mmol) of 3MPA was added dropwise to the remaining monomer solution over 1 hour, and the mixture was stirred at 70°C for 6 hours. After cooling to room temperature (25°C), the resulting reaction solution was added to hexane. The precipitate was filtered off and dried under reduced pressure to obtain 6.39 g of polymer CP23 (number average molecular weight (Mn): 10,200, weight average molecular weight (Mw): 23,800).

[0183] <Example 24> A monomer solution was prepared by dissolving 5.23 g (10 mmol) of monomer (M15) and 1.72 g (20 mmol) of methacrylic acid in 40 mL of 1,4-dioxane. 10% by mass of the prepared monomer solution was placed in a 100 mL three-necked flask and heated to 70°C under a nitrogen stream. Then, a solution containing 0.099 g (0.6 mmol) of AIBN and 0.016 g (0.15 mmol) of 3MPA was added dropwise to the remaining monomer solution over 1 hour, and the mixture was stirred at 70°C for 6 hours. After cooling to room temperature (25°C), the resulting reaction solution was added to hexane. The precipitate was filtered off and dried under reduced pressure to obtain 6.32 g of polymer CP24 (number average molecular weight (Mn): 13,000, weight average molecular weight (Mw): 30,000).

[0184] <Example 25> A monomer solution was prepared by dissolving 5.37 g (10 mmol) of monomer (M16) and 1.72 g (20 mmol) of methacrylic acid in 40 mL of 1,4-dioxane. 10% by mass of the prepared monomer solution was placed in a 100 mL three-necked flask and heated to 70°C under a nitrogen stream. Then, a solution containing 0.099 g (0.6 mmol) of AIBN and 0.016 g (0.15 mmol) of 3MPA was added dropwise to the remaining monomer solution over 1 hour, and the mixture was stirred at 70°C for 6 hours. After cooling to room temperature (25°C), the resulting reaction solution was added to hexane. The precipitate was filtered off and dried under reduced pressure to obtain 6.52 g of copolymer CP25 (number average molecular weight (Mn): 13,200, weight average molecular weight (Mw): 29,700).

[0185] <Example 26> A monomer solution was prepared by dissolving 6.34 g (10 mmol) of monomer (M17) and 2.32 g (20 mmol) of 2-hydroxyethyl acrylate (HEA) in 40 mL of 1,4-dioxane. 10% by mass of the prepared monomer solution was placed in a 100 mL three-necked flask and heated to 70°C under a nitrogen stream. Then, a solution containing 0.099 g (0.6 mmol) of AIBN and 0.032 g (0.3 mmol) of 3MPA was added dropwise to the remaining monomer solution over 1 hour, and the mixture was stirred at 70°C for 6 hours. After cooling to room temperature (25°C), the resulting reaction solution was added to hexane. The precipitate was filtered off and dried under reduced pressure to obtain 7.70 g of polymer CP26 (number average molecular weight (Mn): 11,100, weight average molecular weight (Mw): 24,400).

[0186] <Example 27> A monomer solution was prepared by dissolving 6.34 g (10 mmol) of monomer (M17) and 1.72 g (20 mmol) of methacrylic acid in 40 mL of 1,4-dioxane. 10% by mass of the prepared monomer solution was placed in a 100 mL three-necked flask and heated to 70°C under a nitrogen stream. Then, a solution containing 0.099 g (0.6 mmol) of AIBN and 0.032 g (0.3 mmol) of 3MPA was added dropwise to the remaining monomer solution over 1 hour, and the mixture was stirred at 70°C for 6 hours. After cooling to room temperature (25°C), the resulting reaction solution was added to hexane. The precipitate was filtered off and dried under reduced pressure to obtain 7.42 g of copolymer CP27 (number average molecular weight (Mn): 10,500, weight average molecular weight (Mw): 24,600).

[0187] <Example 28> A monomer solution was prepared by dissolving 5.88 g (10 mmol) of monomer (M18) and 1.72 g (20 mmol) of methacrylic acid in 40 mL of 1,4-dioxane. 10% by mass of the prepared monomer solution was placed in a 100 mL three-necked flask and heated to 70°C under a nitrogen stream. Then, a solution containing 0.099 g (0.6 mmol) of AIBN and 0.032 g (0.3 mmol) of 3MPA was added dropwise to the remaining monomer solution over 1 hour, and the mixture was stirred at 70°C for 6 hours. After cooling to room temperature (25°C), the resulting reaction solution was added to hexane. The precipitate was filtered off and dried under reduced pressure to obtain 6.53 g of copolymer CP28 (number average molecular weight (Mn): 10,900, weight average molecular weight (Mw): 23,900).

[0188] <Example 29> A monomer solution was prepared by dissolving 5.74 g (10 mmol) of monomer (M19) and 1.72 g (20 mmol) of methacrylic acid in 40 mL of 1,4-dioxane. 10% by mass of the prepared monomer solution was placed in a 100 mL three-necked flask and heated to 70°C under a nitrogen stream. Then, a solution containing 0.099 g (0.6 mmol) of AIBN and 0.016 g (0.15 mmol) of 3MPA was added dropwise to the remaining monomer solution over 1 hour, and the mixture was stirred at 70°C for 6 hours. After cooling to room temperature (25°C), the resulting reaction solution was added to hexane. The precipitate was filtered off and dried under reduced pressure to obtain 6.71 g of copolymer CP29 (number average molecular weight (Mn): 13,900, weight average molecular weight (Mw): 30,300).

[0189] <Example 30> A monomer solution was prepared by dissolving 5.87 g (10 mmol) of monomer (M20) and 1.72 g (20 mmol) of methacrylic acid in 40 mL of 1,4-dioxane. 10% by mass of the prepared monomer solution was placed in a 100 mL three-necked flask and heated to 70°C under a nitrogen stream. Then, a solution containing 0.099 g (0.6 mmol) of AIBN and 0.016 g (0.15 mmol) of 3MPA was added dropwise to the remaining monomer solution over 1 hour, and the mixture was stirred at 70°C for 6 hours. After cooling to room temperature (25°C), the resulting reaction solution was added to hexane. The precipitate was filtered off and dried under reduced pressure to obtain 7.06 g of copolymer CP30 (number average molecular weight (Mn): 13,500, weight average molecular weight (Mw): 29,300).

[0190] <Example 67> A monomer solution was prepared by dissolving 3.96 g (10 mmol) of monomer (M1) and 0.58 g (5 mmol) of 2-hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) in 25 mL of 1,4-dioxane. 10% by mass of the prepared monomer solution was placed in a 100 mL three-necked flask and heated to 70°C under a nitrogen stream. Then, a solution containing 0.123 g (0.75 mmol) of AIBN and 0.159 g (1.50 mmol) of 3MPA was added dropwise to the remaining monomer solution over 1 hour, and the mixture was stirred at 70°C for 6 hours. After cooling to room temperature (25°C), the resulting reaction solution was added to hexane. The precipitate was filtered off and dried under reduced pressure to obtain 4.40 g of polymer CP31 (number average molecular weight (Mn): 1,900, weight average molecular weight (Mw): 4,000).

[0191] <Example 68> A monomer solution was prepared by dissolving 3.98 g (10 mmol) of monomer (M2) and 0.65 g (5 mmol) of 2-methoxyethyl acrylate (MTA) (manufactured by Tokyo Chemical Industry Co., Ltd.) in 25 mL of 1,4-dioxane. 10% by mass of the prepared monomer solution was placed in a 100 mL three-necked flask and heated to 70°C under a nitrogen stream. Then, a solution containing 0.123 g (0.75 mmol) of AIBN and 0.159 g (1.50 mmol) of 3MPA was added dropwise to the remaining monomer solution over 1 hour, and the mixture was stirred at 70°C for 6 hours. After cooling to room temperature (25°C), the resulting reaction solution was added to hexane. The precipitate was filtered off and dried under reduced pressure to obtain 4.44 g of polymer CP32 (number average molecular weight (Mn): 2,000, weight average molecular weight (Mw): 4,500).

[0192] <Example 69> A monomer solution was prepared by dissolving 3.80 g (10 mmol) of monomer (M6) and 0.58 g (5 mmol) of 2-hydroxyethyl acrylate (HEA) in 15 mL of 1,4-dioxane. 10% by mass of the prepared monomer solution was placed in a 100 mL three-necked flask and heated to 70°C under a nitrogen stream. Then, a solution containing 0.049 g (0.3 mmol) of AIBN and 0.002 g (0.018 mmol) of 3MPA was added dropwise to the remaining monomer solution over 1 hour, and the mixture was stirred at 70°C for 6 hours. After cooling to room temperature (25°C), the resulting reaction solution was added to hexane. The precipitate was filtered off and dried under reduced pressure to obtain 4.24 g of polymer CP33 (number average molecular weight (Mn): 19,000, weight average molecular weight (Mw): 52,000).

[0193] <Example 70> A monomer solution was prepared by dissolving 4.10 g (10 mmol) of monomer (M12) and 0.43 g (5 mmol) of methacrylic acid in 12 mL of 1,4-dioxane. 10% by mass of the prepared monomer solution was placed in a 100 mL three-necked flask and heated to 70°C under a nitrogen stream. Then, a solution containing 0.049 g (0.3 mmol) of AIBN and 0.002 g (0.018 mmol) of 3MPA was added dropwise to the remaining monomer solution over 1 hour, and the mixture was stirred at 70°C for 6 hours. After cooling to room temperature (25°C), the resulting reaction solution was added to hexane. The precipitate was filtered off and dried under reduced pressure to obtain 4.38 g of copolymer CP34 (number average molecular weight (Mn): 20,000, weight average molecular weight (Mw): 55,000).

[0194] <Comparative Example 1> 3.60 g (20 mmol) of comparative monomer (RM1) was dissolved in 15 mL of 1,4-dioxane in a 100 mL three-necked flask and heated to 70 °C under a nitrogen stream. A solution of 0.066 g (0.4 mmol) of AIBN and 0.021 g (0.2 mmol) of 3MPA dissolved in 5 mL of 1,4-dioxane was added dropwise over 1 hour, and the mixture was stirred at 70 °C for 6 hours. After cooling to room temperature (25 °C), the resulting reaction solution was added to hexane. The precipitate was filtered off and dried under reduced pressure to obtain 3.41 g of comparative polymer RCP1 (number average molecular weight (Mn): 9,100, weight average molecular weight (Mw): 21,800).

[0195] <Comparative Example 2> A monomer solution was prepared by dissolving 3.60 g (20 mmol) of comparative monomer (RM1) and 1.16 g (10 mmol) of 2-hydroxyethyl acrylate (HEA) in 25 mL of 1,4-dioxane. 10% by mass of the prepared monomer solution was placed in a 100 mL three-necked flask and heated to 70°C under a nitrogen stream. Then, a solution containing 0.099 g (0.6 mmol) of AIBN and 0.032 g (0.3 mmol) of 3MPA was added dropwise to the remaining monomer solution over 1 hour, and the mixture was stirred at 70°C for 6 hours. After cooling to room temperature (25°C), the resulting reaction solution was added to hexane. The precipitate was filtered off and dried under reduced pressure to obtain 4.50 g of comparative polymer RCP2 (number average molecular weight (Mn): 9,200, weight average molecular weight (Mw): 22,200).

[0196] <Comparative Example 3> A monomer solution was prepared by dissolving 3.60 g (20 mmol) of comparative monomer (RM1) and 0.72 g (10 mmol) of acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) in 25 mL of 1,4-dioxane. 10% by mass of the prepared monomer solution was placed in a 100 mL three-necked flask and heated to 70°C under a nitrogen stream. Then, a solution containing 0.099 g (0.6 mmol) of AIBN and 0.032 g (0.3 mmol) of 3MPA was added dropwise to the remaining monomer solution over 1 hour, and the mixture was stirred at 70°C for 6 hours. After cooling to room temperature (25°C), the resulting reaction solution was added to hexane. The precipitate was filtered off and dried under reduced pressure to obtain 4.07 g of comparative copolymer RCP3 (number average molecular weight (Mn): 9,500, weight average molecular weight (Mw): 22,800).

[0197] <Comparative Example 4> 3.99 g (15 mmol) of comparative monomer (RM2) was dissolved in 15 mL of 1,4-dioxane in a 100 mL three-necked flask and heated to 70°C under a nitrogen stream. A solution of 0.049 g (0.3 mmol) of AIBN and 0.016 g (0.15 mmol) of 3MPA dissolved in 5 mL of 1,4-dioxane was added dropwise over 1 hour, and the mixture was stirred at 70°C for 6 hours. After cooling to room temperature (25°C), the resulting reaction solution was added to hexane. The precipitate was filtered off and dried under reduced pressure to obtain 3.74 g of comparative polymer RCP4 (number average molecular weight (Mn): 9,800, weight average molecular weight (Mw): 22,700).

[0198] <Comparative Example 5> A monomer solution was prepared by dissolving 3.99 g (15 mmol) of comparative monomer (RM2) and 0.87 g (7.5 mmol) of 2-hydroxyethyl acrylate (HEA) in 25 mL of 1,4-dioxane. 10% by mass of the prepared monomer solution was placed in a 100 mL three-necked flask and heated to 70°C under a nitrogen stream. Then, a solution containing 0.074 g (0.45 mmol) of AIBN and 0.023 g (0.23 mmol) of 3MPA was added dropwise to the remaining monomer solution over 1 hour, and the mixture was stirred at 70°C for 6 hours. After cooling to room temperature (25°C), the resulting reaction solution was added to hexane. The precipitate was filtered off and dried under reduced pressure to obtain 4.63 g of comparative polymer RCP5 (number average molecular weight (Mn): 10,400, weight average molecular weight (Mw): 23,500).

[0199] <Comparative Example 6> A monomer solution was prepared by dissolving 3.99 g (15 mmol) of comparative monomer (RM2) and 0.72 g (7.5 mmol) of acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) in 25 mL of 1,4-dioxane. 10% by mass of the prepared monomer solution was placed in a 100 mL three-necked flask and heated to 70°C under a nitrogen stream. Then, a solution containing 0.074 g (0.45 mmol) of AIBN and 0.024 g (0.23 mmol) of 3MPA was added dropwise to the remaining monomer solution over 1 hour, and the mixture was stirred at 70°C for 6 hours. After cooling to room temperature (25°C), the resulting reaction solution was added to hexane. The precipitate was filtered off and dried under reduced pressure to obtain 4.44 g of the comparative copolymer RCP6 (number average molecular weight (Mn): 10,600, weight average molecular weight (Mw): 24,000).

[0200] Table 3 summarizes the composition of the polymers or copolymers synthesized in the above synthesis examples, as well as their number-average molecular weight (Mn) and weight-average molecular weight (Mw).

[0201] [Table 3] In Table 3 above, HEA represents 2-hydroxyethyl acrylate, MTA represents 2-methoxyethyl acrylate, and EEA represents 2-ethoxyethyl acrylate.

[0202] (Preparation of water-based ink Ink1) <Example 31> <<Preparation of Pigment Dispersion PD1>> 35.0 parts of deionized water and 5.0 parts of ethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) were placed in a glass container and stirred. Then, 15 parts of polymer CP1 prepared in Example 1 were added and dissolved. Next, 40.0 parts of titanium dioxide JR-600A (manufactured by Teika Co., Ltd.) were added little by little while stirring, and the mixture was stirred for 12 hours. 540.0 parts of 1 mm diameter zirconia beads were added, and the mixture was dispersed using a Big Rotor BR-2 (manufactured by AS ONE Corporation) at a rotation speed of 90 rpm for 5 days. The contents were filtered through a membrane filter with a pore size of 5 μm, and an adjusted amount of deionized water was added to obtain 90.0 parts of pigment dispersion PD1 (pigment solid content concentration: 40%). <<Ink Preparation>> 20.0 parts of pigment dispersion PD1, 18.0 parts of ethylene glycol, 4.0 parts of 3-methoxy-N,N-dimethylpropionamide (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.0 part of Zonyl FS-300 (manufactured by Dupont, a fluorine-based surfactant, 40% solids), 0.2 parts of triethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.0 part of 1,2-benzothiazolin-3-one (manufactured by Tokyo Chemical Industry Co., Ltd.), and 57.0 parts of deionized water were mixed and stirred for 1 hour, then filtered through a membrane filter with a pore size of 1.2 μm to obtain Ink 1 of the present invention.

[0203] (Preparation of water-based ink Ink2) <Example 32> Pigment dispersion PD2 and ink Ink2 were obtained in the same manner as in Example 31, except that polymer CP2 prepared in Example 2 was used instead of polymer CP1 used in Example 31.

[0204] (Preparation of water-based ink Ink3) <Example 33> <<Preparation of Pigment Dispersion PD3>> 35.0 parts of deionized water and 5.0 parts of glycerol (manufactured by Tokyo Chemical Industry Co., Ltd.) were placed in a glass container and stirred. Then, 15 parts of copolymer CP3 prepared in Example 3 and 2.9 parts of (2-hydroxyethyl)dimethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and dissolved. Next, 40.0 parts of titanium dioxide JR-600A (manufactured by Teika Co., Ltd.) were added little by little while stirring, and the mixture was stirred for 12 hours. 540.0 parts of 1 mm diameter zirconia beads were added, and the mixture was dispersed using a Big Rotor BR-2 (manufactured by AS ONE Corporation) at a rotation speed of 90 rpm for 5 days. The contents were filtered through a membrane filter with a pore size of 5 μm, and an adjusted amount of deionized water was added to obtain 90.0 parts of pigment dispersion PD3 (pigment solid content concentration: 40%). <<Ink Preparation>> Ink 3 was obtained in the same manner as in Example 31, except that pigment dispersion PD3 was used instead of pigment dispersion PD1 used in Example 31.

[0205] (Preparation of water-based ink Ink4) <Example 34> Pigment dispersion PD4 and ink Ink4 were obtained in the same manner as in Example 31, except that polymer CP4 prepared in Example 4 was used instead of polymer CP1 used in Example 31.

[0206] (Preparation of water-based ink Ink5) <Example 35> Pigment dispersion PD5 and ink Ink5 were obtained in the same manner as in Example 31, except that polymer CP5 prepared in Example 5 was used instead of polymer CP1 used in Example 31.

[0207] (Preparation of water-based ink Ink6) <Example 36> Pigment dispersion PD6 and ink Ink6 were obtained in the same manner as in Example 33, except that copolymer CP6 prepared in Example 6 was used instead of copolymer CP3 used in Example 33, and 2.3 parts of (2-hydroxyethyl)dimethylamine were used instead of 2.9 parts of (2-hydroxyethyl)dimethylamine used in Example 33.

[0208] (Preparation of water-based ink Ink7) <Example 37> Pigment dispersion PD7 and ink Ink7 were obtained in the same manner as in Example 31, except that polymer CP7 prepared in Example 7 was used instead of polymer CP1 used in Example 31.

[0209] (Preparation of water-based ink Ink8) <Example 38> Pigment dispersion PD8 and ink Ink8 were obtained in the same manner as in Example 33, except that copolymer CP8 prepared in Example 8 was used instead of copolymer CP3 used in Example 33, and 2.0 parts of (2-hydroxyethyl)dimethylamine was used instead of 2.9 parts of (2-hydroxyethyl)dimethylamine used in Example 33.

[0210] (Preparation of water-based ink Ink9) <Example 39> Pigment dispersion PD9 and ink Ink9 were obtained in the same manner as in Example 31, except that polymer CP9 prepared in Example 9 was used instead of polymer CP1 used in Example 31.

[0211] (Preparation of water-based ink Ink10) <Example 40> Pigment dispersion PD10 and ink Ink10 were obtained in the same manner as in Example 33, except that copolymer CP10 prepared in Example 10 was used instead of copolymer CP3 used in Example 33, and 1.8 parts of (2-hydroxyethyl)dimethylamine was used instead of 2.9 parts of (2-hydroxyethyl)dimethylamine used in Example 33.

[0212] (Preparation of water-based ink Ink11) <Example 41> Pigment dispersion PD11 and ink Ink11 were obtained in the same manner as in Example 31, except that polymer CP11 prepared in Example 11 was used instead of polymer CP1 used in Example 31.

[0213] (Preparation of water-based ink Ink12) <Example 42> Pigment dispersion PD12 and ink Ink12 were obtained in the same manner as in Example 33, except that copolymer CP12 prepared in Example 12 was used instead of copolymer CP3 used in Example 33, and 2.3 parts of (2-hydroxyethyl)dimethylamine were used instead of 2.9 parts of (2-hydroxyethyl)dimethylamine used in Example 33.

[0214] (Preparation of water-based ink Ink13) <Example 43> Pigment dispersion PD13 and ink Ink13 were obtained in the same manner as in Example 31, except that polymer CP13 prepared in Example 13 was used instead of polymer CP1 used in Example 31.

[0215] (Preparation of water-based ink Ink14) <Example 44> Pigment dispersion PD14 and ink Ink14 were obtained in the same manner as in Example 33, except that copolymer CP14 prepared in Example 14 was used instead of copolymer CP3 used in Example 33, and 2.3 parts of (2-hydroxyethyl)dimethylamine were used instead of 2.9 parts of (2-hydroxyethyl)dimethylamine used in Example 33.

[0216] (Preparation of water-based ink Ink15) <Example 45> Pigment dispersion PD15 and ink Ink15 were obtained in the same manner as in Example 33, except that copolymer CP15 prepared in Example 15 was used instead of copolymer CP3 used in Example 33, and 2.4 parts of (2-hydroxyethyl)dimethylamine were used instead of 2.9 parts of (2-hydroxyethyl)dimethylamine used in Example 33.

[0217] (Preparation of water-based ink Ink16) <Example 46> Pigment dispersion PD16 and ink Ink16 were obtained in the same manner as in Example 33, except that copolymer CP16 prepared in Example 16 was used instead of copolymer CP3 used in Example 33, and 2.4 parts of (2-hydroxyethyl)dimethylamine were used instead of 2.9 parts of (2-hydroxyethyl)dimethylamine used in Example 33.

[0218] (Preparation of water-based ink Ink17) <Example 47> Pigment dispersion PD17 and ink Ink17 were obtained in the same manner as in Example 33, except that copolymer CP17 prepared in Example 17 was used instead of copolymer CP3 used in Example 33, and 2.3 parts of (2-hydroxyethyl)dimethylamine were used instead of 2.9 parts of (2-hydroxyethyl)dimethylamine used in Example 33.

[0219] (Preparation of water-based ink Ink18) <Example 48> Pigment dispersion PD18 and ink Ink18 were obtained in the same manner as in Example 33, except that copolymer CP18 prepared in Example 18 was used instead of copolymer CP3 used in Example 33, and 2.3 parts of (2-hydroxyethyl)dimethylamine were used instead of 2.9 parts of (2-hydroxyethyl)dimethylamine used in Example 33.

[0220] (Preparation of water-based ink Ink19) <Example 49> Pigment dispersion PD19 and ink Ink19 were obtained in the same manner as in Example 33, except that copolymer CP19 prepared in Example 19 was used instead of copolymer CP3 used in Example 33, and 2.2 parts of (2-hydroxyethyl)dimethylamine were used instead of 2.9 parts of (2-hydroxyethyl)dimethylamine used in Example 33.

[0221] (Preparation of water-based ink Ink20) <Example 50> Pigment dispersion PD20 and ink Ink20 were obtained in the same manner as in Example 33, except that copolymer CP20 prepared in Example 20 was used instead of copolymer CP3 used in Example 33, and 1.8 parts sodium hydroxide (manufactured by Kanto Chemical Co., Ltd.) was used instead of 2.9 parts (2-hydroxyethyl)dimethylamine used in Example 33.

[0222] (Preparation of water-based ink Ink21) <Example 51> Pigment dispersion PD21 and ink Ink21 were obtained in the same manner as in Example 31, except that polymer CP21 prepared in Example 21 was used instead of polymer CP1 used in Example 31.

[0223] (Preparation of water-based ink Ink22) <Example 52> Pigment dispersion PD22 and ink Ink22 were obtained in the same manner as in Example 33, except that copolymer CP22 prepared in Example 22 was used instead of copolymer CP3 used in Example 33, and 1.6 parts of (2-hydroxyethyl)dimethylamine was used instead of 2.9 parts of (2-hydroxyethyl)dimethylamine used in Example 33.

[0224] (Preparation of water-based ink Ink23) <Example 53> Pigment dispersion PD23 and ink Ink23 were obtained in the same manner as in Example 33, except that copolymer CP23 prepared in Example 23 was used instead of copolymer CP3 used in Example 33, and 1.7 parts of (2-hydroxyethyl)dimethylamine was used instead of 2.9 parts of (2-hydroxyethyl)dimethylamine used in Example 33.

[0225] (Preparation of water-based ink Ink24) <Example 54> Pigment dispersion PD24 and ink Ink24 were obtained in the same manner as in Example 33, except that copolymer CP24 prepared in Example 24 was used instead of copolymer CP3 used in Example 33, and 1.8 parts of (2-hydroxyethyl)dimethylamine was used instead of 2.9 parts of (2-hydroxyethyl)dimethylamine used in Example 33.

[0226] (Preparation of water-based ink Ink25) <Example 55> Pigment dispersion PD25 and ink Ink25 were obtained in the same manner as in Example 33, except that copolymer CP25 prepared in Example 25 was used instead of copolymer CP3 used in Example 33, and 1.7 parts of (2-hydroxyethyl)dimethylamine was used instead of 2.9 parts of (2-hydroxyethyl)dimethylamine used in Example 33.

[0227] (Preparation of water-based ink Ink26) <Example 56> Pigment dispersion PD26 and ink Ink26 were obtained in the same manner as in Example 31, except that polymer CP26 prepared in Example 26 was used instead of polymer CP1 used in Example 31.

[0228] (Preparation of water-based ink Ink27) <Example 57> Pigment dispersion PD27 and ink Ink27 were obtained in the same manner as in Example 33, except that copolymer CP27 prepared in Example 27 was used instead of copolymer CP3 used in Example 33, and 1.5 parts of (2-hydroxyethyl)dimethylamine was used instead of 2.9 parts of (2-hydroxyethyl)dimethylamine used in Example 33.

[0229] (Preparation of water-based ink Ink28) <Example 58> Pigment dispersion PD28 and ink Ink28 were obtained in the same manner as in Example 33, except that copolymer CP28 prepared in Example 28 was used instead of copolymer CP3 used in Example 33, and 1.6 parts of (2-hydroxyethyl)dimethylamine was used instead of 2.9 parts of (2-hydroxyethyl)dimethylamine used in Example 33.

[0230] (Preparation of water-based ink Ink29) <Example 59> Pigment dispersion PD29 and ink Ink29 were obtained in the same manner as in Example 33, except that copolymer CP29 prepared in Example 29 was used instead of copolymer CP3 used in Example 33, and 1.6 parts of (2-hydroxyethyl)dimethylamine was used instead of 2.9 parts of (2-hydroxyethyl)dimethylamine used in Example 33.

[0231] (Preparation of water-based ink Ink30) <Example 60> Pigment dispersion PD30 and ink Ink30 were obtained in the same manner as in Example 33, except that copolymer CP30 prepared in Example 30 was used instead of copolymer CP3 used in Example 33, and 1.6 parts of (2-hydroxyethyl)dimethylamine was used instead of 2.9 parts of (2-hydroxyethyl)dimethylamine used in Example 33.

[0232] (Preparation of water-based ink Ink31) <Example 61> <<Ink Preparation>> 25.0 parts of pigment dispersion PD1, 18.0 parts of ethylene glycol, 4.0 parts of 3-methoxy-N,N-dimethylpropionamide (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.0 part of Zonyl FS-300 (fluorine-based surfactant, manufactured by Dupont, 40% solids), 0.2 parts of triethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.0 part of 1,2-benzothiazolin-3-one (manufactured by Tokyo Chemical Industry Co., Ltd.), and 50.8 parts of deionized water were mixed and stirred for 1 hour, then filtered through a membrane filter with a pore size of 1.2 μm to obtain Ink31 of the present invention.

[0233] (Preparation of water-based ink Ink32) <Example 62> <<Preparation of Pigment Dispersion PD31>> 35.0 parts of deionized water and 5.0 parts of ethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) were placed in a glass container and stirred. Then, 15 parts of polymer CP1 prepared in Example 1 were added and dissolved. Next, 8.06 parts of titanium dioxide pigment (JR-600A, manufactured by Teika Co., Ltd.) were added little by little while stirring, and the mixture was stirred for 12 hours. 540.0 parts of 1 mm diameter zirconia beads were added, and the mixture was dispersed using a Big Rotor BR-2 (manufactured by AS ONE Corporation) at a rotation speed of 90 rpm for 5 days. The contents were filtered through a membrane filter with a pore size of 5 μm, and an adjusted amount of deionized water was added to obtain 90.0 parts of pigment dispersion PD31 (pigment solid content concentration: 40%). <<Ink Preparation>> 45.0 parts of pigment dispersion PD31, 20.0 parts of urethane resin emulsion (Takelac WS-6021, manufactured by Mitsui Chemicals, Inc.), 6.9 parts of glycerin (manufactured by Kanto Chemical Co., Ltd.), 4.5 parts of silica microparticle dispersion (Snowtex ST-CM, manufactured by Nissan Chemical Corporation, prepared so that the silica microparticle content is 1.93% by mass of the total ink amount), 2.9 parts of triethylene glycol monobutyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.9 parts of BYK-387 (polyether-modified silicone-based surfactant, manufactured by Big Chemie Co., Ltd.), and 0.4 parts of triethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and then ion-exchanged water was added to bring the total volume to 100 parts. The mixture was then stirred for 1 hour, and then filtered through a membrane filter with a pore size of 1.2 μm to obtain the ink Ink32 of the present invention.

[0234] (Preparation of water-based ink Ink33) <Example 71> Pigment dispersion PD32 and ink Ink33 were obtained in the same manner as in Example 31, except that polymer CP31 prepared in Example 67 was used instead of polymer CP1 used in Example 31.

[0235] (Preparation of water-based ink Ink34) <Example 72> Pigment dispersion PD33 and ink In34 were obtained in the same manner as in Example 31, except that polymer CP32 prepared in Example 68 was used instead of polymer CP1 used in Example 31.

[0236] (Preparation of water-based ink Ink35) <Example 73> Pigment dispersion PD34 and ink Ink35 were obtained in the same manner as in Example 31, except that polymer CP33 prepared in Example 69 was used instead of polymer CP1 used in Example 31.

[0237] (Preparation of water-based ink Ink36) <Example 74> Pigment dispersion PD35 and ink Ink36 were obtained in the same manner as in Example 33, except that copolymer CP34 prepared in Example 70 was used instead of copolymer CP3 used in Example 33, and 1.8 parts sodium hydroxide (manufactured by Kanto Chemical Co., Ltd.) was used instead of 2.9 parts (2-hydroxyethyl)dimethylamine used in Example 33.

[0238] (Preparation of comparative water-based ink RInk1) <Comparative Example 7> A comparative pigment dispersion RPD1 and a comparative ink RInk1 were obtained in the same manner as in Example 31, except that a comparative polymer RCP1 was used instead of the polymer CP1 used in Example 31.

[0239] (Preparation of comparative water-based ink RInk2) <Comparative Example 8> A comparative pigment dispersion RPD2 and a comparative ink RInk2 were obtained in the same manner as in Example 31, except that a comparative copolymer RCP2 was used instead of the polymer CP1 used in Example 31.

[0240] (Preparation of comparative water-based ink RInk3) <Comparative Example 9> A comparative pigment dispersion PD3 and a comparative ink RInk3 were obtained in the same manner as in Example 33, except that comparative copolymer RCP3 was used instead of copolymer CP3 used in Example 33, and 4.2 parts of (2-hydroxyethyl)dimethylamine were used instead of 2.9 parts of (2-hydroxyethyl)dimethylamine used in Example 33.

[0241] (Preparation of comparative water-based ink RInk4) <Comparative Example 10> A comparative pigment dispersion RPD4 and a comparative ink RInk4 were obtained in the same manner as in Example 31, except that the comparative polymer RCP4 was used instead of the polymer CP1 used in Example 31.

[0242] (Preparation of comparative water-based ink RInk5) <Comparative Example 11> A comparative pigment dispersion RPD5 and a comparative ink RInk5 were obtained in the same manner as in Example 31, except that a comparative polymer RCP5 was used instead of the polymer CP1 used in Example 31.

[0243] (Preparation of comparative water-based ink RInk6) <Comparative Example 12> A comparative pigment dispersion PD6 and a comparative ink RInk6 were obtained in the same manner as in Example 33, except that comparative copolymer RCP6 was used instead of copolymer CP3 used in Example 33, and 2.7 parts of sodium hydroxide were used instead of 2.9 parts of (2-hydroxyethyl)dimethylamine used in Example 33.

[0244] (Evaluation of storage stability of pigment dispersions) Each pigment dispersion was filled into a glass container and stored at 70°C for two weeks. The percentage change in viscosity after storage compared to the viscosity before storage was calculated using the following formula and evaluated according to the following criteria. A viscometer (RE80L, manufactured by Toki Sangyo Co., Ltd.) was used to measure the viscosity at 25°C at 50 revolutions per minute. Viscosity change rate (%) = 100 × (Viscosity of pigment dispersion after storage - Viscosity of pigment dispersion before storage) / Viscosity of pigment dispersion before storage [Evaluation Criteria] A: Viscosity change rate within ±5% B: Viscosity change rate exceeds ±5% but is within ±8%. C: Viscosity change rate exceeds ±8% but is within ±10% D: Viscosity change rate is greater than ±10% but within ±30%. E: Viscosity change rate exceeds ±30% (gelling makes evaluation impossible)

[0245] (Evaluation of ink storage stability) Each ink was filled into an ink cartridge and stored at 70°C for one week. The percentage change in viscosity after storage compared to the viscosity before storage was calculated using the following formula and evaluated according to the following criteria. A viscometer (RE80L, manufactured by Toki Sangyo Co., Ltd.) was used to measure the viscosity at 25°C over 50 revolutions per minute. Viscosity change rate (%) = 100 × (Viscosity of ink after storage - Viscosity of ink before storage) / Viscosity of ink before storage [Evaluation Criteria] A: Viscosity change rate within ±5% B: Viscosity change rate exceeds ±5% but is within ±8%. C: Viscosity change rate exceeds ±8% but is within ±10% D: Viscosity change rate is greater than ±10% but within ±30%. E: Viscosity change rate exceeds ±30% (gelling makes evaluation impossible)

[0246] (Evaluation of ink redispersibility) Since the settling of ink components by standing requires a long period of time, a centrifuge was used to accelerate the settling of the ink components. First, ink was poured into a PYREX® IWAKI TE-32 test tube (16.5 mm × 105 mm, manufactured by AGC Corporation) to a depth of 45 mm, and the tube was sealed with a silicone stopper to prepare the evaluation sample. Next, to define the initial state of the evaluation sample, immediately after preparing the evaluation sample, the tip of a pipette dropper (2-3 mm) was dipped into the ink surface to collect approximately 0.02 mL (approximately 20 mg) of ink. Of the collected ink, 4-10 mg was placed in a 50 mL sample bottle and diluted 4000 times with deionized water. The sample bottle was placed on the stand of a Mix Rotor VMR-5R (manufactured by AS ONE) and rotated at a rotation speed of 60 rpm for more than 10 minutes. Immediately afterward, the UV-VIS absorption spectrum was measured using a UV-Vis-Near Infrared Spectrophotometer V-680 (manufactured by JASCO Corporation) and used as the reference spectrum before accelerated sedimentation. The measurement conditions are shown below. -UV-VIS measurement conditions- Wavelength range: 350~800nm Cell length: 3mm Measurement conditions: UV / VIS bandwidth 2.0nm, NIR bandwidth 4.0nm, response FAST, scanning speed 400nm / min Next, the evaluation sample was placed in an inverter hematocrit centrifuge 3220 (manufactured by KUBOTA) and accelerated to sedimentation at a rotation speed of 300 rpm for 14 hours. The removed evaluation sample was gently tilted on its side and gently placed on a mix rotor VMR-5R, which was rotated at a rotation speed of 60 rpm for 1, 2, 3, or 4 minutes. Immediately afterward, the evaluation sample was returned to its original vertical position, and a sample was taken from the ink surface as described above. The absorption spectrum was measured, and the redispersion spectra after 1, 2, 3, or 4 minutes were recorded. The redispersibility of the ink was evaluated by calculating the rate of change of the redispersion spectrum relative to the reference spectrum using the following formula, and then evaluating it according to the following criteria. Redispersion (%) = 100 × (absorbance at the peak wavelength of the redispersion spectrum / absorbance at the peak wavelength of the reference spectrum) [Evaluation Criteria] A: The redispersion spectrum after 1 minute shows a redispersion of 90% or more. B: Redispersion spectrum after 2 minutes shows redispersion of 90% or more. C: Redispersion spectrum after 3 minutes shows redispersion of 90% or more. D: Redispersion spectrum after 4 minutes shows redispersion of 90% or more. E: Redispersion spectrum after 4 minutes shows redispersion of 89% or less.

[0247] Table 4 summarizes the storage stability and redispersibility results for the pigment dispersions PD1-PD31 from Examples 31-62, the pigment dispersions PD32-35 and inks Ink1-Ink36 from Examples 71-74, and the comparative pigment dispersions RPD1-RPD6 and comparative inks RInk1-RInk6 from Comparative Examples 7-12.

[0248] [Table 4]

[0249] (Fabrication of solar cell backsheet BS1) <Example 63> <<Preparation of protective layer forming solution PC1>> 45 parts dimethylformamide (manufactured by Kanto Chemical Co., Ltd.) and 36 parts polymer CP2 obtained in Example 2 were added to a glass container and stirred to dissolve. Then, 10 parts titanium dioxide JR-405 (manufactured by Teika Co., Ltd.) were added little by little while stirring, and the mixture was stirred for 12 hours. 540.0 parts 1 mm diameter zirconia beads were added and the mixture was dispersed using a Big Rotor BR-2 (manufactured by AS ONE Corporation) at a rotation speed of 90 rpm for 5 days. The contents were filtered through a membrane filter with a pore size of 5 μm, and the adjusted amount of dimethylformamide (manufactured by Kanto Chemical Co., Ltd.) and 4.0 parts hexamethylene diisocyanate (manufactured by Tokyo Chemical Co., Ltd.) were added to obtain 100.0 parts protective layer forming solution PC1 (pigment solid content concentration: 10%). <<Fabrication of solar cell backsheet BS1>> A protective layer forming solution PC1 was applied to the surface of a 75 μm thick white polyethylene terephthalate film (Lumirror MX11, manufactured by Toray Industries, Inc.) using a wire bar. After drying at 150°C for 5 minutes to form a protective layer with a thickness of 2 μm, the film was aged at 50°C for 3 days to obtain a solar cell backsheet BS1.

[0250] (Fabrication of solar cell backsheet BS2) <Example 64> A protective layer forming liquid PC2 and a solar cell backsheet BS2 were obtained in the same manner as in Example 63, except that polymer CP11 prepared in Example 11 was used instead of polymer CP2 used in Example 63.

[0251] (Fabrication of solar cell backsheet BS3) <Example 65> A protective layer forming liquid PC3 and a solar cell backsheet BS3 were obtained in the same manner as in Example 63, except that polymer CP21 prepared in Example 21 was used instead of polymer CP2 used in Example 63.

[0252] (Fabrication of solar cell backsheet BS4) <Example 66> A protective layer forming liquid PC4 and a solar cell backsheet BS4 were obtained in the same manner as in Example 63, except that polymer CP26 prepared in Example 26 was used instead of polymer CP2 used in Example 63.

[0253] (Fabrication of solar cell backsheet RBS1) <Comparative Example 13> A protective layer forming liquid RPC1 and a comparative solar cell backsheet RBS1 were obtained in the same manner as in Example 63, except that a comparative polymer RCP2 was used instead of the polymer CP2 used in Example 63.

[0254] (Fabrication of solar cell backsheet RBS2) <Comparative Example 14> A protective layer forming liquid RPC2 and a comparative solar cell backsheet RBS2 were obtained in the same manner as in Example 63, except that a comparative polymer RCP5 was used instead of the polymer CP2 used in Example 63.

[0255] (Weather resistance evaluation) <Measurement of initial break elongation Es> Each fabricated solar cell backsheet was cut to a size of 1 cm x 10 cm, and the elongation at break of the solar cell backsheet was measured according to ASTM-D882 (ANNUAL BOOK OF ASTM STANDARDS 1999 edition), and the result was defined as the initial elongation at break Es. <Measurement of elongation at break (Ee) over time> Using a Super Xenon Weather Meter SX75 (manufactured by Suga Test Instruments Co., Ltd.), measurements were taken at a black panel temperature of 65°C, relative humidity of 50% RH, and illuminance of 180 W / m². 2 Under conditions of wavelength range (300-400 nm), a 10 cm x 20 cm solar cell backsheet test specimen was subjected to repeated UV irradiation for 108 minutes and UV irradiation with water spraying for 12 minutes (without humidity control), for a total of 3000 hours of UV irradiation. The removed test specimen was then cut to a size of 1 cm x 10 cm, and the elongation at break was measured using the method described above. The result was defined as the elongation at break over time, Ee. <Weather resistance evaluation> As an indicator of weather resistance, the rate of elongation at break (%) = (Ee / Es) × 100 was calculated, and the following judgments were made based on the evaluation criteria below. [Evaluation Criteria] A: Breaking elongation retention rate of 50% or more B: Breaking elongation retention rate is 30% or more but less than 50% C: Breaking elongation retention rate is less than 30%

[0256] Table 5 summarizes the weather resistance results for the solar cell backsheets BS1 to BS4 of Examples 63 to 66 and the comparative solar cell backsheets RBS1 to RBS2 of Comparative Examples 13 to 14.

[0257] [Table 5]

[0258] Examples of the present invention are as follows: <1> It is a polymer having a structural unit represented by the following general formula (1). JPEG0007920686000042.jpg49112 (In general formula (1), R1 is hydrogen or a methyl group, L1 is -COO-, -CONH-, or a bond, X is a hydrocarbon group having 2 to 10 carbon atoms, or a hydrocarbon group having 2 to 10 carbon atoms containing oxygen, L2 is -O- or -NH-, Y is a hydrocarbon group having 2 to 12 carbon atoms, L3 is -NH-C2H4-R2, -O-Ph-CH2CH(R2)2, or -O-Np-CH2CH(R2)2, where Ph is a phenylene group, Np is a naphthylene group, and R2 is a phosphonic acid group.) <2> The aforementioned <1> This copolymer has a structural unit represented by the general formula (1) described below and a structural unit represented by the general formula (2) below. JPEG0007920686000043.jpg2976 (In general formula (2), R3 is hydrogen, or a methyl group, X + (This is a proton or a positive ion.) <3> An ink containing water, a colorant, and a resin, The resin <1> The polymer described above, and the <2> This ink is characterized by containing at least one of the copolymers described above. <4> The aforementioned <1> The polymer described above, or the above <2> The weight-average molecular weight of the copolymer described is 5,000 to 50,000. <3> This is the ink described. <5> The colorant is titanium oxide, <3> From the above <4> The ink is one of the inks listed in either of the following. <6> The aforementioned <3> from the above <5> This is an ink container characterized by containing the ink described in any of the following. <7> The aforementioned <3> From the above <5> This is an image forming method characterized by ejecting an ink described in any of the above onto a recording medium to form an image. <8> The aforementioned <6> The image forming apparatus is characterized by comprising an ink storage container as described above, and a dispensing means for dispensing the ink contained in the ink storage container onto a recording medium. <9> A solar cell backsheet having a protective layer made of titanium dioxide and resin, The resin <1> The polymer described above, and the <2> This solar cell backsheet is characterized by containing at least one of the copolymers.

[0259] The aforementioned <1> The polymer of the above <2> copolymer, the <3> ~ <5> The ink, the aforementioned <6> The ink container, the <7> Image formation method, the <8> Image forming apparatus, and the <9> The solar cell backsheet solves the problems of the conventional method and achieves the objectives of the present invention. [Explanation of Symbols]

[0260] 400 Image forming apparatus 401 Exterior of the image forming apparatus 401c Cover of the main unit of the device 404 Cartridge Holder 410 Main Tank Main tanks for each color: 410k, 410c, 410m, 410y (Black (K), Cyan (C), Magenta (M), Yellow (Y)) 411 Ink reservoir 413 Ink outlet 414 Storage container case 420 Mechanism Department 434 Discharge head 436 Supply Tube [Prior art documents] [Patent Documents]

[0261] [Patent Document 1] Patent No. 5863600

Claims

1. A polymer having a structural unit represented by the following general formula (1). (In general formula (1), R1 is hydrogen or a methyl group, L1 is -COO-, -CONH-, or a bond, X is a hydrocarbon group having 2 to 10 carbon atoms, or a hydrocarbon group having 2 to 10 carbon atoms containing oxygen, L2 is -O- or -NH-, Y is a hydrocarbon group having 2 to 12 carbon atoms, L3 is -NH-C2H4-R2, -O-Ph-CH2CH(R2)2, or -O-Np-CH2CH(R2)2, where Ph is a phenylene group, Np is a naphthylene group, and R2 is a phosphonic acid group.)

2. A copolymer having a structural unit represented by the general formula (1) described in claim 1 and a structural unit represented by the following general formula (2). (In general formula (2), R3 is hydrogen or a methyl group, and X+ is a proton or a cation.)

3. The polymer according to claim 1, wherein the weight-average molecular weight is 5,000 to 50,000.

4. The copolymer according to claim 2, wherein the weight-average molecular weight is 5,000 to 50,000.

5. An ink containing water, a colorant, and a resin, An ink characterized in that the resin comprises the polymer according to claim 1 or claim 3, or the copolymer according to claim 2 or claim 4.

6. The ink according to claim 5, wherein the colorant is titanium dioxide.

7. An ink container characterized by containing the ink described in claim 5.

8. An image forming method characterized by ejecting the ink described in claim 5 onto a recording medium to form an image.

9. An image forming apparatus comprising an ink storage container according to claim 7, and a dispensing means for dispensing the ink stored in the ink storage container onto a recording medium.

10. A solar cell backsheet having a protective layer made of titanium dioxide and resin, A solar cell backsheet characterized in that the resin comprises at least one of the polymer described in claim 1 and the copolymer described in claim 2.

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