Polymer, resin particles containing the polymer, aqueous dispersion, ink, method for producing printed matter using the ink, image-fixed article, and polymerizable monomer

Abstract

The present invention addresses the problem of providing a polymer that has excellent adhesion to a substrate comprising a polyolefin. The problem is solved by using a polymer characterized by including a structure derived from a polymerizable monomer (M) represented by formula (1) as a structural unit. (In the formula, A1 represents a hydrocarbon group including at least two aromatic ring skeletons, the hydrocarbon group may have a substituent, and the substituent is a non-ionic substituent. A2 represents an alkylene chain with 1-10 carbon atoms, and the alkylene chain may have a substituent. In addition, the plurality of A2 may be the same or different from each other. n is an integer of 3-100. X1 represents a group having an ethylenically unsaturated double bond.)

Description

[Technical Field]

[0001] The present invention relates to a polymer, resin particles containing the polymer, an aqueous dispersion, an ink, a method for producing a printed matter using the ink, an image-fixed article, and a polymerizable monomer. [Background technology]

[0002] Traditionally, polyolefins such as polypropylene have excellent processability and are less expensive than other polymeric materials, and therefore have been processed into films or fibers and used as flexible packaging films, nonwoven fabrics, etc. Flexible packaging films are generally used after undergoing printing processes such as front printing and reverse printing. Flexible packaging films that have been reverse printed and laminated are widely used from the viewpoints of print clarity, ink run-off prevention, and durability of the printed film. However, a shift to front printing is desired from the viewpoints of improving work efficiency and reducing the environmental and economic burden by eliminating the use of adhesives and solvents used in lamination. In addition, while gravure printing and flexographic printing have been mainstream in printing on flexible packaging films, inkjet printing, which can handle small-lot, high-mix production, has begun to be adopted. Inks used in these printing processes are shifting from solvent-based to water-based systems in order to reduce environmental impact, and various aqueous ink compositions capable of forming printed images on flexible packaging films, etc. by inkjet printing have been proposed.

[0003] For example, Patent Document 1 describes an aqueous inkjet ink composition that contains a binder resin composition for aqueous inkjet ink, characterized by containing specific core-shell type resin particles, and a specific moisturizing solvent. Furthermore, Patent Document 2 describes an ink composition containing a pigment, specific self-dispersing resin particles, at least two types of nonionic surfactants having HLB values ​​in different specific ranges, a water-soluble organic solvent, and water. Furthermore, Patent Document 3 describes an aqueous inkjet ink composition containing a pigment, a specific anionic group-containing resin, an emulsion, an acetylene diol surfactant, a specific silicone surfactant, a water-soluble solvent, and water. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-201692 [Patent Document 2] Japanese Patent Application Laid-Open No. 2013-18951 [Patent Document 3] Japanese Patent Application Laid-Open No. 2016-222754 Summary of the Invention [Problem to be solved by the invention]

[0005] However, even when ink (or ink) compositions described in these documents are used to inkjet print onto a polyolefin substrate such as a polypropylene film, the adhesion of the printed image to the substrate is not sufficient.

[0006]

[0006] Therefore, the present inventors have focused on the resin components contained in the ink and conducted extensive research in order to develop an ink that can be printed with excellent adhesion to polyolefin substrates. As a result, they have found that a polymer containing a structure derived from a specific polymerizable monomer as a constituent unit exhibits excellent adhesion to polyolefins, and further that an ink containing such a polymer enables printing with excellent adhesion to polyolefins. Therefore, an object of the present invention is to provide a polymer that has excellent adhesion to polyolefin substrates and a compound that constitutes such a polymer. [Means for solving the problem]

[0007] The present invention is as follows. [1] A polymer comprising, as a constituent unit, a structure derived from a polymerizable monomer (M) represented by the following formula (1): [ka] [In formula (1), A 1 represents a hydrocarbon group containing two or more aromatic ring skeletons, and the hydrocarbon group may have a substituent, and the substituent is a nonionic substituent. A 2 represents an alkylene chain having 1 to 10 carbon atoms, and the alkylene chain may have a substituent. 2 may be the same or different. n is an integer of 3 to 100. X 1 represents a group having an ethylenically unsaturated double bond.] [2] A. 1 is any one of groups represented by the following formulas (1-a) to (1-f): [ka] [In the formula, R 1 and R 2 each independently represents a hydrogen atom or a monovalent aliphatic hydrocarbon group. R 3 , R 5 , R 6 , and R 8 each independently represents a monovalent aliphatic hydrocarbon group. R 4 , R 7 , and R 9 each independently represents a divalent aliphatic hydrocarbon group. k represents an integer of 1 to 5, and p represents an integer of 0 to 4. k+p is an integer of 1 to 5. q represents an integer of 0 to 3, and r represents an integer of 0 to 4. s represents an integer of 0 to 4, and j represents an integer of 1 to 5. s+j is an integer of 1 to 5. * is the "(OA 2 ) n " represents the bonding site with the terminal O (oxygen atom) in [3] The polymer according to [1] or [2], wherein the structure derived from the polymerizable monomer (M) satisfies the following formula (f1-1): (EM +E P8 )-(E MP )<-80kJ / mol (f1-1) [In formula (f1-1), E M is the absolute value of the zero-point energy of the structural molecule (Ip), E P8 is the absolute value of the zero-point energy of the propylene octamer, E MP is the absolute value of the zero-point energy of the association of the structural molecule (Ip) and the propylene octamer, The structural molecule (Ip) has a structure represented by the following formula (1-1) when the polymerizable monomer (M) is represented by the formula (1): Each zero-point energy is calculated using the Gaussian16 program from Gaussian, with the density functional B3LYP, the basis set 6-31G(d,p), and dispersion force correction (GD3BJ keyword). [ka] [In formula (1-1), A 1 and A 2 are the A in the formula (1), respectively. 1 and A 2 is the same as [4] Resin particles comprising the polymer according to any one of [1] to [3]. [5] The resin particles according to [4], wherein the resin particles are single-layer particles containing the polymer or particles having a core-shell structure containing the polymer in the shell layer. [6] An aqueous dispersion comprising the resin particles according to [4] or [5]. [7] An ink containing a binder and a solvent, wherein the binder contains the polymer according to any one of [1] to [3]. [8] The ink according to [7], wherein the binder is resin particles containing the polymer. [9] A method for producing a printed matter in which an image is printed on a substrate, the method comprising an image forming step of applying the ink according to [7] or [8] to the substrate to form an image.

[10] An image-fixed article in which an image containing a pigment and a resin is fixed to a part or all of a substrate, wherein the resin contains the polymer according to any one of [1] to [3].

[11] A compound represented by the following formula (2): [ka] [In formula (2), A 3 represents a hydrocarbon group containing two or more aromatic ring skeletons, and the hydrocarbon group may have a substituent, and the substituent is a nonionic substituent. A 4 represents an alkylene chain having 1 to 10 carbon atoms, and the alkylene chain may have a substituent. 4 may be the same or different. m is an integer of 3 to 100. X 2 represents a group having an ethylenically unsaturated double bond.]

[12] The compound according to

[11] , which satisfies the following formula (f2-1): (E M +E P8 )-(E MP )<-80kJ / mol (f2-1) [In the above formula (f2-1), E M is the absolute value of the zero-point energy of the structural molecule (I), E P8 is the absolute value of the zero-point energy of the propylene octamer, E MP is the absolute value of the zero-point energy of the association of the structural molecule (I) and the propylene octamer, When the compound is represented by the formula (2), the structural molecule (I) has a structure represented by the following formula (2-1): Each zero-point energy is calculated using the Gaussian16 program from Gaussian, with the density functional B3LYP, the basis set 6-31G(d,p), and dispersion force correction (GD3BJ keyword). [ka] [In formula (2-1), A 3 and A 4 are the A in the above formula (2), 3 and A 4 is the same as

[13] A. 3 is any one of groups represented by the following formulae (1-a) to (1-f): [ka] [In the formula, R 1 and R 2 each independently represents a hydrogen atom or a monovalent aliphatic hydrocarbon group. R 3 , R 5 , R 6 , and R 8 each independently represents a monovalent aliphatic hydrocarbon group. R 4 , R 7 , and R 9 each independently represents a divalent aliphatic hydrocarbon group. k represents an integer of 1 to 5, and p represents an integer of 0 to 4. k+p is an integer of 1 to 5. q represents an integer of 0 to 3, and r represents an integer of 0 to 4. s represents an integer of 0 to 4, and j represents an integer of 1 to 5. s+j is an integer of 1 to 5. * is the "(OA 4 ) m " represents the bonding site with the terminal O (oxygen atom) in [Effects of the Invention]

[0008] Due to the above-mentioned constitution, the polymer of the present invention has excellent adhesion to polyolefin substrates. Therefore, by using an ink (preferably an aqueous ink) containing the polymer, it is possible to print images that have excellent adhesion to polyolefin substrates such as polyolefin films and fabrics made of polyolefin fibers. In particular, even in aqueous inks, the use of the polymer of the present invention as a resin component can improve adhesion to polyolefin substrates. DETAILED DESCRIPTION OF THE INVENTION

[0009] The present invention will be described in detail below. In addition, a combination of two or more of the individual preferred embodiments of the present invention described below is also a preferred embodiment of the present invention. In addition, in this specification, "(meth)acrylate" means "acrylate" or "methacrylate," "(meth)acrylic" means "acrylic" or "methacrylic," and "(meth)acryloyl" means "acryloyl" or "methacryloyl." (Meth)acrylate is also sometimes referred to as a (meth)acrylic acid ester. Furthermore, unless otherwise specified in this specification, "A to B" representing a numerical range means "A or more and B or less."

[0010] 1. Polymer The polymer of the present disclosure is characterized by including, as a constituent unit, a structure (M) derived from a polymerizable monomer (M) represented by the following formula (1): The polymer of the present disclosure may also be referred to as a polymer (Pm).

[0011] [ka]

[0012] In formula (1), A 1 represents a hydrocarbon group containing two or more aromatic ring skeletons, and the hydrocarbon group may have a substituent, and the substituent is a nonionic substituent. 2represents an alkylene chain having 1 to 10 carbon atoms, and the alkylene chain may have a substituent. 2 may be the same or different, and n is an integer of 3 to 100. X 1 represents a group having an ethylenically unsaturated double bond.

[0013] <Polymerizable monomer (M)> The polymerizable monomer (M) is represented by the formula (1). 1 represents a polycyclic phenyl group, and the polycyclic phenyl group refers to a hydrocarbon group containing two or more aromatic ring skeletons. In this specification, a "hydrocarbon group containing two or more aromatic ring skeletons" may be referred to as a "polycyclic phenyl group." In the present invention, a structure in which two aromatic hydrocarbons with a monocyclic structure are condensed is considered to contain two aromatic ring skeletons. Therefore, in the present invention, "containing two or more aromatic ring skeletons" means satisfying at least one of the following: containing two or more aromatic hydrocarbon skeletons with a monocyclic structure such as a benzene ring (i.e., an unsaturated hydrocarbon ring that exhibits aromaticity by itself), or containing at least one aromatic hydrocarbon skeleton with a condensed ring structure (i.e., a condensed aromatic ring that exhibits aromaticity by condensing two or more unsaturated hydrocarbon rings).

[0014] Therefore, the polycyclic phenyl group may have two or more aromatic hydrocarbon skeletons of a monocyclic structure, one or more aromatic hydrocarbon skeletons of a fused ring structure, or one or more aromatic hydrocarbon skeletons of a monocyclic structure and one or more aromatic hydrocarbon skeletons of a fused ring structure. The aromatic ring skeletons contained in the polycyclic phenyl group may be the same or different.

[0015] The polycyclic phenyl group may be a hydrocarbon group consisting of only the aromatic ring skeleton (i.e., a hydrocarbon group consisting of only unsaturated hydrocarbon rings that exhibit aromaticity either alone or through condensed rings), or may have a hydrocarbon group other than the aromatic ring skeleton (i.e., a hydrocarbon group other than an unsaturated hydrocarbon ring that exhibits aromaticity either alone or through condensed rings). Examples of the other hydrocarbon group include monovalent or divalent or higher aliphatic hydrocarbon groups, such as alkyl groups, alkylene groups, alkenyl groups, alkenylene groups, and alkynyl groups, each having a chain structure or a cyclic structure. Of these, alkyl groups are preferred.

[0016] More specifically, the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, and may have a chain structure (aliphatic chain hydrocarbon group) or a cyclic structure (aliphatic cyclic hydrocarbon group).

[0017] Examples of the monovalent saturated aliphatic hydrocarbon group having a chain structure include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, and n-dodecyl groups; and branched alkyl groups such as isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, 2,3-dimethyl-2-butyl, 3-methylheptyl, and 2-ethylhexyl groups. Furthermore, examples of the n-valent (n = an integer of 2 or more) saturated aliphatic hydrocarbon group having a chain structure include groups in which (n-1) hydrogen atoms constituting the monovalent saturated aliphatic hydrocarbon group having a chain structure are replaced with bonds. Specific examples include alkylene groups having a chain structure such as a methylene group, an ethylene-1,1-diyl group, an ethylene-1,2-diyl group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group. The number of carbon atoms in the monovalent or divalent or higher chain saturated aliphatic hydrocarbon group (for example, when the alkyl group or alkylene group has a chain structure, the number of carbon atoms constituting the alkyl group or alkylene group) is preferably 1 to 18, more preferably 1 to 12, even more preferably 1 to 6, and still more preferably 1 to 3.

[0018] Examples of the monovalent saturated aliphatic hydrocarbon group having a cyclic structure include alkyl groups having a cyclic structure (i.e., cycloalkyl groups) such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a 3-methylcyclohexyl group, a 4-methylcyclohexyl group, a 4-ethylcyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Furthermore, examples of the n-valent (n = an integer of 2 or more) saturated aliphatic hydrocarbon group having a cyclic structure include groups in which (n-1) hydrogen atoms constituting the monovalent saturated aliphatic hydrocarbon group having a cyclic structure are replaced with bonds. Specific examples include divalent saturated alicyclic hydrocarbon groups such as a cyclohexyl-1,2-diyl group and a cyclohexyl-1,4-diyl group; trivalent saturated alicyclic hydrocarbon groups such as a cyclohexyl-1,3,5-triyl group; and tetravalent saturated alicyclic hydrocarbon groups such as a cyclohexyl-1,2,4,5-tetrayl group. The number of carbon atoms in the monovalent or divalent or higher cyclic saturated aliphatic hydrocarbon group (for example, when the alkyl group has a cyclic structure, the number of carbon atoms constituting the alkyl group) is preferably 3 to 18, more preferably 4 to 12, even more preferably 5 to 8, and particularly preferably 6 (specifically, a cyclohexyl group, etc.).

[0019] Examples of the monovalent unsaturated aliphatic hydrocarbon group having a chain structure include alkenyl groups having a chain structure such as vinyl group, n-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, 2-pentenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, and 3-methyl-1-butenyl group; and alkynyl groups having a chain structure such as ethynyl group, 2-propynyl group, 3-butynyl group, 4-pentynyl group, 1-methyl-3-butynyl group, 1,1-dimethyl-2-propynyl group, and 6-heptynyl group. Furthermore, examples of the n-valent (n = an integer of 2 or more) unsaturated aliphatic hydrocarbon group with a chain structure include groups in which (n-1) hydrogen atoms constituting the monovalent unsaturated aliphatic hydrocarbon group with a chain structure have been replaced with bonds. The monovalent or divalent or higher chain unsaturated aliphatic hydrocarbon group preferably has 2 to 18 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms.

[0020] Examples of the monovalent unsaturated aliphatic hydrocarbon group having a cyclic structure include alkenyl groups having a cyclic structure (that is, cycloalkenyl groups) such as a cyclohexenyl group, a cycloheptenyl group, and a cyclooctenyl group. Furthermore, examples of the n-valent (n = an integer of 2 or more) unsaturated aliphatic hydrocarbon group with a cyclic structure include groups in which (n-1) hydrogen atoms constituting the monovalent unsaturated aliphatic hydrocarbon group with a cyclic structure have been replaced with bonds. The monovalent or divalent or higher cyclic unsaturated aliphatic hydrocarbon group preferably has 3 to 18 carbon atoms, more preferably 4 to 12 carbon atoms, and even more preferably 5 to 8 carbon atoms.

[0021] The monocyclic aromatic hydrocarbon skeleton is not particularly limited as long as it has a structure derived from a monocyclic aromatic hydrocarbon, but is preferably a 4- to 7-membered aromatic hydrocarbon ring, and more preferably a 6-membered aromatic hydrocarbon ring, i.e., a benzene ring. Furthermore, the monocyclic aromatic hydrocarbon is preferably a 4- to 7-membered aromatic hydrocarbon, and more preferably a 6-membered ring, i.e., a benzene ring. When the polycyclic phenyl group has two or more monocyclic aromatic hydrocarbon skeletons (i.e., unsaturated hydrocarbon rings that independently exhibit aromaticity), it is not particularly limited as long as it does not form a fused-ring aromatic hydrocarbon skeleton (i.e., two or more unsaturated hydrocarbon rings that independently exhibit aromaticity). Generally, when the polycyclic phenyl group has two or more monocyclic aromatic hydrocarbon skeletons, the monocyclic aromatic hydrocarbon skeletons (i.e., unsaturated hydrocarbon rings that independently exhibit aromaticity) are preferably linked by a linking group to form a polycyclic phenyl group. The linking group is preferably a single bond or another divalent or higher hydrocarbon group as described above, more preferably a single bond or a divalent or higher aliphatic hydrocarbon group, even more preferably a single bond or a divalent aliphatic hydrocarbon group, still more preferably a single bond or an alkylene group, and particularly preferably a single bond or a chain alkylene group. In the embodiment where the polycyclic phenyl group has two or more aromatic hydrocarbon skeletons of a monocyclic structure (i.e., unsaturated hydrocarbon rings that independently exhibit aromaticity), the number of independently aromatic unsaturated hydrocarbon rings that the polycyclic phenyl group has is preferably 2 to 6, more preferably 2 to 4, and even more preferably 3 to 4.

[0022] The aromatic hydrocarbon skeleton of the fused ring structure is not particularly limited as long as it is a structure exhibiting aromaticity formed by the fusion of two or more unsaturated hydrocarbon rings, but is preferably a structure derived from a fused ring aromatic hydrocarbon in which aromatic hydrocarbons of a monocyclic structure are fused, more preferably a structure derived from a fused ring aromatic hydrocarbon in which aromatic hydrocarbon rings of a 4- to 7-membered ring structure are fused, and even more preferably a structure derived from a fused ring aromatic hydrocarbon in which a 6-membered aromatic hydrocarbon ring (i.e., a benzene ring) is fused. Preferred examples of the fused ring aromatic hydrocarbon (i.e., aromatic hydrocarbon skeleton with a fused ring structure) include structures in which only 6-membered aromatic hydrocarbon rings are fused, such as naphthalene, anthracene, pentacene, benzopyrene, chrysene, pyrene, triphenylene, corannulene, coronene, ovalene, and kekulene; and structures in which a 5-membered unsaturated hydrocarbon ring and a 7-membered unsaturated hydrocarbon ring are fused, such as azulene. Among these, those containing a structure derived from a 6-membered aromatic hydrocarbon ring are more preferred, and those having a structure in which only 6-membered aromatic hydrocarbon rings are fused are even more preferred. In particular, the aromatic hydrocarbon skeleton of the fused ring structure is preferably a structure in which 2 to 12 benzene rings are fused, more preferably a structure in which 2 to 5 benzene rings are fused, and even more preferably a structure in which 2 benzene rings are fused. When the polycyclic phenyl group has an aromatic hydrocarbon skeleton with a fused ring structure (i.e., a structure exhibiting aromaticity formed by condensing two or more unsaturated hydrocarbon rings), the number of aromatic hydrocarbon skeletons with a fused ring structure that the polycyclic phenyl group has is preferably 1 to 3, and more preferably 1.

[0023] Above A 1 The polycyclic phenyl group represented by the formula (I) is preferably a monovalent group. The polycyclic phenyl group may be bonded to the oxygen atom in formula (1) through a carbon atom constituting the aromatic ring skeleton (i.e., an unsaturated hydrocarbon ring that exhibits aromaticity alone or through condensed rings), or may be bonded to the oxygen atom in formula (1) through a carbon atom constituting another hydrocarbon group other than the aromatic ring skeleton, such as an aliphatic hydrocarbon group such as an alkyl group or an alkylene group.

[0024] Above A 1 The polycyclic phenyl group represented by the formula (I) may have a substituent, but the substituent is a nonionic substituent. That is, the polycyclic phenyl group does not have an anionic group. The nonionic substituent refers to a nonionic substituent, and specifically includes polyalkylene glycol groups such as polyethylene glycol groups and polypropylene glycol groups; halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms; hydroxyl groups; alkyl ether groups such as methoxy groups, ethoxy groups, propoxy groups, and butoxy groups (preferably C 1-4 alkoxy group; aryl ether group such as phenoxy group, naphthoxy group (preferably C 6-15 aryloxy group; acyl groups such as acetyl group and benzoyl group (preferably alkylcarbonyl groups in which the alkyl group has 1 to 4 carbon atoms, and arylcarbonyl groups in which the aryl group has 6 to 15 carbon atoms), and the like.

[0025] The nonionic substituent may be directly bonded to the aromatic ring skeleton constituting the polycyclic phenyl group (i.e., an unsaturated hydrocarbon ring that exhibits aromaticity either alone or as a condensed ring), or may be bonded to a hydrocarbon group other than the aromatic ring skeleton (for example, the aliphatic hydrocarbon group such as an alkyl group or alkylene group). In particular, the nonionic substituent bonded to a hydrocarbon group other than the aromatic ring skeleton (for example, the aliphatic hydrocarbon group such as an alkyl group or an alkylene group) is preferably a halogen atom, a hydroxyl group, an alkyl ether group, an aryl ether group, or an acyl group. 1-4 Alkoxy group, C 6-15More preferred are aryloxy groups, alkylcarbonyl groups in which the alkyl group has 1 to 4 carbon atoms, and arylcarbonyl groups in which the aryl group has 6 to 15 carbon atoms. Of the halogen atoms, chlorine, bromine, and fluorine atoms are preferred, with chlorine atoms being more preferred.

[0026] Above A 1 Examples of the polycyclic phenyl group represented by the formula: Preferably, the hydrocarbon group A1 has two or more benzene rings which may have a monovalent aliphatic hydrocarbon group, and each benzene ring is linked by a single bond or a divalent aliphatic hydrocarbon group, and any one of the benzene rings is bonded to the oxygen atom in formula (1) directly or via a divalent aliphatic hydrocarbon group, or the hydrocarbon group B1 has one fused ring in which 2 to 12 benzene rings are fused, and the fused ring may have a monovalent aliphatic hydrocarbon group, and the fused ring is bonded to the oxygen atom in formula (1) directly or via a divalent aliphatic hydrocarbon group; more preferably, the hydrocarbon group A2 has 2 to 6 benzene rings which may have an alkyl group, each benzene ring being linked by a single bond or an alkylene group, and any one of the benzene rings is bonded to the oxygen atom in formula (1) directly or via a divalent alkylene group, or has one fused ring in which 2 to 5 benzene rings are fused, and the fused ring may have an alkyl group, and the fused ring is bonded to the oxygen atom in formula (1) directly or via an alkylene group; It is more preferred that the hydrocarbon group A3 has 2 to 6 benzene rings which may have an alkyl group having a chain structure, and each benzene ring is linked by a single bond or an alkylene group having a chain structure, and any one of the benzene rings is bonded to the oxygen atom in formula (1) directly or via a divalent alkylene group having a chain structure, or that the hydrocarbon group B3 has one fused ring in which 2 to 5 benzene rings are fused, and the fused ring may have an alkyl group having a chain structure, and the fused ring is bonded to the oxygen atom in formula (1) directly or via an alkylene group having a chain structure. The hydrocarbon group A1, hydrocarbon group B1, hydrocarbon group A2, hydrocarbon group B2, hydrocarbon group A3, and hydrocarbon group B3 may each have the nonionic substituents exemplified above, but it is preferable that they do not have any of the nonionic substituents.

[0027] Above A 1 The polycyclic phenyl group represented by the formula (I) is more preferably at least one selected from the group consisting of structures represented by the following formulas (1-a) to (1-f).

[0028] [ka]

[0029] In the above formula (1-a), R 1 and R 2 each independently represents a hydrogen atom or a monovalent aliphatic hydrocarbon group, and R 3 Each of the symbols independently represents a monovalent aliphatic hydrocarbon group. Furthermore, k represents an integer of 1 to 5, and p represents an integer of 0 to 4. k+p is an integer of 1 to 5. * represents "(OA 2 ) n " represents the bonding site with the terminal O (oxygen atom) in ".

[0030] R 1 , R 2 , and R 3 Examples of the monovalent aliphatic hydrocarbon group represented by the formula (I) include the monovalent aliphatic hydrocarbon groups described above (for example, alkyl groups, alkenyl groups, and alkynyl groups), of which an alkyl group is preferred, an alkyl group having 1 to 18 carbon atoms is more preferred, an alkyl group having 1 to 12 carbon atoms is even more preferred, an alkyl group having 1 to 6 carbon atoms is still more preferred, and an alkyl group having 1 to 3 carbon atoms is particularly preferred. Furthermore, the above k is preferably 1 to 3, and more preferably 2 to 3. The above p is preferably 0 to 1. The above alkyl group is preferably an alkyl group having a chain structure, and the preferred range of the number of carbon atoms in the alkyl group having a chain structure is the same as the preferred range of the number of carbon atoms in the above alkyl group.

[0031] In formula (1-a), R 1 and R 2 is a hydrogen atom or an alkyl group, and R 3 is preferably an alkyl group, k is an integer of 1 to 5, and p is an integer of 0 to 4 (wherein k+p is an integer of 1 to 5), R 1 is a hydrogen atom, and R 2 is an alkyl group, and R 3 is an alkyl group, k is an integer of 1 to 3, and p is an integer of 0 to 1, R 1 is a hydrogen atom, and R 2 C 1-3 is an alkyl group, and R 3 C 1-12 It is more preferable that the group is an alkyl group, k is an integer of 1 to 3, and p is an integer of 0 to 1.

[0032] [ka]

[0033] In the above formula (1-b), R 1 , R 2 , R 3 , k, p, and * respectively represent R 1 , R 2 , R 3 , k, p, and *, including preferred forms. 4 represents a divalent aliphatic hydrocarbon group.

[0034] R 4Examples of the divalent aliphatic hydrocarbon group represented by the formula (I) include the divalent aliphatic hydrocarbon groups explained above (for example, alkylene groups, divalent saturated alicyclic hydrocarbon groups, etc.), and among these, alkylene groups are preferred, alkylene groups having 1 to 18 carbon atoms are more preferred, alkylene groups having 1 to 12 carbon atoms are even more preferred, alkylene groups having 1 to 6 carbon atoms are still more preferred, and alkylene groups having 1 to 3 carbon atoms are particularly preferred.

[0035] In formula (1-b), R 1 and R 2 is a hydrogen atom or an alkyl group, and R 3 is an alkyl group, and R 4 is preferably an alkylene group, k is an integer of 1 to 5, and p is an integer of 0 to 4 (wherein k+p is an integer of 1 to 5), R 1 is a hydrogen atom, and R 2 is an alkyl group, and R 3 is an alkyl group, and R 4 is an alkylene group, k is an integer of 1 to 3, and p is an integer of 0 to 1, R 1 is a hydrogen atom, and R 2 C 1-3 is an alkyl group, and R 3 C 1-12 is an alkyl group, and R 4 C 1-12 It is more preferable that the group is an alkylene group, k is an integer of 1 to 3, and p is an integer of 0 to 1.

[0036] [ka]

[0037] In the above formula (1-c), R 5 and R 6 each independently represents a monovalent aliphatic hydrocarbon group. q represents an integer of 0 to 3, and r represents an integer of 0 to 4. * represents "(OA 2 )n " represents the bonding site with the terminal O (oxygen atom) in ".

[0038] Above R 5 and R 6 Examples of the monovalent aliphatic hydrocarbon group represented by the formula (I) include the monovalent aliphatic hydrocarbon groups explained above (for example, alkyl groups, alkenyl groups, and alkynyl groups), of which an alkyl group is preferred, an alkyl group having 1 to 18 carbon atoms is more preferred, an alkyl group having 1 to 12 carbon atoms is even more preferred, an alkyl group having 1 to 6 carbon atoms is still more preferred, and an alkyl group having 1 to 3 carbon atoms is particularly preferred. Furthermore, the above q is preferably 0 to 1. The above r is preferably 0 to 1. The above alkyl group is preferably an alkyl group having a chain structure, and the preferred range of the number of carbon atoms in the alkyl group having a chain structure is the same as the preferred range of the number of carbon atoms in the above alkyl group.

[0039] In formula (1-c), R 5 and R 6 are each independently an alkyl group, q is an integer of 0 to 3, and r is an integer of 0 to 4, R 5 and R 6 However, independently, C 1-12 It is more preferable that the group is an alkyl group, q is 0 or 1, and r is 0 or 1.

[0040] [ka]

[0041] In the above formula (1-d), R 5 , R 6 , q, r, and * are R in the above formula (1-c), respectively. 5 , R 6 , q, r, and *, including preferred forms. 7 represents a divalent aliphatic hydrocarbon group.

[0042] R7 Examples of the divalent aliphatic hydrocarbon group represented by the formula (I) include the divalent aliphatic hydrocarbon groups explained above (for example, alkylene groups, divalent saturated alicyclic hydrocarbon groups, etc.), and among these, alkylene groups are preferred, alkylene groups having 1 to 18 carbon atoms are more preferred, alkylene groups having 1 to 12 carbon atoms are even more preferred, alkylene groups having 1 to 6 carbon atoms are still more preferred, and alkylene groups having 1 to 3 carbon atoms are particularly preferred.

[0043] In formula (1-d), R 5 and R 6 are each independently an alkyl group, and R 7 is preferably an alkylene group, q is an integer of 0 to 3, and r is an integer of 0 to 4; R 5 and R 6 However, independently, C 1-12 is an alkyl group, and R 7 C 1-12 It is more preferable that the group is an alkylene group, q is 0 or 1, and r is 0 or 1.

[0044] [ka]

[0045] In the above formula (1-e), R 8 each independently represents a monovalent aliphatic hydrocarbon group. s represents an integer of 0 to 4, and j represents an integer of 1 to 5. s+j is an integer of 1 to 5. * represents "(OA 2 ) n " represents the bonding site with the terminal O (oxygen atom) in ".

[0046] Above R 8Examples of the monovalent aliphatic hydrocarbon group represented by the formula (I) include the monovalent aliphatic hydrocarbon groups explained above (for example, alkyl groups, alkenyl groups, and alkynyl groups), of which alkyl groups are preferred, more preferably alkyl groups having 1 to 18 carbon atoms, even more preferably alkyl groups having 1 to 12 carbon atoms, still more preferably alkyl groups having 1 to 6 carbon atoms, and particularly preferably alkyl groups having 1 to 3 carbon atoms. Furthermore, the above s is preferably 0 to 1. The above j is preferably 1 to 3. The above alkyl group is preferably an alkyl group having a chain structure, and the preferred range of the number of carbon atoms in the alkyl group having a chain structure is the same as the preferred range of the number of carbon atoms in the above alkyl group.

[0047] In formula (1-e), R 8 is preferably an alkyl group, s is an integer of 0 to 4, and j is an integer of 1 to 5 (wherein s+j is an integer of 1 to 5); R 8 is an alkyl group, s is 0 or 1, and j is an integer of 1 to 3, R 8 C 1-12 It is more preferable that the group is an alkyl group, s is 0 or 1, and j is an integer of 1 to 3.

[0048] [ka]

[0049] In the above formula (1-f), R 8 , s, j, and * are R in the above formula (1-e), respectively. 8 , s, j, and *, including preferred forms. 9 represents a divalent aliphatic hydrocarbon group.

[0050] R 9Examples of the divalent aliphatic hydrocarbon group represented by the formula (I) include the divalent aliphatic hydrocarbon groups explained above (for example, alkylene groups, divalent saturated alicyclic hydrocarbon groups, etc.), and among these, alkylene groups are preferred, alkylene groups having 1 to 18 carbon atoms are more preferred, alkylene groups having 1 to 12 carbon atoms are even more preferred, alkylene groups having 1 to 6 carbon atoms are still more preferred, and alkylene groups having 1 to 3 carbon atoms are particularly preferred.

[0051] In formula (1-f), R 8 is an alkyl group, and R 9 is preferably an alkylene group, s is an integer of 0 to 4, and j is an integer of 1 to 5 (wherein s+j is an integer of 1 to 5); R 8 is an alkyl group, and R 9 is an alkylene group, s is 0 or 1, and j is an integer of 1 to 3, R 8 C 1-12 is an alkyl group, and R 9 C 1-12 It is more preferable that the group is an alkylene group, s is 0 or 1, and j is an integer of 1 to 3.

[0052] Above A 1 The polycyclic phenyl group represented by the formula (1-a) is preferably at least one selected from the group consisting of the structures represented by the formulas (1-a) to (1-f) above, and more preferably the structure represented by the formula (1-a).

[0053] The polymer of the present disclosure has, in its side chain, a structure derived from the polymerizable monomer (M), represented by X in formula (1). 1 Structures other than A 1 -(OA 2 ) n Therefore, the polymer of the present disclosure has excellent adhesion to polyolefin substrates. In particular, the adhesion to the substrate is improved by the structure of the terminal portion of the side chain of the polymer, particularly A 1 -(OA 2)2- (hereinafter also referred to as the terminal structure) is thought to contribute significantly. The present inventors have focused on a calculation method for estimating the adhesion of a polymer to a substrate, using the Gaussian16 program manufactured by Gaussian, applying B3LYP as the functional of the density functional theory, 6-31G (d, p) as the basis function, and dispersion force correction (GD3BJ keyword). In this calculation method, the zero-point energy of the terminal structure of the side chain of the polymer of the present disclosure is substituted with the zero-point energy of a molecule having a structure similar to the terminal structure, specifically, a molecule represented by the following formula (1-1) (hereinafter also referred to as the structural molecule (Ip)). The inventors have found that there is a correlation between the magnitude of the difference between the absolute value of the zero-point energy of the structural molecule (Ip) and the absolute value of the zero-point energy of the aggregate of the structural molecule (Ip) and the substrate molecule, obtained by this calculation method, and the adhesion of the polymer of the present disclosure to a substrate.

[0054] [ka]

[0055] In the above formula, A 1 and A 2 are the A in equation (1), respectively. 1 and A 2 is the same as

[0056] Specifically, the structure derived from the polymerizable monomer (M) contained in the polymer of the present disclosure preferably satisfies the following formula (f1-1). (E M +E P8 )-(E MP )<-80kJ / mol (f1-1) In the above formula (f1-1), E M is the absolute value of the zero-point energy of the above structural molecule (Ip), E P8 is the absolute value of the zero-point energy of the propylene octamer, E MP is the absolute value of the zero-point energy of the association of the structural molecule (Ip) and the propylene octamer.

[0057] Here, the structural molecule (Ip) has a structure represented by the formula (1-1). 1 is A in the above formula (1) 1 and (OA 2 )2 is A in the above formula (1). 1 Directly bonded to consecutive (OA 2 )2 in formula (1-1). 2 )2 is a formula (1) A 1 -(OA 2 )2-(OA 2 ) n-2 -OX 1 When rewritten as (OA 2 )2. The zero-point energy of the aggregate means the zero-point energy when the structural molecule (Ip) (structural molecule represented by the formula (1-1)) and the propylene octamer are present in the same space. The zero-point energies in formula (f1-1) are calculated using the Gaussian16 program manufactured by Gaussian, with B3LYP as the density functional, 6-31G(d,p) as the basis function, and dispersion force correction (GD3BJ keyword) applied. Since the zero-point energies calculated by this calculation method are negative values, the absolute values ​​of the zero-point energies are used in formula (f1-1) above. The same applies to the zero-point energies in formulas (f1-2), (f2-1), and (f2-2) described below.

[0058] The above formula (f1-1) is the absolute value of the zero-point energy (E M ) and the absolute value of the zero-point energy of the propylene octamer (E P8 ) and the absolute value of the zero-point energy of the association of the structural molecule (Ip) and the propylene octamer (E MP ) means that the difference d1 is less than -80kJ / mol.

[0059] The absolute value of the zero-point energy of the above structure molecule (Ip) (E M When the difference d1 satisfies the above formula (f1-1), the polymer (Pm) having as a structural unit a structure derived from the polymerizable monomer (M) having the corresponding terminal structure tends to have better adhesion to polyolefin substrates, particularly polypropylene substrates. The difference d1 is preferably -85 kJ / mol or less, more preferably -90 kJ / mol or less.

[0060] It is also preferable that the structure derived from the polymerizable monomer (M) contained in the polymer of the present disclosure satisfies the following formula (f1-2). (E M +E P8 )-(E MP )<(E P6 +E P8 )-(E PP ) (f1-2) In the above formula (f1-2), E M , E P8 , and E MP are the E in the above formula (f1-1), M , E P8 , and E MP It has the same meaning as and is calculated in the same way. In the above formula (f1-2), E P6 is the absolute value of the zero-point energy of the propylene hexamer, E PP is the absolute value of the zero-point energy of the association complex of the propylene octamer and the propylene hexamer. The zero-point energy of the association complex of the propylene octamer and the propylene hexamer means the zero-point energy when the propylene octamer and the propylene hexamer are in the same space.

[0061] The above formula (f1-2) is the absolute value of the zero-point energy (E M ) and the absolute value of the zero-point energy of the propylene octamer (E P8 ) and the absolute value of the zero-point energy of the association of the structural molecule (Ip) and the propylene octamer (E MP) and the difference d1 is the absolute value of the zero-point energy of the propylene hexamer (E P6 ) and the absolute value of the zero-point energy of the propylene octamer (E P8 ) and the absolute value of the zero-point energy of the association of the propylene hexamer and the propylene octamer (E PP ) is smaller than the difference d2 (a negative value means it is larger).

[0062] In the polymer of the present disclosure, the absolute value of the zero-point energy (E M ) satisfies the above relational formula (f1-2), a polymer having, as a constituent unit, a structure derived from a polymerizable monomer (M) having a corresponding terminal structure tends to have better adhesion to polyolefin substrates, particularly polypropylene substrates. In the above relational expression (f1-2), the difference (d1-d2) between the difference d1 and the difference d2 is preferably −15 kJ / mol or less, and more preferably −20 kJ / mol or less.

[0063] Above X 1 The group having an ethylenically unsaturated double bond represented by the formula (I) is not particularly limited, but is preferably a radically polymerizable group, such as a (meth)acryloyl group, a vinyl group, a styryl group, an allyl group, etc. Among these, a (meth)acryloyl group is preferred from the viewpoint of increasing the polymerization rate.

[0064] A in the above formula (1) 2 represents an alkylene chain having 1 to 10 carbon atoms, and the alkylene chain may have a substituent. 2 may be the same or different, but are preferably the same.

[0065] Above A 2 Examples of the alkylene chain represented by the formula include the groups explained above as the alkylene group. The number of carbon atoms in the alkylene chain is preferably 1 to 3, and more preferably 2. In particular, the alkylene chain is preferably an ethylene-1,1-diyl group.

[0066] The substituent that the alkylene chain may have is not particularly limited, and examples thereof include a halogen atom, a polar functional group, an alkoxy group, and a thioalkoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a chlorine atom, a bromine atom, and a fluorine atom are preferred, and a fluorine atom is more preferred. Preferred examples of the polar functional group include a hydroxyl group, a carboxyl group, an amino group, and a mercapto group. The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, and even more preferably an alkoxy group having 1 carbon atom, ie, a methoxy group. The above thioalkoxy group is, for example, preferably a thioalkoxy group having 1 to 10 carbon atoms, more preferably a thioalkoxy group having 1 to 4 carbon atoms, and even more preferably a thioalkoxy group having 1 carbon atom, ie, a thiomethoxy group.

[0067] In the above formula (1), n ​​is not particularly limited as long as it is an integer of 3 to 100, but is preferably 4 to 30.

[0068] The polymerizable monomer (M) is 1 The polycyclic phenyl group represented by the formula (1-a) to (1-f) is preferably one having any of the structures represented by the formula (1-a) to (1-f), and in addition, the polycyclic phenyl group represented by the formula (1-a) to (1-f) is preferably one having any of the structures represented by the formula (1-a) to (1-f), 2 It is more preferable that the alkylene chain represented by the formula (I) is an alkylene chain having 1 to 3 carbon atoms, and in addition to these, the above-mentioned X 1 It is particularly preferred that the group having an ethylenically unsaturated double bond represented by the formula (I) is a (meth)acryloyl group.

[0069] The polymerizable monomer (M) also contains the above-mentioned A 1 Preferably, the terminal structure containing the polycyclic phenyl group represented by the formula (f1-1) and / or the formula (f1-2) satisfies the relationship represented by the formula (f1-1) and / or the formula (f1-2), and in addition, the terminal structure containing the polycyclic phenyl group represented by the formula (f1-2) satisfies the relationship represented by the formula (f1-1) and / or the formula (f1-2), and 2It is more preferable that the alkylene chain represented by the formula (I) is an alkylene chain having 1 to 3 carbon atoms, and in addition to these, the above-mentioned X 1 It is particularly preferred that the group having an ethylenically unsaturated double bond represented by the following formula is a (meth)acryloyl group.

[0070] The polymerizable monomer (M) can be produced by the same production method as that described in <Production Method of Compound> in "7. Compound" below. Therefore, the description of the production method of the polymerizable monomer (M) can be applied mutatis mutandis to the description of the production method described in <Production Method of Compound>, and will not be repeated here.

[0071] <Polymer (Pm) composition, properties, etc.> The polymer (Pm) of the present disclosure may be a polymer containing only the structure (M) as a constituent unit, or may be a polymer containing a structure other than the structure (M) as a constituent unit. From the viewpoint of adjusting the hardness of the polymer (Pm), the polymer (Pm) is preferably a polymer containing the structure (M) and a structure other than the structure (M) as a constituent unit.

[0072] The other structure is not particularly limited, but is preferably a structure derived from at least one monomer selected from the group consisting of a (meth)acrylic monomer and a styrene-based monomer. The polymer (Pm) of the present disclosure may contain a structure derived from a (meth)acrylic monomer and a structure derived from a styrene-based monomer as constituent units. That is, the polymer (Pm) of the present disclosure is preferably a (meth)acrylic polymer containing, as structural units, the structure (M) and a structure derived from a (meth)acrylic monomer (but excluding a structure derived from a styrene monomer); a styrene polymer containing, as structural units, the structure (M) and a structure derived from a styrene monomer (but excluding a structure derived from a (meth)acrylic monomer); or a (meth)acrylic-styrene polymer containing, as structural units, the structure (M), a structure derived from a (meth)acrylic monomer, and a structure derived from a styrene monomer, with a (meth)acrylic polymer being more preferred.

[0073] The polymer (Pm) of the present disclosure contains the above structure (M) as a structural unit, and preferably contains a plurality of the above structure (M) as a structural unit, and more preferably contains a plurality of the above structure (M) as a repeating structural unit. When the polymer (Pm) contains a plurality of structures (M) as structural units, the plurality of structures (M) may be the same or different.

[0074] The content of structure (M) in polymer (Pm) of the present disclosure is not particularly limited, but the content of structure (M) in 100% by mass of polymer (Pm) is preferably 1 to 100% by mass, more preferably 2 to 80% by mass, even more preferably 4 to 50% by mass, and even more preferably 5 to 50% by mass.

[0075] The (meth)acrylic monomer is not particularly limited, and one or more types may be selected from conventionally known (meth)acrylic acid esters and (meth)acrylic acids and used. The total content of the structure (M) and the structure derived from a (meth)acrylic monomer in the polymer (Pm) of the present disclosure is not particularly limited, but is, for example, 30 to 100% by mass, preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, still more preferably 90% by mass or more, and particularly preferably 95% by mass or more, based on 100% by mass of the polymer (Pm). In particular, it is more preferable to adjust the total content of the structure (M), the structure derived from a linear (meth)acrylic acid ester described below, the structure derived from a branched (meth)acrylic acid ester described below, the structure derived from a (meth)acrylic acid ester having a cyclic aliphatic hydrocarbon group described below, and the structure derived from an acid group-containing monomer described below, within the above range. It is even more preferable to adjust the total content of the structure (M), the structure derived from a low Tg (meth)acrylic acid alkyl ester described below, the structure derived from a (meth)acrylic acid ester having a cyclic aliphatic hydrocarbon group described below, and the structure derived from an acid group-containing monomer described below, within the above range.

[0076] Examples of the (meth)acrylic acid ester include (meth)acrylic acid esters having a linear alkyl group, (meth)acrylic acid esters having a cyclic aliphatic hydrocarbon group, (meth)acrylic acid esters having a branched alkyl group, and (meth)acrylic acid esters having an aromatic hydrocarbon group, and the like, of which (meth)acrylic acid esters having a linear alkyl group, (meth)acrylic acid esters having a cyclic aliphatic hydrocarbon group, and (meth)acrylic acid esters having a branched alkyl group are preferred. Furthermore, the (meth)acrylic acid ester may be either a monofunctional (meth)acrylic acid ester or a polyfunctional (meth)acrylic acid ester, but monofunctional (meth)acrylic acid esters are preferred.

[0077] Examples of the (meth)acrylic acid ester having a linear alkyl group include: linear alkyl (meth)esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, n-decyl (meth)acrylate, lauryl (meth)acrylate, n-tridecyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, and behenyl (meth)acrylate; (meth)acrylic acid esters having a linear alkyl ether group, such as methoxyethyl (meth)acrylate, ethyl carbitol (meth)acrylate, and ethoxy polyethylene glycol (meth)acrylate; amino group-containing linear alkyl (meth)acrylates such as aminoethyl (meth)acrylate; Examples include halogen atom-containing linear alkyl (meth)acrylates such as chloroethyl (meth)acrylate, trifluoroethyl (meth)acrylate, and heptadecafluorooctylethyl (meth)acrylate.

[0078] From the viewpoint of adhesion and scratch resistance, the (meth)acrylic acid ester having a linear alkyl group is preferably a linear alkyl (meth)acrylic acid ester, more preferably methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, n-decyl (meth)acrylate, lauryl (meth)acrylate, n-tridecyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, or behenyl (meth)acrylate, and even more preferably methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, n-octyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, or behenyl (meth)acrylate.

[0079] Examples of the (meth)acrylic acid ester having a cyclic aliphatic hydrocarbon group include: cycloalkyl (meth)acrylates such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, and t-butylcyclohexyl (meth)acrylate; Esters of (meth)acrylic acid and polycyclic alcohols such as isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and dicyclopentenyl (meth)acrylate; and the like. Among these, cycloalkyl (meth)acrylate and isobornyl (meth)acrylate are preferred, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate and isobornyl (meth)acrylate are more preferred, cyclohexyl (meth)acrylate and isobornyl (meth)acrylate are even more preferred, and cyclohexyl methacrylate and isobornyl acrylate are even more preferred.

[0080] Examples of the (meth)acrylic acid ester having a branched alkyl group include: branched alkyl (meth)acrylates such as isopropyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, neopentyl (meth)acrylate, 2-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, and isostearyl (meth)acrylate; alkoxy group-containing branched alkyl (meth)acrylates such as 3-methoxybutyl (meth)acrylate and methoxytripropylene glycol (meth)acrylate; Examples include halogen atom-containing branched alkyl (meth)acrylates such as hexafluoroisopropyl (meth)acrylate; and the like. Among these, branched alkyl (meth)acrylates are preferred. From the viewpoint of adhesion and scratch resistance, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, neopentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-octyl (meth)acrylate, isodecyl (meth)acrylate, and isostearyl (meth)acrylate are preferred, and isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-octyl (meth)acrylate, and isostearyl (meth)acrylate are more preferred.

[0081] Examples of the (meth)acrylic acid ester having an aromatic hydrocarbon group include: aryl (meth)acrylates such as phenyl (meth)acrylate and naphthyl (meth)acrylate; aralkyl (meth)acrylates such as benzyl (meth)acrylate and phenethyl (meth)acrylate; and the like.

[0082] These (meth)acrylic acid esters may be used alone or in combination of two or more kinds.

[0083] In particular, from the viewpoint of further enhancing adhesion to polyolefin substrates, the (meth)acrylic acid ester preferably includes a (meth)acrylic acid alkyl ester having a homopolymer glass transition temperature (Tg) of −20° C. or lower (hereinafter, sometimes referred to as a low-Tg (meth)acrylic acid alkyl ester) and / or a (meth)acrylic acid ester having a cyclic aliphatic hydrocarbon group, and more preferably includes a low-Tg (meth)acrylic acid alkyl ester and a (meth)acrylic acid ester having a cyclic aliphatic hydrocarbon group.

[0084] In this specification, the "glass transition temperature of a homopolymer" may be, for example, the value (if multiple Tg values ​​are listed, the lowest value) described in "POLYMER HANDBOOK THIRD EDITION" (by J. BRANDRUP and EHIMMERGUT, 1989, published by John Wiley & Sons, Inc., pp. VI / 209-VI / 277). For compounds not described in "POLYMER HANDBOOK THIRD EDITION," a value (calculated value) determined by computer using commercially available glass transition temperature calculation software (e.g., "MATERIALS STUDIO" manufactured by Accelrys Software Inc., version 4.0.0.0, module: Synthia, calculation conditions: weight average molecular weight 100,000) may be used.

[0085] The Tg of the low Tg (meth)acrylic acid alkyl ester is −20° C. or lower, preferably −100 to −20° C., and more preferably −80 to −30° C. Examples of the low Tg (meth)acrylic acid alkyl ester include ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-octyl acrylate, 2-ethylhexyl acrylate, n-nonyl acrylate, and isononyl acrylate, and among these, n-butyl acrylate, 2-octyl acrylate, and 2-ethylhexyl acrylate are preferred.

[0086] The content of the structure derived from the low Tg (meth)acrylic acid alkyl ester in the polymer (Pm) of the present disclosure is preferably adjusted so that the Tg of the polymer (Pm) falls within the range described below. For example, the content of the structure derived from the low Tg (meth)acrylic acid alkyl ester in the polymer (Pm) is preferably 2 to 80 mass%, more preferably 10 to 50 mass%, and even more preferably 15 to 30 mass%, based on 100 mass% of the polymer (Pm).

[0087] In the polymer (Pm) of the present disclosure, the content of the structure derived from the (meth)acrylic acid ester having a cyclic aliphatic hydrocarbon group is preferably 5 to 90 mass %, more preferably 15 to 85 mass %, even more preferably 30 to 80 mass %, and particularly preferably 50 to 80 mass %, based on 100 mass % of the polymer (Pm). In particular, it is preferable to adjust the total content of the structure derived from the cycloalkyl (meth)acrylate and the structure derived from isobornyl (meth)acrylate to fall within the above range.

[0088] As the (meth)acrylic monomer, (meth)acrylic acid can be preferably used as an acid group-containing monomer, but acid group-containing monomers other than (meth)acrylic acid can also be preferably used. That is, the polymer (Pm) may further contain a structure derived from an acid group-containing monomer as a constituent unit. When the polymer (Pm) contains a structure derived from an acid group-containing monomer as a constituent unit, the dispersion stability of resin particles containing the polymer (Pm) in an aqueous dispersion can be improved. Examples of the acid group-containing monomer include unsaturated monocarboxylic acids such as (meth)acrylic acid and crotonic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid and citraconic acid; anhydrides of unsaturated dicarboxylic acids such as maleic anhydride; monoesters of unsaturated dicarboxylic acids such as maleic acid monomethyl ester, maleic acid monobutyl ester, itaconic acid monomethyl ester and itaconic acid monobutyl ester; and carboxyl group-containing aliphatic monomers such as vinylbenzoic acid; however, the present invention is not limited to these examples. These acid group-containing monomers may be used alone or in combination of two or more. Among these acid group-containing monomers, from the viewpoint of improving dispersion stability, adhesion, and scratch resistance in an aqueous dispersion when the polymer (Pm) is made into emulsion particles, unsaturated monocarboxylic acids and unsaturated dicarboxylic acids are preferred, acrylic acid, methacrylic acid, and itaconic acid are more preferred, and acrylic acid and methacrylic acid are even more preferred.

[0089] In the polymer (Pm) of the present disclosure, the content of the structure derived from an acid group-containing monomer (particularly (meth)acrylic acid) is preferably 0.5 to 10 mass %, more preferably 1 to 8 mass %, and even more preferably 3 to 5 mass %, based on 100 mass % of the polymer (Pm).

[0090] The styrene-based monomer is not particularly limited, but may be an alkyl group (e.g., a methyl group, a tert-butyl group, or the like) 1-4 alkyl group), nitro group, nitrile group, alkoxyl group (e.g., methoxy group, ethoxy group, etc.) 1-4 alkoxyl group), acyl group (for example, an alkylcarbonyl group having 1 to 4 carbon atoms in the alkyl group such as an acetyl group), sulfone group, hydroxyl group, halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), vinyl group, alkoxysilyl group (for example, a tri-C such as a trimethoxysilyl group or a triethoxysilyl group), 1-4 Examples of the functional group include styrene which may have a functional group such as an alkoxysilyl group. The position of the functional group is not particularly limited, but it is preferably directly bonded to the benzene ring. Specific examples of the styrene-based monomer include monofunctional styrene-based monomers such as styrene, α-methylstyrene, vinyltoluene (e.g., p-methylstyrene), tert-methylstyrene, chlorostyrene, and 2-styrylethyltrimethoxysilane. Furthermore, polyfunctional styrene-based monomers can also be used as the styrene-based monomer. A preferred example of the polyfunctional styrene-based monomer is divinylbenzene. These styrene-based monomers may be used alone or in combination of two or more kinds. As the styrene-based monomer, styrene is preferred from the viewpoint of enhancing water resistance.

[0091] When the polymer (Pm) of the present disclosure contains a structure derived from a styrene-based monomer (preferably a (meth)acrylic-styrene-based polymer), the content of the structure derived from a styrene-based monomer is not particularly limited, but is preferably 1 to 70 mass %, more preferably 5 to 50 mass %, and even more preferably 10 to 30 mass %, relative to 100 mass % of the polymer (Pm).

[0092] The polymer (Pm) of the present disclosure may also contain structural units derived from a monomer other than the polymerizable monomer (M), (meth)acrylic acid ester, acid group-containing monomer, and styrene-based monomer (hereinafter, sometimes referred to as monomer Q). vinyl group-containing silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; Epoxy group-containing silane coupling agents such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; Epoxy group-containing vinyl monomers such as allyl glycidyl ether; vinyl lactam monomers such as N-methylvinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinylpyrrolidone, N-vinyl-2-pyrrolidone, and N-(meth)acryloylpyrrolidone; Maleimide-based monomers such as maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide; addition-polymerizable oxazolines such as 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, and 2-isopropenyl-5-ethyl-2-oxazoline; (Meth)acrylonitrile; (meth)acrylamide-based monomers such as (meth)acrylamide, N-monomethyl(meth)acrylamide, N-monoethyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, and Nn-propyl(meth)acrylamide; vinyl monomers such as vinyl acetate, vinyl chloride, and vinyl benzoate; Olefin monomers such as ethylene and propylene; and the like.

[0093] The content of the structure derived from the monomer (Q) is preferably 30% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 0% by mass, based on 100% by mass of the polymer (Pm).

[0094] The polymer (Pm) of the present disclosure is a polymerizable monomer (M) constituting the polymer (Pm), wherein X 1 is a (meth)acryloyl group, and the polymer (Pm) is more preferably a copolymer of the monomer (M1) with a (meth)acrylic monomer and / or a styrene-based monomer, and even more preferably a copolymer of the monomer (M1), a (meth)acrylic monomer, and a styrene-based monomer.

[0095] The weight-average molecular weight of the polymer (Pm) of the present disclosure is not particularly limited, but from the viewpoint of adhesion, it is preferably 50,000 or more, more preferably 100,000 or more, even more preferably 200,000 or more, and particularly preferably 600,000 or more. From the viewpoint of viscosity and film-forming properties, the upper limit of the weight-average molecular weight is preferably 5,000,000 or less. The weight-average molecular weight refers to the weight-average molecular weight (polystyrene equivalent) measured using gel permeation chromatography (Tosoh Corporation, product number: HLC-8120GPC, columns: TSKgel G-5000HXL and TSKgel GMHXL-L used in series).

[0096] The glass transition temperature (Tg) of the polymer (Pm) of the present disclosure is not particularly limited, but is preferably in the range of -70 to 100°C, for example, from the viewpoint of conformability to the substrate. The lower limit of the Tg is more preferably -65°C or higher, and even more preferably -60°C or higher. On the other hand, the upper limit of the Tg is more preferably 80°C or lower, and even more preferably 60°C or lower.

[0097] The glass transition temperature (Tg) of the polymer (Pm) of the present disclosure is also preferably in the range of -40 to 50°C. When the polymer (Pm) is used as a binder for the ink of the present disclosure described below, a glass transition temperature of -40°C or higher tends to result in an image with excellent thermal stability, while a glass transition temperature of 50°C or lower tends to result in an ink with excellent film-forming properties at low temperatures. The upper limit of the Tg is more preferably 45°C or lower, and even more preferably 40°C or lower. Meanwhile, the lower limit of the Tg is more preferably -35°C or higher, and even more preferably -30°C or higher.

[0098] The glass transition temperature may be a value obtained by differential scanning calorimetry (DSC), differential thermal analysis (DTA), or thermomechanical analysis (TMA). However, it is preferable to use a value obtained by differential scanning calorimetry (DSC). Unless otherwise specified, the glass transition temperature in this specification refers to a value obtained by differential scanning calorimetry (DSC). Examples of differential scanning calorimetry (DSC) measurement devices include a DSC220C manufactured by Seiko Instruments Inc. Furthermore, when measuring differential scanning calorimetry (DSC), there are no particular limitations on the method for plotting a DSC curve, the method for obtaining a first derivative curve from a DSC curve, the method for performing smoothing processing, or the method for determining the target peak temperature. For example, when using the above-mentioned measurement device, a graph may be created from data obtained using the measurement device. In this case, analytical software capable of performing mathematical processing may be used. Examples of the analysis software include analysis software (Seiko Instruments Inc., product number: EXSTAA6000). Measurement conditions are preferably a temperature increase rate of 15°C / min and a temperature decrease rate of 15°C / min, and the values ​​obtained under these conditions are adopted. The glass transition onset temperature, midpoint temperature, inflection point temperature, and end temperature are observed in the above measurement, and the midpoint temperature is taken as the glass transition temperature (Tg) of the resin emulsion particles.

[0099] <Method for producing polymer (Pm)> The polymer (Pm) of the present disclosure can be produced by polymerizing a polymerizable monomer composition containing the polymerizable monomer (M) represented by the above formula (1). Examples of the monomer other than the polymerizable monomer (M) include the above-mentioned (meth)acrylic monomer, styrene-based monomer, acid group-containing monomer, monomer (Q), etc., and preferably a (meth)acrylic monomer and / or a styrene-based monomer. The content (charge amount) and blending ratio of each polymerizable monomer in the polymerizable monomer composition may be appropriately selected so as to obtain the content of the structure derived from each monomer in the target polymer. The polymerization method is not particularly limited, and any conventionally known polymerization method can be used, such as solution polymerization, suspension polymerization, emulsion polymerization, UV curing, etc.

[0100] 2. Resin particles The resin particles of the present disclosure include the polymer (Pm) of the present disclosure. The resin particles of the present disclosure may also be referred to as resin particles (Pp). The resin particles (Pp) may contain only the polymer (Pm) as a resin component, or may contain the polymer (Pm) and a polymer different from the polymer (Pm) (hereinafter, polymer (Pm2)). Examples of the resin particles (Pp) containing the polymer (Pm) and the polymer (Pm2) include: form A, in which the resin particles (Pp) have a multilayer structure, with one or more layers being composed of the polymer (Pm) and the remaining layers being composed of the polymer (Pm2); and form B, in which the resin particles (Pp) are composed of a polymer alloy of the polymer (Pm) and the polymer (Pm2). However, form A is preferred. The polymer (Pm) constituting the resin particles of the present disclosure, including preferred embodiments thereof, is the same as the polymer (Pm) explained in "1. Polymer," and the explanation therefor can be applied mutatis mutandis.

[0101] The shape of the resin particles (Pp) of the present disclosure is not particularly limited, and examples thereof include spherical, plate-like, and needle-like shapes. Spherical shapes are preferred. The shape can be measured using a transmission electron microscope or a scanning electron microscope.

[0102] The average particle size of the resin particles (Pp) of the present disclosure is not particularly limited, but is preferably 10 nm or more and 1000 nm or less. When the resin particles (Pp) of the present disclosure are used in a dispersion system (e.g., ink) in which they are dispersed in a solvent, the average particle size is more preferably 10 nm or more and 1 μm or less, from the viewpoint of facilitating uniform dispersion and obtaining a dispersion system with excellent dispersion stability. From the viewpoint of facilitating blending of the resin particles (Pp) at high concentrations while maintaining the viscosity of the dispersion system within an appropriate range, the average particle size is more preferably 50 nm or more and 500 nm or less, even more preferably 100 nm or more and 400 nm or less, and particularly preferably 150 nm or more and 350 nm or less. In this specification, the average particle diameter of the resin particles is the average particle diameter (hydrodynamic diameter) obtained by using a particle size distribution analyzer (manufactured by Otsuka Electronics Co., Ltd., product number: nanoSAQLA) based on dynamic light scattering, determining the autocorrelation function by photon correlation analysis, and then performing cumulant analysis.

[0103] The structure of the resin particles (Pp) of the present disclosure is not particularly limited, and may be a form in which the composition of the entire particle is uniform, or a core-shell structure consisting of a core and a shell with different compositions and / or physical properties. The core-shell structure is not limited to two layers, but may be three or more layers. That is, the resin particles (Pp) may be particles with a single-layer structure in which the entire particle is composed of the polymer (Pm), or particles with a multilayer structure composed of polymer (Pm) and polymer (Pm2). When the resin particles (Pp) have a single-layer structure, it is preferable that the entire particle is composed of polymer (Pm), and when the resin particles (Pp) have a multilayer structure, it is preferable that the outermost layer (i.e., the shell) is composed of polymer (Pm). By adopting such a structure, inks containing the resin particles (Pp) can exhibit better adhesion to substrates made of polyolefin. Among these, the resin particles (Pp) preferably have a core-shell structure of two or more layers, which can improve the balance between the elongation and hardness of the coating film. In the core-shell structure, it is preferable from the viewpoint of adhesion that the polymer of the polymerizable monomer (M) is present in a large amount in the outermost shell layer (specifically, the polymer (Pm) is present in a large amount in the outermost shell layer).

[0104] When the resin particles (Pp) have a core-shell structure, the polymer constituting the layer other than the outermost shell (for example, the core portion) may be either polymer (Pm) or polymer (Pm2), but is preferably polymer (Pm2). When both the core and the shell are composed of polymer (Pm), it is preferable that the mass proportion of the structure derived from the polymerizable monomer (M) in the polymer (Pm) in the shell portion is greater than the mass proportion of the structure derived from the polymerizable monomer (M) in the polymer (Pm) in the core portion.

[0105] The polymer (Pm2) is not particularly limited, and examples thereof include vinyl resins, (meth)acrylic resins, olefin resins, urethane resins, fluorine-containing resins, silicone resins, epoxy resins, phenoxy resins, phenol resins, xylene resins, and blocked isocyanates. When the resin particles (Pp) are of the above-mentioned form A, the polymer (Pm2) is preferably a (meth)acrylic resin (hereinafter referred to as (meth)acrylic polymer (2)). Furthermore, from the viewpoint of adhesion, the polymer (Pm2) is preferably an olefin resin. In particular, when the resin particles (Pp) are of the above-mentioned form B, the polymer (Pm2) is preferably an olefin resin.

[0106] The (meth)acrylic polymer (2) is a polymer containing a structural unit derived from a (meth)acrylic monomer. Examples of the (meth)acrylic monomer include the compounds exemplified above as the (meth)acrylic monomer. These (meth)acrylic monomers may be used alone or in combination of two or more. The content of the structure derived from a (meth)acrylic monomer in the (meth)acrylic polymer (2) is not particularly limited, but is, for example, 30 to 100% by mass, preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, still more preferably 90% by mass or more, and particularly preferably 95% by mass or more, based on 100% by mass of the (meth)acrylic polymer (2). In particular, it is more preferable to adjust the total content of the structure derived from a low-Tg (meth)acrylic acid alkyl ester, the structure derived from a (meth)acrylic acid ester having a cyclic aliphatic hydrocarbon group, and the structure derived from an acid group-containing monomer to fall within the above range.

[0107] From the viewpoint of film-forming properties, the (meth)acrylic polymer (2) preferably contains at least a low Tg (meth)acrylic acid alkyl ester. The low Tg (meth)acrylic acid alkyl ester is the same as the low Tg (meth)acrylic acid alkyl ester described above, including its preferred forms. The content of the structure derived from the low Tg (meth)acrylic acid alkyl ester in the (meth)acrylic polymer (2) is preferably adjusted so that the Tg of the (meth)acrylic polymer (2) falls within the range described below. For example, the content of the structure derived from the low Tg (meth)acrylic acid alkyl ester is preferably 2 to 80 mass%, more preferably 10 to 50 mass%, and even more preferably 15 to 30 mass%, based on 100 mass% of the (meth)acrylic polymer (2).

[0108] From the viewpoint of improving adhesion, the (meth)acrylic polymer (2) preferably further contains a structural unit derived from a (meth)acrylic acid ester having a cyclic aliphatic hydrocarbon group. The (meth)acrylic acid ester having a cyclic aliphatic hydrocarbon group is the same as the (meth)acrylic acid ester having a cyclic aliphatic hydrocarbon group described above, including preferred forms thereof. The content of the structure derived from the (meth)acrylic acid ester having a cyclic aliphatic hydrocarbon group in the (meth)acrylic polymer (2) is preferably 30 to 90 mass%, more preferably 50 to 85 mass%, and even more preferably 65 to 80 mass%, based on 100 mass% of the (meth)acrylic polymer (2). In particular, it is preferable to adjust the total content of the structure derived from the cycloalkyl (meth)acrylate and the structure derived from isobornyl (meth)acrylate to fall within the above range.

[0109] From the viewpoint of enhancing dispersion stability during polymerization, the (meth)acrylic polymer (2) preferably further contains a structural unit derived from an acid group-containing monomer. The acid group-containing monomer is the same as the acid group-containing monomer described above, including its preferred form. The content of the structure derived from an acid group-containing monomer (particularly (meth)acrylic acid) in the (meth)acrylic polymer (2) is preferably 0.5 to 10 mass %, more preferably 1 to 8 mass %, and even more preferably 3 to 5 mass %, based on 100 mass % of the (meth)acrylic polymer (2).

[0110] The (meth)acrylic polymer (2) may further contain a structural unit derived from a styrene-based monomer, which is the same as the styrene-based monomer described above, including its preferred forms. The content of the structure derived from a styrene-based monomer (particularly styrene) in the (meth)acrylic polymer (2) is preferably 30% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, based on 100% by mass of the (meth)acrylic polymer (2).

[0111] The (meth)acrylic polymer (2) may further contain, but preferably does not contain, a structure (M). The structure (M) is the same as the structure (M) described above, including its preferred forms. The content of the structure (M) in the (meth)acrylic polymer (2) is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on 100% by mass of the (meth)acrylic polymer (2).

[0112] The (meth)acrylic polymer (2) may further contain, but preferably does not contain, structural units derived from other monomers than the (meth)acrylic monomer, the styrene monomer, the acid group-containing monomer, and the polymerizable monomer (M). Examples of the other monomers include the monomers exemplified as the monomer (Q). The content of the structure derived from the monomer (Q) in the (meth)acrylic polymer (2) is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, based on 100% by mass of the (meth)acrylic polymer (2).

[0113] The weight average molecular weight of the polymer (Pm2) (preferably the (meth)acrylic polymer (2)) is not particularly limited, but from the viewpoint of improving the coating strength, it is preferably 50,000 or more, more preferably 100,000 or more, even more preferably 200,000 or more, and particularly preferably 600,000 or more. From the viewpoint of suppressing a decrease in film-forming properties, the upper limit of the weight average molecular weight is preferably 5,000,000 or less. The weight average molecular weight can be determined in the same manner as the weight average molecular weight of the polymer (Pm).

[0114] The glass transition temperature of the polymer (Pm2) (preferably the (meth)acrylic polymer (2)) is not particularly limited, but is preferably 50 to 120° C., and more preferably 70 to 110° C. The glass transition temperature can be determined in the same manner as for the weight average molecular weight of the polymer (Pm).

[0115] When the resin particles (Pp) contain a polymer (Pm) and a polymer (Pm2), the content ratio of the polymer (Pm) to the polymer (Pm2) (polymer (Pm):polymer (Pm2)) is preferably 5:95 to 95:5 by mass, more preferably 30:70 to 70:30. In particular, it is preferable to adjust the content ratio of the polymer (Pm) to the (meth)acrylic polymer (2) (polymer (Pm):(meth)acrylic polymer (2)) within the above range.

[0116] The content of the polymer (Pm) contained in the resin particles (Pp) of the present disclosure is not particularly limited, but is preferably 50% by mass or more, more preferably 80% by mass or more, even more preferably 95% by mass or more, and particularly preferably 100% by mass, of 100% by mass of the resin components contained in the resin particles (Pp) of the present disclosure. In particular, when the resin particles (Pp) are particles with a single layer structure, it is preferable to adjust the content of the polymer (Pm) contained in the resin particles (Pp) to within the above range, and when the resin particles (Pp) are particles with a multilayer structure, it is preferable to adjust the content of the polymer (Pm) contained in the outermost layer (i.e., shell portion) to within the above range, of 100% by mass of the resin components.

[0117] Furthermore, the content of the resin component contained in the resin particles (Pp) of the present disclosure is not particularly limited, but is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and particularly preferably 98% by mass or more, based on 100% by mass of the resin particles (Pp) of the present disclosure.

[0118] The resin particles (Pp) of the present disclosure may contain components other than the resin component, such as an emulsifier (surfactant).

[0119] The glass transition temperature (Tg) of the resin particles (Pp) of the present disclosure is not particularly limited, but is preferably in the range of -70 to 100°C, for example, from the viewpoint of film-forming ability and adhesion. The lower limit of the Tg is more preferably -65°C or higher, and even more preferably -60°C or higher. On the other hand, the upper limit of the Tg is more preferably 80°C or lower, and even more preferably 60°C or lower. The glass transition temperature (Tg) of the resin particles (Pp) of the present disclosure is also preferably in the range of -40 to 50°C. When the resin particles (Pp) are used as a binder in the ink of the present disclosure described below, a glass transition temperature of -40°C or higher tends to result in an image with excellent thermal stability, while a glass transition temperature of 50°C or lower tends to result in an ink with excellent film-forming properties at low temperatures. The upper limit of the Tg is more preferably 45°C or lower, and even more preferably 40°C or lower. Meanwhile, the lower limit of the Tg is more preferably -35°C or higher, and even more preferably -30°C or higher. The glass transition temperature of the resin particles (Pp) of the present disclosure is a value obtained by the same measurement method as that for the glass transition temperature of the polymer (Pm).

[0120] The method for producing the resin particles (Pp) of the present disclosure is not particularly limited. For example, they can be produced using a conventionally known emulsion polymerization method, suspension polymerization method, or bulk polymerization pulverization method using a polymerizable monomer composition containing a polymerizable monomer (M) represented by the above formula (1) as a raw material. Among these, emulsion polymerization or suspension polymerization carried out in an aqueous medium is preferred as the method for producing the resin particles (Pp) of the present disclosure. These production methods produce a polymerization liquid containing dispersed resin particles, and the resin particles contained in the polymerization liquid tend to have excellent dispersion stability in an aqueous medium. Resin particles obtained by emulsion polymerization carried out in an aqueous medium have particularly excellent dispersion stability. Resin particles obtained by emulsion polymerization carried out in an aqueous medium are also called aqueous emulsion particles. In the emulsion polymerization method, the polymerization may be carried out in one stage or in multiple stages. For example, in the first stage, a polymerizable monomer composition consisting of monomers constituting the polymer (Pm2) is polymerized in an aqueous medium to synthesize seed particles that will become the core (i.e., the polymer (Pm2)), and then a polymerizable monomer composition consisting of monomers constituting the polymer (Pm) is polymerized to synthesize the shell (i.e., the polymer (Pm)), thereby producing resin particles having a core-shell structure. Resin particles having a core-shell structure can also be produced by a method (seed emulsion polymerization method) in which particles obtained by a suspension polymerization method, an emulsion polymerization method, or the like are used as seed particles and emulsion polymerization is carried out in the presence of the seed particles. The content (charge amount) and compounding ratio of each polymerizable monomer in the polymerizable monomer composition may be appropriately selected so as to obtain the content of the structure derived from each polymerizable monomer in the target polymer (Pm) or polymer (Pm2).

[0121] As described above, among the resin particles (Pp) of the present disclosure, resin particles obtained by emulsion polymerization or suspension polymerization carried out in an aqueous medium are preferred, and aqueous emulsion particles are more preferred. The aqueous medium refers to a solvent containing 50% by mass or more of water. The water content is preferably 60% by mass or more, more preferably 80% by mass or more, even more preferably 95% by mass or more, and particularly preferably 100% by mass, based on 100% by mass of the aqueous medium. The solvent other than water in the aqueous medium is preferably a solvent compatible with water, such as alcohol, ether, ketone, ester, etc., and specifically includes the solvents exemplified as organic solvents contained in the aqueous dispersion described below. Even when the resin particles (Pp) of the present disclosure are aqueous emulsion particles, preferred aspects of the particle shape, average particle size, particle structure, particle composition, glass transition temperature, etc. are the same as those described for the resin particles (Pp) of the present disclosure.

[0122] 3.Aqueous dispersion The aqueous dispersion of the present disclosure is characterized by containing the resin particles (Pp) of the present disclosure. More specifically, the aqueous dispersion of the present disclosure is obtained by dispersing the resin particles (Pp) in an aqueous solvent. The aqueous solvent refers to a solvent containing water. The content of water in the aqueous solvent is not particularly limited, but is preferably 10 to 100% by mass, more preferably 25% by mass or more, even more preferably 50% by mass or more, and particularly preferably 80% by mass or more, based on 100% by mass of the aqueous solvent. The remainder is preferably an organic solvent.

[0123] The organic solvent is preferably an organic solvent that is miscible with water, and examples thereof include monohydric alcohols, polyhydric alcohols, polyhydric alcohol derivatives, ethers, ketones, esters, etc. Among these, monohydric alcohols, polyhydric alcohols, and polyhydric alcohol derivatives are preferred.

[0124] The monohydric alcohols are preferably monohydric alcohols having 1 to 3 carbon atoms, such as methanol, ethanol, and 2-propanol.

[0125] As the polyhydric alcohols, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, and glycerin are preferred.

[0126] Glycol derivatives are more preferred as the polyhydric alcohol derivatives, and examples of the glycol derivatives include glycol monoalkyl ethers such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, and diethylene glycol monoisobutyl ether; glycol monocarboxylic acid esters such as ethylene glycol monoacetate; glycol dialkyl ethers such as ethylene glycol dimethyl ether; glycol dicarboxylic acid esters such as ethylene glycol diacetate; and glycol monoalkyl ether monocarboxylic acid esters such as ethylene glycol monomethyl ether acetate.

[0127] The organic solvent is preferably a glycol or a monoalkyl ether of glycol, and is preferably a mono-, di-, or tri-C 2-3 Alkylene glycol, di-C 2-3 Alkylene glycol mono C 1-4 Alkyl ethers are more preferred, and propylene glycol, diethylene glycol, triethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, and diethylene glycol monoisobutyl ether are even more preferred. The above organic solvents may be used alone or in combination of two or more.

[0128] The resin particles (Pp) contained in the aqueous dispersion of the present disclosure, including preferred embodiments thereof, are the same as the resin particles (Pp) explained in "2. Resin Particles," and the explanation therefor can be applied mutatis mutandis. The resin particles (Pp) contained in the aqueous dispersion of the present disclosure are preferably the above-mentioned aqueous emulsion particles. That is, an aqueous dispersion in which aqueous emulsion particles are dispersed in an aqueous solvent is one preferred embodiment of the aqueous dispersion of the present disclosure. An aqueous dispersion in which aqueous emulsion particles are dispersed in an aqueous solvent is also referred to as an aqueous emulsion.

[0129] The aqueous dispersion of the present disclosure may contain, in addition to the resin particles (Pp) and the aqueous solvent, a dispersant for improving the dispersion stability of the resin particles (Pp). Examples of the dispersant include a surfactant and a water-soluble polymer.

[0130] The resin particles (Pp) are preferably stabilized in dispersion in the aqueous dispersion with a surfactant, and the aqueous emulsion particles are preferably stabilized in dispersion in the aqueous emulsion with a surfactant. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants, including conventionally known surfactants. These surfactants may be contained alone or in combination with one another in the aqueous dispersion (preferably the aqueous emulsion). Among the surfactants, nonionic surfactants and / or anionic surfactants are preferred. Furthermore, surfactants containing a polymerizable group in their molecule are also preferred. Examples of the polymerizable group include groups having an ethylenically unsaturated double bond. Among the surfactants, nonionic surfactants containing a polymerizable group and / or anionic surfactants containing a polymerizable group are particularly preferred. Surfactants containing a polymerizable group are also referred to as reactive emulsifiers. Polymer emulsifiers can also be used as surfactants.

[0131] Examples of the anionic surfactant include alkyl sulfate salts such as ammonium dodecyl sulfate and sodium dodecyl sulfate; alkyl sulfonate salts such as ammonium dodecyl sulfonate, sodium dodecyl sulfonate and sodium alkyl diphenyl ether disulfonate; alkyl aryl sulfonate salts such as ammonium dodecyl benzene sulfonate, sodium dodecyl benzene sulfonate and sodium dodecyl naphthalene sulfonate; polyoxyethylene alkyl sulfonate salts; polyoxyethylene alkyl ether sulfate salts; polyoxyethylene alkyl aryl ether sulfate salts; polyoxyethylene polycyclic phenyl ether salts; sulfate salts; dialkyl sulfosuccinate salts; arylsulfonic acid-formalin condensates; fatty acid salts such as ammonium laurate and sodium stearylate; sulfate esters or salts thereof having an allyl group such as bis(polyoxyethylene polycyclic phenyl ether) methacrylate sulfonate salts, propenyl-alkyl sulfosuccinate ester salts, (meth)acrylic acid polyoxyethylene sulfonate salts, (meth)acrylic acid polyoxyethylene phosphonate salts, and sulfonate salts of allyloxymethyl alkyloxy polyoxyethylene; sulfate ester salts of allyloxymethyl alkoxyethyl polyoxyethylene, and polyoxyalkylene alkenyl ether ammonium sulfate salts.

[0132] Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, condensates of polyethylene glycol and polypropylene glycol, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid monoglycerides, condensates of ethylene oxide and aliphatic amines, and polyoxyalkylene alkenyl ethers.

[0133] Examples of polymeric emulsifiers include poly(meth)acrylates such as sodium polyacrylate; polyvinyl alcohol; polyvinylpyrrolidone; polyhydroxyalkyl(meth)acrylates such as polyhydroxyethyl acrylate; and copolymers containing one or more of the monomers constituting these polymers as copolymerization components.

[0134] Examples of reactive emulsifiers include: Propenyl-alkyl sulfosuccinate salts, (meth)acrylic acid polyoxyethylene sulfonate salts, (meth)acrylic acid polyoxyethylene phosphonate salts (e.g., Sanyo Chemical Industries, Ltd., trade name: Eleminol RS-30, etc.), polyoxyethylene alkylpropenylphenyl ether sulfonate salts (e.g., Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon HS-10, etc.), sulfonate salts of allyloxymethyl alkyloxy polyoxyethylene (e.g., Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon KH-10, etc.), polyoxyethylene styrenated propenyl phenyl ether sulfate ammonium anionic surfactants containing a polymerizable group, such as ammonium salts (e.g., trade name: Aqualon AR-10, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), sulfonate salts of allyloxymethyl nonylphenoxyethyl hydroxypolyoxyethylene (e.g., trade name: Adeka Reasoap SE-10, manufactured by ADEKA Corporation), allyloxymethyl alkoxyethyl hydroxypolyoxyethylene sulfate salts (e.g., trade name: Adeka Reasoap SR-10, SR-30, manufactured by ADEKA Corporation), and bis(polyoxyethylene polycyclic phenyl ether) methacrylated sulfonate salts (e.g., trade name: Antox MS-60, manufactured by Nippon Nyukazai Co., Ltd.); nonionic surfactants containing a polymerizable group, such as polyoxyethylene styrenated propenyl phenyl ether (for example, trade name: Aqualon AN-10, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), allyloxymethyl alkoxyethyl hydroxypolyoxyethylene (for example, trade name: Adeka Reasop ER-20, manufactured by ADEKA Corporation), polyoxyethylene alkylpropenyl phenyl ether (for example, trade name: Aqualon RN-20, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), and allyloxymethyl nonylphenoxyethyl hydroxypolyoxyethylene (for example, trade name: Adeka Reasop NE-10, manufactured by ADEKA Corporation).

[0135] The content of the dispersant (preferably a surfactant) is preferably 0.5 to 10 parts by mass, more preferably 1.0 to 5 parts by mass, relative to 100 parts by mass of the resin particles (Pp).

[0136] As described above, the resin particles (Pp) obtained by emulsion polymerization carried out in an aqueous medium are referred to as aqueous emulsion particles, and the aqueous dispersion in which the aqueous emulsion particles are dispersed in the above-mentioned aqueous solvent is referred to as an aqueous emulsion. The polymerization liquid obtained by emulsion polymerization carried out in an aqueous medium is a preferred form of the aqueous dispersion of the present disclosure, and is also a preferred form of the aqueous emulsion.

[0137] The content of the resin particles (Pp) contained in the aqueous dispersion is not particularly limited, but is preferably 10 to 70% by mass relative to 100% by mass of the aqueous dispersion. A content of 10% by mass or more of the resin particles (Pp) tends to provide excellent film-forming properties, while a content of 70% by mass or less tends to provide low viscosity and excellent workability. A content of 20% by mass or more and 65% by mass or less is more preferred, and a content of 30% by mass or more and 60% by mass or less is even more preferred.

[0138] The average dispersed particle size of the resin particles (Pp) in the aqueous dispersion of the present disclosure is not particularly limited, but is preferably 10 nm or more and 1 μm or less from the viewpoint of excellent dispersion stability. From the viewpoint of easily blending the resin particles at a high concentration while maintaining the viscosity of the dispersion in an appropriate range, it is more preferably 50 nm or more and 500 nm or less, even more preferably 100 nm or more and 400 nm or less, and particularly preferably 150 nm or more and 350 nm or less. The average particle size of the dispersed resin particles (Pp) in the aqueous dispersion of the present disclosure can be measured by a measurement method using a laser diffraction / scattering particle size distribution analyzer or by dynamic light scattering. In either measurement method, the aqueous dispersion can be appropriately diluted with ion-exchanged water and used as a sample. Among these, it is preferable to use a particle size distribution analyzer using dynamic light scattering (Otsuka Electronics Co., Ltd., product number: nanoSAQLA) to determine the autocorrelation function using photon correlation analysis and use the average particle size (hydrodynamic diameter) determined by cumulant analysis.

[0139] The pH of the aqueous dispersion of the present disclosure is preferably 5 to 10, more preferably 6 to 9.5, and even more preferably 7 to 9.5, from the viewpoint of the stability of the aqueous dispersion. Any pH adjuster can be used to adjust the pH of the aqueous dispersion of the present disclosure to the aforementioned range. Specific examples of such pH adjusters include alkali metal compounds such as sodium hydroxide and potassium hydroxide; alkaline earth metal compounds such as calcium hydroxide and calcium carbonate; ammonia; and water-soluble organic amines such as dimethylaminoethanol, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dimethylpropylamine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, and diethylenetriamine. These pH adjusters can be used alone or in combination of two or more.

[0140] The method for producing the aqueous dispersion of the present disclosure is not particularly limited. It can be produced by mixing the resin particles (Pp) and an aqueous solvent. For example, a method can be used in which resin particle (Pp) powder is mixed with an aqueous solvent and then dispersed. If necessary, the above-mentioned dispersants can be added. As described above, the aqueous emulsion obtained by emulsion polymerizing a polymerizable monomer composition containing a polymerizable monomer (M) in an aqueous medium can be used as is as the aqueous dispersion of the present disclosure. Alternatively, the aqueous emulsion obtained by emulsion polymerizing a polymerizable monomer composition containing a polymerizable monomer (M) in an aqueous medium can be heated to remove part of the solvent, thereby adjusting the content of aqueous emulsion particles, and the like, to produce the aqueous dispersion of the present disclosure. The aqueous dispersion of the present disclosure can also be prepared by adding water, an organic solvent, or an aqueous solvent to an aqueous emulsion obtained by emulsion polymerizing a polymerizable monomer composition containing a polymerizable monomer (M) in an aqueous medium.

[0141] 4. Ink The ink of the present disclosure is an ink containing a binder and a solvent, and is characterized in that the binder contains the polymer (Pm) of the present disclosure and / or the resin particles (Pp) of the present disclosure. Therefore, by using the ink of the present disclosure, it is likely that printed matter with excellent adhesion to the substrate can be obtained, particularly when the substrate is made of polyolefin.

[0142] The solvent constituting the ink of the present disclosure is not particularly limited. For example, it may be water, an organic solvent, or a combination of these. Among these, water or a combination of water and an organic solvent is preferred, and an aqueous solvent is more preferred. The aqueous solvent has the same meaning as the aqueous solvent described as the aqueous solvent constituting the aqueous dispersion of the present disclosure (meaning a solvent containing water), and the preferred range of the water content in the aqueous solvent is the same as the preferred range of the water content in the aqueous solvent constituting the aqueous dispersion of the present disclosure described above. Furthermore, as a solvent other than water that can be used for the aqueous solvent (i.e., an organic solvent), the same organic solvent as the organic solvent in the aqueous solvent constituting the aqueous dispersion of the present disclosure described above can also be used, and the preferred aspects are also the same. In the ink of the present disclosure, an ink in which the solvent is a water-based solvent is also referred to as a water-based ink.

[0143] The polymer (Pm) and resin particles (Pp) contained as binders in the ink of the present disclosure, including their preferred embodiments, are similar to the polymer (Pm) and resin particles (Pp) described in "1. Polymer" and "2. Resin Particles," including their preferred embodiments, and the descriptions therefor can be applied mutatis mutandis.

[0144] When used as a binder in the ink of the present disclosure, the polymer (Pm) preferably has a glass transition temperature of -40°C or higher from the viewpoint of excellent thermal stability of the resulting image, and preferably 50°C or lower from the viewpoint of excellent film-forming properties at low temperatures. It is more preferably 45°C or lower, and even more preferably 40°C or lower. Meanwhile, the lower limit is more preferably -35°C or higher, and even more preferably -30°C or higher. The method for measuring the glass transition temperature is as described above. That is, the glass transition temperature of the polymer (Pm) contained in the ink of the present disclosure is preferably -40 to 50°C, more preferably -35 to 45°C, and even more preferably -30 to 40°C. The resin particles (Pp) also preferably have a glass transition temperature in the same range as the polymer (Pm) for the same reasons.

[0145] Furthermore, from the viewpoint of excellent image uniformity, the resin particles (Pp) used in the ink of the present disclosure preferably have a dispersed average particle diameter of 10 nm or more and 1 μm or less. The lower limit is more preferably 50 nm or more, and even more preferably 150 nm or more. Meanwhile, the upper limit is more preferably 500 nm or less, and even more preferably 350 nm or less. The method for measuring the dispersed average particle diameter is the same as the method for measuring the dispersed average particle diameter of the resin particles (Pp) in the aqueous dispersion.

[0146] The binder may contain one or more types of polymers (Pm), one or more types of resin particles (Pp), or one or more types of polymers (Pm) and one or more types of resin particles (Pp). Of these, the binder preferably contains at least resin particles (Pp), and more preferably the resin particles (Pp) are aqueous emulsion particles.

[0147] The binder may contain binder components other than the polymer (Pm) and the resin particles (Pp), but the total content of the polymer (Pm) (excluding the polymer (Pm) contained in the resin particles (Pp)) and the resin particles (Pp) is preferably 50 to 100% by mass, more preferably 80% by mass or more, even more preferably 95% by mass or more, and particularly preferably 100% by mass, relative to 100% by mass of the binder. In particular, it is preferable to adjust the content of the resin particles (Pp) to be within the above range.

[0148] The binder components other than the polymer (Pm) and the resin particles (Pp) are not particularly limited, and conventionally known materials can be used. Materials that can be used as the other binder components include, for example, vinyl resins, (meth)acrylic resins, olefin resins, urethane resins, fluorine-containing resins, silicone resins, epoxy resins, phenoxy resins, phenolic resins, xylene resins, and blocked isocyanates. The materials that can be used as the other binder components may be in a form dissolved in a solvent, or may be in particulate form like the resin particles (Pp).

[0149] When the ink of the present disclosure is an aqueous ink, the binder preferably contains at least resin particles (Rp), and more preferably contains the above-mentioned aqueous emulsion particles. That is, an ink containing a binder and a solvent, the solvent being aqueous, and the binder containing the above-mentioned resin particles (Pp), is one of the preferred embodiments of the ink of the present disclosure. Furthermore, an ink containing a binder and a solvent, the solvent being aqueous, and the binder containing the above-mentioned aqueous emulsion particles is one of the more preferred embodiments of the ink of the present disclosure.

[0150] The content of each component contained in the ink of the present disclosure is not particularly limited. The content of the binder in the ink of the present disclosure is preferably 1 to 70% by mass per 100% by mass of the ink. If it is less than 1% by mass, there is a risk that performance such as adhesion will decrease, and if it exceeds 70% by mass, there is a risk that the viscosity will be high and workability will decrease. More preferably, it is 5% by mass or more and 65% by mass or less. The content of the binder in the solid content of the ink of the present disclosure is preferably 4 to 100% by mass, more preferably 20 to 99% by mass, and even more preferably 30 to 98% by mass. When the ink of the present disclosure is a colored ink containing a pigment, the content of the binder in the solid content of the ink is preferably 4 to 100% by mass, more preferably 10 to 80% by mass, even more preferably 20 to 60% by mass, and even more preferably 30 to 50% by mass. When the ink of the present disclosure is a clear ink containing no pigment, the content of the binder in the solid content of the ink is preferably 4 to 100% by mass, more preferably 50 to 99% by mass, even more preferably 60 to 98% by mass, and even more preferably 70 to 98% by mass. In this specification, the term "solid content" refers to components excluding the solvent.

[0151] The content of the solvent in the ink of the present disclosure is preferably 30 to 99% by mass, and more preferably 35 to 95% by mass, relative to 100% by mass of the ink of the present disclosure. Note that the above solvent content refers to the total content of the solvent contained in the ink of the present disclosure.

[0152] In addition to the components described above, the ink of the present disclosure may contain pigments, crosslinking agents, other components, and the like, as described below, as needed.

[0153] The ink of the present disclosure preferably further contains a pigment. By containing a pigment, the hue of the ink can be adjusted. In this specification, an ink containing a pigment may be referred to as a "colored ink." Note that the ink of the present disclosure may also be a clear ink that does not contain a pigment. The hue of the pigment is not particularly limited and may be selected from black, white, and chromatic colors. Chromatic colors include the three primary subtractive colors of magenta, yellow, and cyan, as well as colors of different shades such as light cyan, dark yellow, light magenta, and light black. Furthermore, the pigment may have one or more hues selected from red, blue, orange, green, and violet. In this specification, a pigment exhibiting a white hue may be referred to as a white pigment, and a pigment exhibiting a hue other than white (chromatic colors or black) may be referred to as a colored pigment.

[0154] As the pigment, conventionally known pigments can be used. Examples of pigments include organic pigments and inorganic pigments, which can be used alone or in combination of two or more. If necessary, these pigments can also be used in combination with an extender pigment.

[0155] Examples of organic pigments include azo pigments such as benzidine and Hansa Yellow, diazo pigments, azomethine pigments, methine pigments, anthraquinone pigments, phthalocyanine pigments such as phthalocyanine blue, perinone pigments, perylene pigments, diketopyrrolopyrrole pigments, thioindigo pigments, iminoisoindoline pigments, isoindolinone pigments such as iminoisoindolinone, dioxazine pigments, quinacridone pigments such as quinacridone red and quinacridone violet, flavanthrone pigments, indanthrone pigments, anthrapyrimidine pigments, carbazole pigments, monoarylide yellow, diarylide yellow, benzimidazolone yellow, tolyl orange, naphthol orange, and quinophthalone pigments.

[0156] The hue of the organic pigment is not particularly limited, and any chromatic pigment such as yellow, magenta, cyan, blue, red, orange, or green can be used. Specific examples include CI Pigment Yellow, CI Pigment Red, CI Pigment Orange, CI Pigment Violet, CI Pigment Blue, and CI Pigment Green. When targeting polypropylene substrates such as polypropylene fabrics, it is preferable to use organic pigments that do not contain metals, so as not to promote thermal decomposition of the polypropylene. Specifically, pigments such as Pigment Blue 16 can be selected.

[0157] Examples of inorganic pigments include titanium dioxide, antimony trioxide, zinc oxides such as zinc white, lithopone, white lead, red iron oxide, black iron oxide, chromium oxide green, carbon black, yellow lead, molybdenum red, ferric ferrocyanide (Prussian blue), ultramarine, and lead chromate. Other examples of inorganic pigments include flat-shaped pigments such as mica, clay, aluminum powder, talc, and aluminum silicate, as well as extender pigments such as calcium carbonate, magnesium hydroxide, aluminum hydroxide, barium sulfate, and magnesium carbonate. Examples of carbon black include furnace black, thermal lamp black, acetylene black, and channel black.

[0158] Among inorganic pigments, preferred white pigments are titanium dioxide, antimony trioxide, zinc oxide such as zinc white, lithopone, white lead, calcium carbonate, magnesium hydroxide, aluminum hydroxide, barium sulfate, magnesium carbonate, clay, talc, and aluminum silicate. Of these, titanium dioxide is preferred from the viewpoint of its high refractive index and excellent hiding power. Of titanium dioxide, titanium dioxide having a rutile crystal structure is preferred.

[0159] As the color pigment, the above-mentioned organic pigments, red iron oxide, black iron oxide, chromium oxide green, carbon black, yellow lead, molybdenum red, ferric ferrocyanide (Prussian blue), ultramarine, lead chromate, etc. are preferred.

[0160] The average particle size of the pigment is preferably 10 to 1,000 nm, more preferably 20 to 500 nm, from the viewpoints of dispersion stability, color development, and hiding power. In the case of a white pigment, the average particle size is preferably 100 to 500 nm, more preferably 150 to 450 nm, and even more preferably 200 to 400 nm, from the viewpoint of superior hiding power. In the case of a colored pigment, the average particle size is preferably 20 to 200 nm, more preferably 40 to 150 nm, and even more preferably 50 to 100 nm, particularly from the viewpoint of color development.

[0161] The average particle size is preferably the average dispersed particle size of the pigment in the ink of the present disclosure. The average dispersed particle size of the pigment can be measured by a measurement method using a laser diffraction / scattering particle size distribution analyzer or dynamic light scattering, similar to the average dispersed particle size of the resin particles (Pp) in the aqueous dispersion of the present disclosure. It is particularly preferable to use a particle size distribution analyzer using dynamic light scattering (Otsuka Electronics Co., Ltd., product number: nanoSAQLA) to determine the autocorrelation function using photon correlation analysis and then use the average particle size (hydrodynamic diameter) determined by cumulant analysis. However, in cases where measurement by dynamic light scattering is difficult, such as with black pigments, the 50% particle size in the volume-based particle size distribution obtained by measurement using a laser diffraction / scattering particle size distribution analyzer can be used as the average particle size.

[0162] The pigment is preferably dispersed and stabilized in the ink of the present disclosure with a dispersant. That is, the ink of the present disclosure preferably contains a dispersant together with the pigment. Examples of the dispersant include poly(meth)acrylic acid (salts) such as poly(meth)acrylic acid and poly(meth)acrylate salts; copolymers of (meth)acrylic acid (salts) with one or more ethylenically unsaturated double bond-containing monomers such as (meth)acrylic acid esters, (meth)acrylonitrile, (meth)acrylamide, styrene, maleic acid, maleic anhydride, maleic acid esters, and vinyl acetate; polyvinyl alcohol; polyvinylpyrrolidone; and the like. The content of the dispersant is not particularly limited, but is preferably 1 to 50 parts by mass relative to 100 parts by mass of the pigment.

[0163] When the ink of the present disclosure contains a pigment, the pigment content is not particularly limited, but is preferably 1 to 40% by mass per 100% by mass of the ink. If it is less than 1% by mass, there is a risk that the color development will be insufficient, and if it exceeds 40% by mass, there is a risk that the coating film will become brittle. A content of 2% by mass or more and 35% by mass or less is more preferred. Furthermore, when the ink of the present disclosure contains a pigment, the content of the pigment relative to 100 parts by mass of the binder is preferably 10 to 400 parts by mass, more preferably 20 to 300 parts by mass, and even more preferably 30 to 200 parts by mass.

[0164] The ink of the present disclosure may further contain a crosslinking agent, which exhibits a crosslinking effect through interaction with the components contained in the ink of the present disclosure, such as the polymer (Pm) and / or resin particles (Pp), and the pigment (if a pigment is included), dispersant, etc., or through a chemical reaction, making it easier to form a tough coating film.

[0165] The crosslinking agent may be one that initiates a crosslinking reaction at room temperature or one that initiates a crosslinking reaction by heat. Suitable crosslinking agents include, for example, oxazoline group-containing compounds, isocyanate group-containing compounds, aminoplast resins, polyvalent metal compounds, carbodiimide compounds, etc. These crosslinking agents may be used alone or in combination of two or more.

[0166] Among these crosslinking agents, oxazoline group-containing compounds are preferred from the viewpoint of excellent crosslinking performance. The oxazoline group-containing compound means a compound having two or more oxazoline groups in the molecule. Examples of the oxazoline group-containing compound include 2,2'-bis(2-oxazoline), 2,2'-methylene-bis(2-oxazoline), 2,2'-ethylene-bis(2-oxazoline), 2,2'-trimethylene-bis(2-oxazoline), 2,2'-tetramethylene-bis(2-oxazoline), 2,2'-hexamethylene-bis(2-oxazoline), 2,2'-octamethylene-bis(2-oxazoline), and 2,2'-ethylene-bis Examples of suitable oxazoline-containing compounds include, but are not limited to, 2,2'-p-phenylene-bis(2-oxazoline), 2,2'-m-phenylene-bis(2-oxazoline), 2,2'-m-phenylene-bis(4,4'-dimethyl-2-oxazoline), bis(2-oxazolinylcyclohexane) sulfide, bis(2-oxazolinylnorbornane) sulfide, and oxazoline group-containing polymers. These oxazoline group-containing compounds may be used alone or in combination of two or more.

[0167] Among the above oxazoline group-containing compounds, water-soluble oxazoline group-containing compounds and / or oxazoline group-containing polymers are preferred, and water-soluble oxazoline group-containing polymers are more preferred, due to their excellent crosslinking performance. The oxazoline group-containing polymers can be produced by conventionally known production methods. For example, a method of polymerizing a monomer component containing one or more addition-polymerizable oxazolines, or an addition-polymerizable oxazoline and a monomer copolymerizable with the addition-polymerizable oxazoline, is exemplified. The copolymerizable monomer is preferably a monomer that does not have a functional group reactive with the oxazoline group but is copolymerizable with the addition-polymerizable oxazoline. For example, the above ethylenically unsaturated double bond-containing monomer (specifically, the monomers exemplified as monomers constituting the polymer (Pm)) that does not have a functional group reactive with the oxazoline group can be exemplified. Examples include vinyl monomers such as vinyl acetate, vinyl chloride, and vinyl benzoate; acrylonitrile; (meth)acrylamide monomers such as acrylamide; (meth)acrylic monomers such as (meth)acrylic acid esters (preferably (meth)acrylic acid linear alkyl esters and (meth)acrylic acid branched alkyl esters); styrene monomers such as styrene, α-methylstyrene, and chloromethylstyrene; and olefin monomers such as ethylene and propylene.

[0168] Examples of the addition-polymerizable oxazoline include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, and 2-isopropenyl-5-ethyl-2-oxazoline.

[0169] Among the oxazoline group-containing polymers, water-soluble oxazoline group-containing polymers are preferred, and can be produced by the same method as the above-mentioned method for producing the oxazoline group-containing polymer. Examples of the water-soluble oxazoline group-containing polymer include polymers having an acrylic polymer, an acrylic-styrene polymer, or the like as a main chain and containing oxazoline groups in the side chains.

[0170] Commercially available oxazoline group-containing polymers can also be used. Examples include water-soluble polymers such as Epocross WS-500 and Epocross WS-700, manufactured by Nippon Shokubai Co., Ltd., and emulsion polymers such as Epocross K-2010, Epocross K-2020, and Epocross K-2030. Among these, water-soluble polymers such as Epocross WS-500 and Epocross WS-700, manufactured by Nippon Shokubai Co., Ltd., are preferred.

[0171] When the ink of the present disclosure contains a crosslinking agent, the content of the crosslinking agent is not particularly limited, but is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the binder. If the content is less than 0.1 part by mass, it may be difficult to improve the coating film strength, and if the content exceeds 30 parts by mass, water resistance may be reduced. More preferably, it is 0.2 to 20 parts by mass. From the viewpoint of improving the coating film strength, it is preferably 0.5 to 10 parts by mass, more preferably 5 parts by mass or less, relative to 100 parts by mass of the binder. In other words, the content of the crosslinking agent is preferably 0.1 to 30 parts by mass, more preferably 0.2 to 20 parts by mass, even more preferably 0.5 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass relative to 100 parts by mass of the binder.

[0172] The ink of the present disclosure may further contain other components in addition to the binder component, solvent, pigment, and crosslinking agent described above, as long as the object of the present invention is not impaired. For example, the ink may contain appropriate amounts of additives such as surfactants, dispersants, leveling agents, UV absorbers, UV stabilizers, thickeners, wetting agents, plasticizers, stabilizers, antifoaming agents, dyes, antioxidants, crosslinking accelerators, pH adjusters, and preservatives. As the leveling agent, for example, acetylene glycol-based, silicone-based, or fluorine-based surfactants are preferably used, and among these, polyether-modified silicone compounds are preferred.

[0173] When the other components are added, their content is not particularly limited, but is preferably 2% by mass or less, and more preferably 1% by mass or less, relative to 100% by mass of the ink of the present disclosure. In order to exert the effect of addition, their content is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more.

[0174] The method for producing the ink of the present disclosure is not particularly limited. The ink can be produced by mixing a binder and a solvent, as well as a pigment, a crosslinking agent, and additives, which are used as needed. In a preferred embodiment, it is preferable to prepare an aqueous dispersion containing resin particles (Pp) (preferably an aqueous emulsion containing aqueous emulsion particles) in advance, and then mix the aqueous dispersion (preferably the aqueous emulsion) with other components. In addition, in the preparation of a pigment-containing ink, it is preferable to prepare a pigment dispersion containing the pigment in advance, and then mix the aqueous dispersion (preferably the aqueous emulsion) with other components such as a crosslinker. An example of the production of a water-based ink using water-based emulsion particles as a binder will be described below.

[0175] First, an emulsion containing aqueous emulsion particles is prepared. As described above, an emulsion containing aqueous emulsion particles can be produced by a conventional emulsion polymerization method. For example, an aqueous emulsion is prepared by emulsion polymerization in an aqueous medium using a polymerizable monomer composition containing a polymerizable monomer (M) as a raw material. The aqueous emulsion contains aqueous emulsion particles containing the polymer (Pm) (preferably the resin (Pp)) of the present disclosure dispersed in the aqueous solvent at a predetermined ratio. The content of aqueous emulsion particles in the aqueous emulsion is not particularly limited, but is preferably 30 to 65% by mass relative to 100% by mass of the aqueous emulsion. Although aqueous emulsions obtained by emulsion polymerization typically contain an emulsifier such as a surfactant used in the emulsification, the aqueous emulsion may be used directly as the aqueous emulsion for preparing the ink of the present disclosure.

[0176] In preparing an ink containing a pigment, it is preferable to prepare a pigment dispersion in advance. The pigment dispersion can be produced by mixing a pigment and a dispersant in water or an aqueous solvent and dispersing the mixture using a bead mill or the like. The pigment content in the pigment dispersion is not particularly limited, but is preferably 15 to 65% by mass relative to 100% by mass of the pigment dispersion. The dispersant content is also not particularly limited, but is preferably 1 to 10 parts by mass relative to 100 parts by mass of the pigment in the pigment dispersion.

[0177] Next, the aqueous emulsion and other components, such as the pigment dispersion and the crosslinking agent, which are used as needed, are mixed to prepare a mixture. When mixing, the other components, such as the crosslinking agent, may be used as they are or may be used as a solution diluted with a solvent. The method and order of mixing the above components are not particularly limited. For example, when a pigment dispersion and a crosslinking agent are used as other components, the water-based emulsion and the pigment dispersion may be mixed together, and then the crosslinking agent may be mixed therewith; the pigment dispersion and the crosslinking agent may be mixed together, and then the water-based emulsion may be mixed therewith; the water-based emulsion and the crosslinking agent may be mixed together, and then the pigment dispersion may be mixed therewith; or the pigment dispersion, the water-based emulsion, and the crosslinking agent may be mixed together almost simultaneously.

[0178] A solvent (adjustment solvent) can be added to the mixture to adjust the concentration of each component in the ink of the present disclosure or to adjust the physical properties of the ink. The solvent can be water, an organic solvent such as a glycol, or a mixture of water and an organic solvent. Components such as additives other than those described above may also be mixed. The timing for mixing these solvents (adjustment solvents), additives, etc. can be selected appropriately. After mixing the components, centrifugation, filtration, etc. can be performed as needed. The above-described production method can produce an aqueous ink containing aqueous emulsion particles and an aqueous solvent (for example, an aqueous ink containing a pigment, aqueous emulsion particles, a crosslinking agent, and an aqueous solvent). Although one example of the ink production method of the present disclosure has been shown above, the present disclosure is not limited to the above.

[0179] 5. Manufacturing method of printed matter A method for producing a printed matter according to the present disclosure will now be described. The method for producing a printed matter of the present disclosure uses the ink of the present disclosure, that is, the method for producing a printed matter of the present disclosure includes an image forming step of applying the ink of the present disclosure to a substrate to form an image, and the image is printed on the substrate. Therefore, the printed matter obtained by the method for producing a printed matter of the present disclosure has excellent adhesion to the substrate, and when the substrate is made of polyolefin, it is easy to obtain a printed matter having excellent adhesion to the substrate.

[0180] The ink used in the method for producing printed matter of the present disclosure is an ink containing a binder and a solvent, characterized in that the binder contains the polymer (Pm) of the present disclosure and / or the resin particles (Pp) of the present disclosure (preferably contains the resin particles (Pp) of the present disclosure). The specific configuration of the ink (e.g., the type and amount of solvent and binder contained in the ink), including preferred embodiments thereof, is the same as the specific configuration of the ink (e.g., the type and amount of solvent and binder contained in the ink), including preferred embodiments thereof, described in the description of "4. Ink," and the description thereof can be applied mutatis mutandis. From the viewpoint of low environmental impact, the ink used in the method for producing printed matter of the present disclosure is preferably a water-based ink.

[0181] The substrate is not particularly limited, but is preferably a fabric, a polymer film, a polymer molded product, or the like. The term "fabric" encompasses all textile products, such as cloth and textiles, made from natural and / or synthetic fibers. Examples of fabric include woven fabric, nonwoven fabric, and knitted fabric. The fibers constituting the fabric are also not particularly limited, and examples include natural fibers, chemical fibers, and mixtures thereof. Hereinafter, a printed matter obtained using a fabric as the substrate may be referred to as a "printed item."

[0182] Preferred examples of the natural fibers include silk, cotton, and wool. The chemical fibers include synthetic fibers, regenerated fibers, and semi-synthetic fibers. Preferred examples of synthetic fibers include polyester fibers, nylon fibers, acrylic fibers, polyurethane fibers, polyolefin fibers such as polyethylene fibers and polypropylene fibers, and vinylon fibers. Preferred examples of regenerated fibers include rayon. Preferred examples of semi-synthetic fibers include acetate and triacetate. When the substrate is a fabric, the fabric preferably contains at least one fiber selected from the group consisting of polyolefin fibers such as polyethylene fibers and polypropylene fibers, polyester fibers, and cotton, more preferably a fabric containing polyolefin fibers, and even more preferably a fabric containing polypropylene fibers.

[0183] In particular, when the fabric used as the substrate is a nonwoven fabric, examples of the material include polyolefins such as polyethylene and polypropylene, rayon, cotton, celluloses, etc., and among these, polyolefins are preferred, with polypropylene being particularly preferred.

[0184] When the substrate is a polymer film, examples of the material include polyolefin, polyester resin, amide resin, (meth)acrylic resin, polyurethane resin, polyvinyl alcohol resin, cellulose, etc. Among these, when the substrate is a polymer film, polyolefin film and polyester film are preferred. Preferred examples of the polyolefin film include polyethylene film and polypropylene film, and preferred examples of the polypropylene film include CPP (non-oriented polypropylene) and OPP (biaxially oriented polypropylene), with OPP being particularly preferred. Furthermore, preferred examples of the polyester film include polyethylene terephthalate film.

[0185] Examples of the polymer molded article include polyolefin plates such as SBR (styrene butadiene rubber) plates, polyethylene plates, and polypropylene plates, with polyolefin plates being preferred and polypropylene plates being particularly preferred.

[0186] In particular, the ink of the present invention is suitably used for substrates made of polyolefin. In this specification, a substrate made of polyolefin may be referred to as a polyolefin substrate. Examples of the polyolefin substrate include fabrics such as woven fabrics, nonwoven fabrics, and knitted fabrics made of polyolefin fibers (e.g., polyethylene fibers, polypropylene fibers); films made of polyolefins (e.g., polyethylene, polypropylene); and molded products of polyolefins such as polyolefin plates (e.g., polyethylene plates, polypropylene plates). Among the polyolefin substrates, fabrics made of polyolefin fibers and films made of polyolefin are preferred, and fabrics made of polyethylene fibers, fabrics made of polypropylene fibers, polyethylene films, and polypropylene films are more preferred.

[0187] The surface of the substrate to be printed with the ink of the present invention may be chemically or physically modified by corona treatment, anchor coating treatment, or the like. This improves adhesion to the image formed from the ink of the present invention. Specific examples include corona-treated polyolefin films.

[0188] The method for forming an image by applying the ink of the present disclosure to the substrate is not particularly limited, but is preferably at least one printing method selected from the group consisting of silk screen printing, spray printing, letterpress printing, intaglio printing such as gravure printing, lithographic printing such as offset printing, and inkjet printing. By using the above printing method to perform an image formation step in which the ink of the present disclosure is applied to a substrate, a substrate on which the image is formed can be obtained.

[0189] Among the printing methods used in the method for producing printed matter of the present disclosure, inkjet printing is preferred. Inkjet printing refers to a printing method using an inkjet printer. The inkjet printer is not particularly limited, and any conventionally known inkjet printer can be used. Any inkjet printer, such as a piezoelectric type, a thermal type, or a charge change control type (continuous ejection type), can be used. Among these, a piezoelectric type inkjet printer is preferred. When using a piezoelectric type inkjet printer, the ink ejection conditions are not particularly limited. They may be appropriately selected depending on the properties of the ink of the present disclosure, the type of substrate, the type of image to be printed, and the like. Furthermore, when using inkjet printing, the viscosity of the ink of the present disclosure is preferably in the range of 2 to 20 mPa / s. Furthermore, when using inkjet printing, the surface tension of the ink of the present disclosure is preferably in the range of 25 to 45 mN / m.

[0190] In the image forming process, ink is ejected from the nozzle openings of the inkjet printer head and adheres to the surface of the substrate to form an image. The substrate on which an image has been formed by inkjet printing is preferably subjected to a heat treatment, as described below. The heating method, timing of the heat treatment, heating temperature, and the like, including preferred embodiments of each, are as described below. By employing the printing method using the inkjet printer, in addition to the effects of using the ink of the present disclosure described above, it is possible to easily obtain an article in which any image, such as letters, pictures, or diagrams, is printed on a substrate such as fabric or polymer film.

[0191] The method for producing a printed matter according to the present disclosure preferably includes a heating step (also referred to as a heat treatment step). That is, the substrate on which an image has been formed by the above-described method is preferably subjected to a heat treatment. The heat treatment can promote the removal of volatile components, such as the aqueous solvent derived from the ink, contained in the image formed on the substrate, and can also promote fixation of the image by melting the binder component contained in the ink.

[0192] The heat treatment step may be carried out simultaneously with the image formation step or after the image formation step. Alternatively, both may be combined. For example, a method of carrying out the heat treatment step simultaneously with the image formation step includes a method of carrying out the image formation step while heating the substrate. Preferred examples of the heat treatment method when carrying out the heat treatment step after the image formation step include a heating method using a heating and drying oven, a heating method using a heat press, a heating method using an infrared lamp, an electrically heated hot plate method, and a method using steam such as atmospheric steam or high-pressure steam. Among these heating methods, the heat treatment step is preferably carried out after the image formation, since simultaneous heating may cause disturbances in the airflow.

[0193] The heating temperature is not particularly limited, but is preferably 60 to 180°C. The upper limit is more preferably 150°C or less, even more preferably 110°C or less, and the lower limit is more preferably 70°C or more, even more preferably 80°C or more. The heating time is also not particularly limited, but is preferably 0.5 to 30 minutes. The upper limit is more preferably 20 minutes or less, even more preferably 10 minutes or less, and the lower limit is more preferably 1 minute or more, even more preferably 2 minutes or more. When the substrate is a fabric, the heating temperature and time in the heat treatment step vary depending on the material of the fabric. For example, for cotton, the heating temperature is 120 to 190°C (preferably 160°C), for polypropylene, 70 to 130°C (preferably 125°C), and for polyester, 110 to 170°C (preferably 110°C), all preferably within 5 minutes.

[0194] When the substrate is a fabric, the printed matter (printed matter) on which an image is formed on the fabric obtained after the heat treatment step may be washed with water and dried.

[0195] The above-described method for producing a printed matter makes it possible to produce a printed matter having excellent image adhesion in an energy-saving and environmentally friendly manner, particularly when the substrate is polyolefin.

[0196] 6. Image fixing articles The image fixing article of the present disclosure will now be described. The image-fixed article of the present disclosure is an image-fixed article in which an image containing a pigment and a resin is fixed to a part or all of a substrate, and is characterized in that the resin contains a polymer (Pm) containing, as a constituent unit, a structure derived from the polymerizable monomer (M) represented by the above formula (1).

[0197] The resin contains a polymer (Pm) that contains, as a constituent unit, a structure derived from the polymerizable monomer (M) represented by the formula (1). The polymer (Pm) contained in the above resin, including its preferred embodiments, is the same as the polymer (Pm) described in "1. Polymer," and the description in "1. Polymer" can be applied mutatis mutandis.

[0198] The resin may be resin particles containing only the polymer (Pm) as a resin component, or may be resin particles containing a resin component other than the polymer (Pm). In the present disclosure, resin components other than the polymer (Pm) are also referred to as other resin components. The other resin components are not particularly limited, but examples include vinyl resins, (meth)acrylic resins, olefin resins, urethane resins, fluorine-containing resins, silicone resins, epoxy resins, phenoxy resins, phenolic resins, xylene resins, and blocked isocyanates. The other resin component is preferably polymer (Pm2). The polymer (Pm2), including its preferred embodiments, is similar to the polymer (Pm2) described in "2. Resin Particles," and the description thereof can be applied mutatis mutandis. Furthermore, from the viewpoint of adhesion, an olefin resin is preferred as the other resin component. The content of the polymer (Pm) contained in the resin is not particularly limited, but is preferably 50% by mass or more, more preferably 80% by mass or more, even more preferably 95% by mass or more, and particularly preferably 100% by mass, of 100% by mass of the resin.

[0199] The above pigments, including their preferred embodiments, are the same as the pigments that may be contained in the ink of the present disclosure described in "4. Ink," and the description given in "4. Ink" can be applied mutatis mutandis.

[0200] The image contains the resin and the pigment. The total content of the resin and pigment in the image is preferably 70 to 100% by mass, more preferably 90 to 100% by mass, and even more preferably 95 to 100% by mass, relative to 100% by mass of the image. The content of the resin in the image is preferably 20% by mass or more but less than 100% by mass, more preferably 25 to 90% by mass, and even more preferably 30 to 85% by mass, relative to 100% by mass of the total content of the resin and pigment in the image.

[0201] The image may be fixed to a part or the whole of the substrate. The film thickness of the image is not particularly limited, but is preferably 0.1 to 1000 μm, more preferably 0.3 to 500 μm, and even more preferably 0.5 to 100 μm. The film thickness can be, for example, a value measured by observation using a laser microscope or the like.

[0202] The image may contain other components in addition to the resin and pigment. For example, it may contain appropriate amounts of additives such as crosslinkers, surfactants, dispersants, leveling agents, UV absorbers, UV stabilizers, thickeners, wetting agents, plasticizers, stabilizers, defoamers, dyes, antioxidants, crosslinking accelerators, pH adjusters, and preservatives. The content of the other components is not particularly limited, but is preferably 30% by weight or less, more preferably 10% by weight or less, and even more preferably 5% by weight or less, relative to 100% by weight of the image. To maximize the effect of the addition, the content is preferably 0.01% by weight or more, and more preferably 0.05% by weight or more.

[0203] The substrate, including its preferred embodiments, is the same as the substrate serving as the printing medium described in "5. Method for manufacturing printed matter," and the explanation given in "5. Method for manufacturing printed matter" can be applied mutatis mutandis.

[0204] The method for manufacturing the image-fixed article of the present disclosure is not particularly limited, and for example, the method for manufacturing the printed matter of the present disclosure described above can be used. Preferred aspects of the manufacturing method are the same as the manufacturing method described in "5. Method for manufacturing printed matter" and its preferred aspects, and the explanation given in "5. Method for manufacturing printed matter" can be applied mutatis mutandis. The image-fixed article of the present disclosure has been described above. The image-fixed article of the present disclosure has excellent image adhesion. In particular, even if the substrate is a polyolefin substrate (for example, a film, molded body, nonwoven fabric, or fabric made of fiber, made of polyolefin), the article has excellent image adhesion to the substrate.

[0205] 7. Compound The compound of the present disclosure will be described. The compound of the present disclosure is characterized by being represented by the following formula (2).

[0206] [ka]

[0207] In the above formula, A 3 represents a hydrocarbon group containing two or more aromatic ring skeletons, and the hydrocarbon group may have a substituent, and the substituent is a nonionic substituent. A 4 represents an alkylene chain having 1 to 10 carbon atoms, and the alkylene chain may have a substituent. 4 may be the same or different. m is an integer from 3 to 100. X 2 represents a group having an ethylenically unsaturated double bond.

[0208] The above compound, including its preferred embodiments, is the same as the compound represented by formula (1) (i.e., polymerizable monomer (M)) described in "1. Polymer," and the description of the polymerizable monomer (M) can be applied mutatis mutandis. That is, the compound of the present disclosure can be suitably used as a polymerizable monomer, and a polymer containing a structural unit derived from the compound of the present disclosure has excellent adhesion to polyolefin substrates. Therefore, by applying the compound of the present disclosure to a polymer for ink, an image having excellent adhesion to polyolefin substrates can be printed.

[0209] For example, A in the above formula (2) 3 , A 4 , X 2 Specific and preferred embodiments of each of A and m in the above formula (1) are 1 , A 2 , X 1 The specific embodiments and preferred embodiments of each of , and n are the same as those of , and the explanations therefor can be applied mutatis mutandis.

[0210] For example, in the compounds of the present disclosure, 3 The "hydrocarbon group containing two or more aromatic ring skeletons" represented by the formula (1) is A 1 The hydrocarbon group having two or more aromatic ring skeletons (i.e., polycyclic phenyl group) represented by the formula (1-a) to (1-f) is preferably at least one selected from the group consisting of the structures represented by the formula (1-a) to (1-f) shown as preferred structures, and the structure represented by the formula (1-a) is more preferred.

[0211] The compound of the present disclosure is represented by the formula (2) X 2 Structures other than A 3 -(OA 4 ) m Since the compound has the structure -O-, it tends to have excellent adhesion to a substrate made of polyolefin. Furthermore, as described in the description of the polymerizable monomer (M) constituting the polymer of the present disclosure, the polymer obtained by polymerizing the compound of the present disclosure as a polymerizable monomer component has the above structure (A 3 -(OA4 ) m -O- structure), especially A 3 -(OA 4 )2- (terminal structure), it has excellent adhesion to substrates made of polyolefins. As a method for estimating the adhesion of a polymer using the compound of the present disclosure to a substrate, a calculation method can be adopted in which the Gaussian16 program manufactured by Gaussian Corporation is used to apply B3LYP to the functional of the density functional theory, 6-31G (d, p) to the basis function, and dispersion force correction (GD3BJ keyword). In this calculation method, the zero-point energy of the terminal structure of the compound of the present disclosure is substituted with the zero-point energy of a molecule having a structure similar to the terminal structure, specifically, a molecule represented by the following formula (2-1) (hereinafter also referred to as structural molecule (I)). The absolute value of the zero-point energy of the structural molecule (I) obtained by this calculation method and the sum of the absolute value of the zero-point energy of the base molecule and the absolute value of the zero-point energy of the aggregate of the structural molecule (I) and the base molecule are found to be correlated with the adhesion of a polymer using a compound of the present disclosure to a substrate.

[0212] [ka]

[0213] In the above formula, A 3 and A 4 are the A in equation (2), respectively. 3 and A 4 is the same as

[0214] In addition, A in the above formula (2-1) 3 is A in the above formula (2) 3 and (OA 4 )2 is A in the above formula (2). 3 Directly bonded to consecutive (OA 4 )2.

[0215] Specifically, the compound of the present disclosure preferably satisfies the following formula (f2-1): (E M +E P8 )-(E MP )<-80kJ / mol (f2-1) In the above formula (f2-1), E M is the absolute value of the zero-point energy of the structural molecule (I), E P8 is the absolute value of the zero-point energy of the propylene octamer, E MP is the absolute value of the zero-point energy of the association of the structural molecule (I) and the propylene octamer, and the structural molecule (I) has a structure represented by the formula (2-1) when the compound is represented by the formula (2).

[0216] The above formula (f2-1) represents the absolute value of the zero-point energy (E M ) and the absolute value of the zero-point energy of the propylene octamer (E P8 ) and the absolute value of the zero-point energy of the association of the structural molecule (I) and the propylene octamer (E MP ) means that the difference d10 from is less than -80kJ / mol. The zero-point energy of the aggregate means the zero-point energy when the structural molecule (I) and the propylene octamer are present in the same space.

[0217] In the compound of the present disclosure, the absolute value of the zero-point energy of the structural molecule (I) (E M ) satisfies the above formula (f2-1), a polymer having as a structural unit a structure derived from a compound having a corresponding terminal structure tends to have better adhesion to polyolefin substrates, particularly polypropylene substrates. The difference d10 is preferably -85 kJ / mol or less, more preferably -90 kJ / mol or less.

[0218] It is also preferable that the compound of the present disclosure satisfies the following formula (f2-2): (E M +E P8 )-(EMP )<(E P6 +E P8 )-(E PP ) (f2-2) In the above formula (f2-2), E M , E P8 , and E MP are the E in the above formula (f2-1), M , E P8 , and E MP It has the same meaning as and is calculated in the same way. In the upper floor ceremony (f2-2), E P6 is the absolute value of the zero-point energy of the propylene hexamer, E PP is the absolute value of the zero-point energy of the association complex of the propylene octamer and the propylene hexamer. The zero-point energy of the association of the propylene octamer and the propylene hexamer means the zero-point energy when the propylene octamer and the propylene hexamer are present in the same space.

[0219] The above formula (f2-2) represents the absolute value of the zero-point energy (E M ) and the absolute value of the zero-point energy of the propylene octamer (E P8 ) and the absolute value of the zero-point energy of the association of the structural molecule (I) and the propylene octamer (E MP ) and the difference d10 is the absolute value of the zero-point energy of the propylene hexamer (E P6 ) and the absolute value of the zero-point energy of the propylene octamer (E P8 ) and the absolute value of the zero-point energy of the association of the propylene hexamer and the propylene octamer (E PP ) is smaller than the difference d20 (a negative value means it is larger).

[0220] In the compound of the present disclosure, the absolute value of the zero-point energy of the structural molecule (I) (E M) satisfies the above relational formula (f2-2), a polymer having, as a structural unit, a structure derived from a compound having a corresponding terminal structure tends to have better adhesion to polyolefin substrates, particularly polypropylene substrates. In the above relational formula (f2-2), the difference (d10-d20) between the difference d10 and the difference d20 is preferably -15 kJ / mol or less, and more preferably -20 kJ / mol or less.

[0221] <Method of manufacturing the compound> The method for producing the above compound is not particularly limited, but a preferred production method will be described below. The method for producing the compound described here can also be used as a method for producing the above polymerizable monomer (M).

[0222] The above compound can be obtained by reacting a compound (A) represented by the following formula (3) with a compound (B) having an ethylenically unsaturated double bond and a group reactive with a hydroxyl group.

[0223] [ka]

[0224] In the above formula, A 5 represents a hydrocarbon group containing two or more aromatic ring skeletons, and the hydrocarbon group may have a substituent, and the substituent is a nonionic substituent. 6 represents an alkylene chain having 1 to 10 carbon atoms, and the alkylene chain may have a substituent. 6 may be the same or different, and z is an integer of 3 to 100.

[0225] The compound (A) is not particularly limited as long as it is represented by the formula (3). Above A 5 is A in the compound represented by the above formula (2). 3 Similarly, the specific embodiments and preferred embodiments of A in the above formula (1) 1 The specific embodiments and preferred embodiments are the same as those of the above A1 The explanation regarding the above can be applied mutatis mutandis. Above A 6 is A in the compound represented by the above formula (2). 4 Similarly, the specific embodiments and preferred embodiments of A in the above general formula (1) are 2 The specific and preferred embodiments are the same as those of the above, and the explanation regarding A2 can be applied mutatis mutandis. The above z, including its specific and preferred embodiments, is the same as the specific and preferred embodiments of n in the above general formula (1), as is m in the compound represented by the above formula (2), and the above explanation regarding n can be applied mutatis mutandis.

[0226] As the compound (A), commercially available products can also be used. Preferred commercially available products include, for example, Newcol 714, Newcol 707, and Newcol 704 manufactured by Nippon Nyukazai Co., Ltd., Noigen EA167 and Noigen EA137 manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and Emulgen A-60 and Emulgen A-90 manufactured by Kao Corporation.

[0227] The compound (B) is not particularly limited as long as it is a compound having a group reactive with a hydroxyl group and a group having an ethylenically unsaturated double bond. The group having an ethylenically unsaturated double bond is not particularly limited, but is preferably a radically polymerizable group, such as a (meth)acryloyl group, a vinyl group, a styryl group, an allyl group, etc. Among these, a (meth)acryloyl group is preferred from the viewpoint of copolymerizability. In particular, the compound (B) contains a group capable of reacting with a hydroxyl group and the above X 2 In the production of the polymerizable monomer (M), it is preferable to use a compound having a group capable of reacting with a hydroxyl group and the above-mentioned X. 1 It is preferable to use a compound having the following formula:

[0228] Examples of the group reactive with the hydroxyl group include a carboxyl group, anhydrous carboxyl group, an isocyanate group, and an ester group. Among these, anhydrous carboxyl group is preferred because it easily reacts with the hydroxyl group of compound (A) to form an ester bond even under mild conditions. From an economical perspective, transesterification with methyl ester or acid esterification of methacrylic acid is preferred. The group having an ethylenically unsaturated double bond and the group capable of reacting with a hydroxyl group may be a combination in which they share a part of each other. For example, acrylic acid, which is an example of compound (B), has an acryloyl group "CH2=CH-C(=O)-" which is a group having an ethylenically unsaturated double bond, and a carboxy group "-C(=O)OH" which is a group capable of reacting with a hydroxyl group, and the "-C(=O)" moiety is present in each group redundantly.

[0229] The compound (B) is, for example, (meth)acrylic acid, (meth)acrylic anhydride, 2-(meth)acryloyloxyethyl isocyanate, (meth)acrylic acid ester such as methyl (meth)acrylate (preferably (meth)acrylic acid C 1-4 Among these, (meth)acrylic acid, (meth)acrylic acid anhydride, 2-methacryloyloxyethyl isocyanate, and methyl methacrylate are preferred, and (meth)acrylic acid anhydride and methyl methacrylate are more preferred.

[0230] The method and conditions for reacting the compound (A) with the compound (B) are not particularly limited. For example, a method of heating a mixture containing the compound (A) and the compound (B), or a method of subjecting the compound (A) to an ester exchange reaction with a (meth)acrylic acid ester such as methyl methacrylate is preferred.

[0231] When an acid anhydride is used as compound (B), a catalyst may be present to promote the reaction. Examples of the catalyst include tertiary amines such as triethylamine, tributylamine, N-methylpiperidine, N-methylmorpholine, 1,4-diazabicyclo[2.2.2]octane, 1,7-diazabicyclo[4.3.0]non-6-ene, 1,8-diazabicyclo[5.4.0]undec-7-ene, dimethylaniline, and dimethylaminopyridine; nitrogen-containing heterocyclic aromatic compounds such as pyridine; and the like.

[0232] When (meth)acrylic acid is used as compound (B), it is preferable to use a catalyst or co-catalyst in the (meth)acrylation reaction, such as a sulfonic acid compound such as paratoluenesulfonic acid, benzenesulfonic acid, xylenesulfonic acid, methanesulfonic acid, or sulfuric acid.

[0233] When a (meth)acrylic acid ester such as a (meth)acrylate is used as compound (B), it is preferable to use an ester exchange catalyst in the ester exchange reaction between compound (A) and the (meth)acrylic acid ester. The transesterification catalyst may be any known one without any particular limitation, and specific examples thereof include oxides such as calcium oxide, barium oxide, lead oxide, zinc oxide, and zirconium oxide; hydroxides such as potassium hydroxide, sodium hydroxide, lithium hydroxide, calcium hydroxide, thallium hydroxide, tin hydroxide, lead hydroxide, and nickel hydroxide; halides such as lithium chloride, calcium chloride, tin chloride, lead chloride, zirconium chloride, and nickel chloride; carbonates such as potassium carbonate, rubidium carbonate, cesium carbonate, lead carbonate, zinc carbonate, and nickel carbonate; hydrogen carbonates such as potassium hydrogen carbonate, rubidium hydrogen carbonate, and cesium hydrogen carbonate; phosphates such as sodium phosphate, potassium phosphate, rubidium phosphate, lead phosphate, zinc phosphate, and nickel phosphate; nitrates such as lithium nitrate, calcium nitrate, lead nitrate, zinc nitrate, and nickel nitrate; carboxylates such as lithium acetate, calcium acetate, lead acetate, zinc acetate, and nickel acetate; sodium methoxide, sodium ethoxide, potassium methoxide, potassium eth ... alkoxy compounds such as lithium t-butoxide, calcium methoxide, calcium ethoxide, barium methoxide, barium ethoxide, tetraethoxytitanium, tetrabutoxytitanium, and tetra(2-ethylhexanoxy)titanium; acetylacetonate complexes such as lithium acetylacetonate, zirconia acetylacetonate, zinc acetylacetonate, dibutoxytin acetylacetonate, and dibutoxytitanium acetylacetonate; quaternary ammonium alkoxides such as tetramethylammonium methoxide, tetramethylammonium t-butoxide, and trimethylbenzylammonium ethoxide; dialkyltin compounds such as dimethyltin oxide, methylbutyltin oxide, dibutyltin oxide, and dioctyltin oxide; distannoxanes such as bis(dibutyltin acetate)oxide and bis(dibutyltin laurate)oxide; and dialkyltin dicarboxylates such as dibutyltin diacetate and dibutyltin dilaurate.These may be used alone or in combination of two or more.

[0234] In the (meth)acrylation reaction using (meth)acrylic acid as the compound (B) and the transesterification reaction using a (meth)acrylic acid ester, a solvent may be used, such as aromatic compound solvents such as benzene, toluene, and xylene, aliphatic compound solvents such as hexane and heptane, alicyclic compound solvents such as cyclohexane, and ether compound solvents such as diisopropyl ether and dibutyl ether. These solvents may be used alone or in combination of two or more. When using a (meth)acrylation reaction, it is preferable to use a solvent that forms an azeotrope with the water produced by the reaction, and when using a transesterification reaction, it is preferable to use a solvent that forms an azeotrope with the alcohol produced by the reaction.

[0235] When the heating is performed, the heating temperature is not particularly limited and may be appropriately selected depending on the compounds (A) and (B) used. From the viewpoints of inhibiting coloration and polymerization and improving productivity, the heating temperature is preferably 50 to 150°C, more preferably 60 to 120°C, and even more preferably 70 to 100°C. When the heating is performed, the heating time is not particularly limited. From the viewpoints of inhibiting coloration and polymerization and improving productivity, the time from mixing the entire amounts of compounds (A) and (B) to completing the reaction is preferably within 24 hours, more preferably within 12 hours, and even more preferably within 8 hours. The reaction may be performed under normal pressure or under pressure.

[0236] The above reaction yields a reaction solution containing the compound of the present disclosure. In addition to the compound of the present disclosure, the reaction solution contains the solvent used in the reaction, residues of Compound (A) and Compound (B), catalyst residues, etc., but the compound of the present disclosure can be isolated by a conventionally known purification method. Examples of the purification method include washing with a basic aqueous solution or an acidic aqueous solution or Glauber's salt solution, and distilling off low-boiling components under reduced pressure. According to the above manufacturing method, the compound of the present disclosure can be obtained efficiently. The obtained compound can be used, for example, as a polymerizable monomer (M) which is a raw material such as the polymer (Pm) and resin particles (Pp) of the present disclosure.

[0237] This application claims the benefit of priority based on Japanese Patent Application No. 2023-36778 filed on March 9, 2023. The entire contents of the specification of Japanese Patent Application No. 2023-36778 filed on March 9, 2023 are incorporated herein by reference.

Examples

[0238] The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to only these examples. Unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass". Each measurement method and evaluation method are as follows.

[0239] <Average particle size> As the average particle size of the resin emulsion particles and the pigment, the resin emulsion or the pigment dispersion as the measurement sample was measured using a particle size distribution measuring instrument (manufactured by Otsuka Electronics Co., Ltd., product number: nanoSAQLA) by the dynamic light scattering method, the autocorrelation function was obtained by the photon correlation method, and the value of the average particle size (hydrodynamic diameter) obtained by cumulant analysis was adopted.

[0240] <Viscosity of ink> Each ink obtained in each example and each comparative example was measured with a TPE-100 E-type viscometer (manufactured by Toki Sangyo Co., Ltd.) at a rotor A24, 0.8 degrees, and 25°C.

[0241] <PP adhesion 1> Substrate: Polypropylene (for automobiles) manufactured by Standard Test Piece Co., Ltd. Evaluation method: A 2-mm-wide checkerboard crosscut was made on the test piece, and a cellophane tape (registered trademark) manufactured by Nichiban Co., Ltd. was attached so as to remove air, and pressure bonding was performed 10 reciprocations at 500 g. After 1 minute, the tape was peeled off at 100 mm / second, and the peeled area was evaluated by the N5 average.

[0242] <PP Adhesion 2> The substrate was changed to a corona-treated OPP film (product number: FOR-AQ) manufactured by Futamura Chemical Co., Ltd., and evaluated in the same manner as PP Adhesion 1 except that a 2-mm-wide cross-cut was not performed. (Judgment Criteria) ◎: No peeling at all. 〇: Peeling area is less than 2%. △: Peeling area is 2 - 5%. ×: Peeling area exceeds 5%.

[0243] <Monomer Production Example> [Example 1-1] In a 300-ml separable flask equipped with a thermometer, a condenser tube, and a stirrer, 40 parts of methacrylic anhydride, 120 parts of Newcol 704 (manufactured by Nippon Emulsion Co., Ltd., an emulsifier having a polycyclic phenyl group and a polyethylene oxide group and no ionic group), 0.9 part of N,N-dimethylaminopyridine, 26 parts of triethylamine, 18 parts of toluene, and 0.005 part of phenothiazine as a polymerization inhibitor were charged. Then, the resulting solution was stirred and reacted at 120°C for 3 hours. After completion of the reaction, the reaction solution was washed twice with 40 parts of a 5 wt% aqueous sodium hydroxide solution and twice with 40 parts of a 20 wt% aqueous sodium sulfate solution, and the light-boiling components were distilled off from the obtained organic phase to obtain 122 parts of a pale yellow transparent liquid of monomer (1), that is, 122 parts of a pale yellow transparent liquid of monomer (1).

[0244] [Example 1-2] Monomer (2) was obtained in the same manner as in Example 1-1 except that 120 parts of Newcol 704 was changed to 120 parts of Newcol 707 (manufactured by Nippon Emulsion Co., Ltd., an emulsifier having a polycyclic phenyl group and a polyethylene oxide group and no ionic group).

[0245] [Example 1-3] Monomer (3) was obtained in the same manner as in Example 1-1, except that 120 parts of Newcol 704 was changed to 120 parts of Noigen EA167 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., an emulsifier having a polycyclic phenyl group and a polyethylene oxide group, but not an ionic group).

[0246] [Examples 1-4] Monomer (4) was obtained in the same manner as in Example 1-1, except that 120 parts of Newcol 704 was changed to 120 parts of Emulgen A-60 (manufactured by Kao Corporation, an emulsifier having a distyrenated phenol group, which is a polycyclic phenyl group, and a polyethylene oxide group, but having no ionic group). In addition, using the Gaussian16 program manufactured by Gaussian, the absolute value of the zero-point energy of the structural molecule (4) represented by formula (2-1-a), the absolute value of the zero-point energy of the propylene octamer, and the absolute value of the zero-point energy of the aggregate of the structural molecule (4) and the propylene octamer were calculated using a calculation method applying B3LYP as the density functional, 6-31G(d,p) as the basis function, and dispersion force correction (GD3BJ keyword). The absolute value of the zero-point energy of the structural molecule (4) (3,343,411 kJ / mol) and the absolute value of the zero-point energy of the propylene octamer (2,582,206 kJ / mol) were subtracted from the absolute value of the zero-point energy of the aggregate of the structural molecule (4) and the propylene octamer (5,925,708 kJ / mol), which was -91 kJ / mol.

[0247] [ka]

[0248] [Comparative Example 1-1] Monomer (5) was obtained in the same manner as in Example 1-1, except that Newcol 704 was replaced with Nonipol 200 (manufactured by Sanyo Chemical Industries, Ltd., an emulsifier having a nonylphenyl group and a polyethylene oxide group, but not an ionic group). In addition, using the Gaussian16 program manufactured by Gaussian Corporation, the absolute value of the zero-point energy of the structural molecule (5) represented by formula (2-1-b), the absolute value of the zero-point energy of the propylene octamer, and the absolute value of the zero-point energy of the complex of the structural molecule (5) and the propylene octamer were calculated by a calculation method that applies B3LYP as the functional of the density functional theory, 6-31G(d,p) as the basis function, and dispersion force correction (GD3BJ keyword). The difference obtained by subtracting the absolute value of the zero-point energy of the association complex of the structural molecule (5) and the propylene octamer (5,228,482 kJ / mol) from the sum of the absolute value of the zero-point energy of the structural molecule (5) (2,646,200 kJ / mol) and the absolute value of the zero-point energy of the propylene octamer (2,582,206 kJ / mol) was −76 kJ / mol.

[0249] [ka]

[0250] [Comparative Example 1-2] Monomer (6) was obtained in the same manner as in Example 1-1, except that Newcol 704 was replaced with Emulgen 404 (manufactured by Kao Corporation, an emulsifier having an oleyl group and a polyethylene oxide group but no ionic group).

[0251] [Comparative Example 1-3] Antox MS-60 (manufactured by Nippon Nyukazai Co., Ltd.) was prepared as a monomer having a polycyclic phenyl group and a polyethylene oxide group, with an ionic group in the polycyclic phenyl group.

[0252] <Emulsion manufacturing example> [Example 2-1] A flask equipped with a dropping funnel, stirrer, nitrogen gas inlet, thermometer, and reflux condenser was charged with 355 parts of deionized water. A pre-emulsion for the first stage of addition was prepared in the dropping funnel. The pre-emulsion consisted of 98 parts of deionized water, 32 parts of a 25% aqueous solution of emulsifier (ADEKA Corporation, trade name: ADEKA REASOAP SR-10), 152 parts of cyclohexyl methacrylate, 44 parts of 2-ethylhexyl acrylate, and 4 parts of acrylic acid. 13 parts of this pre-emulsion, equivalent to 4% of the total pre-emulsion, was added to the flask. The temperature was raised to 70°C while slowly blowing in nitrogen gas, and 12 parts of a 5% aqueous solution of ammonium persulfate was added to initiate polymerization. The remaining pre-emulsion was then added dropwise evenly to the flask over 120 minutes. After the dropwise addition was completed, the contents of the flask were maintained at 70°C for 60 minutes. Subsequently, a second-stage pre-emulsion consisting of 98 parts deionized water, 32 parts of a 25% aqueous solution of emulsifier [ADEKA Corporation, trade name: ADEKA Reasoap SR-10], 71.6 parts of cyclohexyl methacrylate, 44 parts of 2-ethylhexyl acrylate, 4 parts of acrylic acid, and 80 parts of monomer (1), and 12 parts of a 5% aqueous solution of ammonium persulfate were uniformly added dropwise to the flask over 120 minutes. After the dropwise addition was completed, the contents of the flask were maintained at 70°C for 60 minutes. The pH was adjusted to 8 by adding 25% aqueous ammonia, and the polymerization was terminated. The resulting reaction solution was cooled to room temperature and then filtered through a 300-mesh wire mesh to obtain an aqueous dispersion, emulsion (1). The obtained aqueous dispersion contained a polymer, and the polymer was resin emulsion particles, and the resin emulsion particles were emulsion particles with a two-layer structure having an inner layer and an outer layer. The nonvolatile content of this aqueous dispersion (emulsion (1)) was 40%, the average particle size of the resin emulsion particles was 200 nm, the proportion of structural units derived from monomer (1) in the total of all polymers that were nonvolatile was 20%, and the proportion of structural units derived from monomer (1) in the polymer that constituted the outer layer was 40%.

[0253] [Example 2-2] An emulsion (2) was obtained in the same manner as in Example 2-1, except that 8 parts of the monomer (1) and 72 parts of cyclohexyl methacrylate were used instead of 80 parts of the monomer (1). The obtained emulsion (2) contained a polymer, and the polymer was resin emulsion particles. The resin emulsion particles were emulsion particles with a two-layer structure having an inner layer and an outer layer. The content of nonvolatile matter in emulsion (2) was 40%, the average particle size of the resin emulsion particles was 200 nm, the proportion of structural units derived from monomer (1) in the total of all polymers, which were nonvolatile matter, was 2%, and the proportion of structural units derived from monomer (1) in the polymer constituting the outer layer was 4%.

[0254] [Example 2-3] An emulsion (3) was obtained in the same manner as in Example 2-1, except that 80 parts of the monomer (2) was used instead of 80 parts of the monomer (1). The obtained emulsion (3) contained a polymer, and the polymer was resin emulsion particles. The resin emulsion particles were emulsion particles with a two-layer structure having an inner layer and an outer layer. The content of nonvolatile matter in emulsion (3) was 40%, the average particle size of the resin emulsion particles was 200 nm, the proportion of structural units derived from monomer (2) in the total of all polymers, which were nonvolatile matter, was 20%, and the proportion of structural units derived from monomer (2) in the polymer constituting the outer layer was 40%.

[0255] [Example 2-4] An emulsion (4) was obtained in the same manner as in Example 2-1, except that 80 parts of the monomer (3) was used instead of 80 parts of the monomer (1). The resulting emulsion (4) contained a polymer, which was resin emulsion particles, and the resin emulsion particles were emulsion particles with a two-layer structure having an inner layer and an outer layer. The nonvolatile content of emulsion (4) was 40%, the average particle size of the resin emulsion particles was 200 nm, the proportion of structural units derived from monomer (3) in the total of all polymers (nonvolatile content) was 20%, and the proportion of structural units derived from monomer (3) in the polymer constituting the outer layer was 40%.

[0256] [Example 2-5] An emulsion (5) was obtained in the same manner as in Example 2-1, except that 80 parts of the monomer (4) was used instead of 80 parts of the monomer (1). The obtained emulsion (5) contained a polymer, and the polymer was resin emulsion particles, and the resin emulsion particles were emulsion particles with a two-layer structure having an inner layer and an outer layer. The nonvolatile content of emulsion (5) was 40%, the average particle size of the resin emulsion particles was 200 nm, the proportion of structural units derived from monomer (4) in the total of all polymers that were nonvolatile was 20%, and the proportion of structural units derived from monomer (4) in the polymer that constituted the outer layer was 40%.

[0257] [Comparative Example 2-1] An emulsion (6) was obtained in the same manner as in Example 2-1, except that 80 parts of cyclohexyl methacrylate was used instead of 80 parts of the monomer (1). The resulting emulsion (6) contained a polymer, which was resin emulsion particles, and the resin emulsion particles were emulsion particles with a two-layer structure having an inner layer and an outer layer. The nonvolatile content of emulsion (6) was 40%, and the average particle size of the resin emulsion particles was 200 nm.

[0258] [Comparative Example 2-2] An emulsion (7) was obtained in the same manner as in Example 2-1, except that 80 parts of the monomer (5) was used instead of 80 parts of the monomer (1). The resulting emulsion (7) contained a polymer, which was resin emulsion particles, and the resin emulsion particles were emulsion particles with a two-layer structure having an inner layer and an outer layer. The nonvolatile content of emulsion (7) was 40%, and the average particle size of the resin emulsion particles was 200 nm.

[0259] [Comparative Example 2-3] An emulsion (8) was obtained in the same manner as in Example 2-1, except that 80 parts of the monomer (6) was used instead of 80 parts of the monomer (1). The resulting emulsion (8) contained a polymer, which was resin emulsion particles, and the resin emulsion particles were emulsion particles with a two-layer structure having an inner layer and an outer layer. The nonvolatile content of emulsion (8) was 40%, and the average particle size of the resin emulsion particles was 200 nm.

[0260] [Comparative Example 2-4] An emulsion (9) was obtained in the same manner as in Example 2-1, except that 80 parts of Antox MS-60 was used instead of 80 parts of Monomer (1). The resulting emulsion (9) contained a polymer, which was resin emulsion particles, and the resin emulsion particles were emulsion particles with a two-layer structure having an inner layer and an outer layer. The nonvolatile content of emulsion (9) was 40%, and the average particle size of the resin emulsion particles was 200 nm.

[0261] <Pigment dispersion manufacturing example> 5 parts of the dispersant Discoat N-14 (Dai-ichi Kogyo Seiyaku Co., Ltd.), 6 parts of propylene glycol, 70 parts of deionized water, 100 parts of titanium dioxide CR-95 (Ishihara Sangyo Kaisha, Ltd.), and zirconia beads with a particle size of 0.5 mm were filled to a volume ratio of 50% and dispersed using a bead mill to obtain pigment dispersion (1) with a pigment concentration of 55%. The average particle size of the pigment was 330 nm.

[0262] <Ink manufacturing example> [Example 3-1] (Ink Preparation) Ink (1) was prepared by mixing 25 parts of emulsion (1) (10 parts as emulsion particles), 27.3 parts of pigment dispersion (1) (15 parts as pigment), 2 parts of diethylene glycol monobutyl ether, 15 parts of propylene glycol, 0.3 parts of surfactant KF-6011 (Shin-Etsu Chemical Co., Ltd.), and 30.4 parts of deionized water, and filtering the mixture through a 1 μm pore size filter (Advantec Co., Ltd., MCP-1-C10S). The viscosity of ink (1) was 7 mPa s.

[0263] (Image formation by inkjet method) The ink (1) obtained above was introduced into a Mastermind textile printer MMP-TX13, and a nozzle check print (all 180 nozzles were ejected in sequence to print ruled lines) was performed to confirm that it was being ejected from all nozzles. Next, an image was formed on each substrate by printing a 50 mm x 50 mm solid image at 1440 dpi x 1440 dpi, with a print speed setting of 1. The substrates with the image formed were then heated for 10 minutes in a hot air dryer at 80°C to obtain test specimens with printed images. PP Adhesion Evaluation 1 and PP Adhesion Evaluation 2 were performed on each test specimen. The results are shown in Table 1.

[0264] [Examples 3-2 to 3-5 and Comparative Examples 3-1 to 3-4] Except for using 25 parts of the emulsion shown in Table 1 instead of 25 parts of emulsion (1), the inks of Examples 3-2 to 3-5 and Comparative Examples 3-1 to 3-4 were prepared and images were formed in the same manner as in Example 3-1, and PP Adhesion Evaluation 1 and PP Adhesion Evaluation 2 were performed. The results are shown in Table 1. The viscosity of the inks obtained in these Examples and Comparative Examples was 7 mPa s, and nozzle check printing confirmed that they were being ejected from all nozzles.

[0265] [Table 1]

[0266] [Reference example 1] Using the Gaussian16 program manufactured by Gaussian, the density functional function was B3LYP, the basis set was 6-31G(d,p), and dispersion force correction (GD3BJ keyword) was applied. The difference obtained by subtracting the absolute value of the zero-point energy of the aggregate of the propylene hexamer and the propylene octamer from the sum of the absolute values ​​of the zero-point energy of the propylene hexamer and the propylene octamer was found to be -65 kJ / mol.

[0267] [Reference example 2] Using the Gaussian16 program manufactured by Gaussian, the density functional function was B3LYP, the basis set was 6-31G(d,p), and dispersion force correction (GD3BJ keyword) was applied. The difference obtained by subtracting the absolute value of the zero-point energy of the complex of dodecane and the propylene octamer from the sum of the absolute values ​​of the zero-point energy of dodecane and the absolute value of the zero-point energy of the propylene octamer was calculated, and the result was -51 kJ / mol. [Industrial Applicability]

[0268] The polymer of the present invention has excellent adhesion to polyolefin substrates, and is therefore suitable for use in inks used for printing on polyolefin films such as OPP and CPP, inks used for printing on fabrics made of polyolefin fibers such as polyethylene fibers and polypropylene fibers, and inks and primers used for printing on polyolefin molded products such as polyethylene plates and polypropylene plates.

Claims

1. A polymer comprising, as a constituent unit, a structure derived from a polymerizable monomer (M) represented by the following formula (1): 【Chemistry 1】 [In formula (1), A 1 is any one of groups represented by the following formulas (1-a), (1-b), (1-d), (1-e), and (1-f). A 2 represents an alkylene chain having 1 to 10 carbon atoms, and the alkylene chain may have a substituent. 2 may be the same or different. n is an integer from 3 to 100. X 1 represents a group having an ethylenically unsaturated double bond. 【Chemistry 2】 [In the formula, R 1 and R 2 each independently represent a hydrogen atom or a monovalent aliphatic hydrocarbon group. R 3 , R 5 , R 6 , and R 8 each independently represent a monovalent aliphatic hydrocarbon group. R 4 , R 7 , and R 9 each independently represent a divalent aliphatic hydrocarbon group. k represents an integer of 1 to 5, and p represents an integer of 0 to 4. k+p is an integer of 1 to 5. q represents an integer of 0 to 3; r represents an integer of 0 to 4; s represents an integer of 0 to 4, j1 represents an integer of 2 to 5, and j2 represents an integer of 1 to 5. s+j1 is an integer of 2 to 5, and s+j2 is an integer of 1 to 5. * represents the bonding site with the terminal O (oxygen atom) in "(OA 2 ) n " in formula (1).] 2. The polymer according to claim 1, wherein the polymerizable monomer (M) comprises a compound in which A 1 in formula (1) is a group represented by formula (1-a).

3. 2. The polymer according to claim 1, wherein the structure derived from the polymerizable monomer (M) satisfies the following formula (f1-1): (E M +E P8 )-(E MP )<-80+ / / / mol (f1-1) [In formula (f1-1), E M is the absolute value of the zero-point energy of the structural molecule (Ip), E P8 is the absolute value of the zero-point energy of the propylene octamer, E MP is the absolute value of the zero-point energy of the association of the structural molecule (Ip) and the propylene octamer, When the polymerizable monomer (M) is represented by the formula (1), the structural molecule (Ip) has a structure represented by the following formula (1-1): Each zero-point energy is obtained by a calculation method using the Gaussian16 program manufactured by Gaussian, applying B3LYP as the functional of the density functional theory, 6-31G(d,p) as the basis function, and dispersion force correction (GD3BJ keyword).] 【Transformation 3】 [In formula (1-1), A 1 and A 2 are A in the formula (1), respectively. 1 and A 2 is the same as

4. The polymer described in claim 1, wherein the polymer further comprises, as a constituent unit, at least one structure selected from a structure derived from a low Tg (meth)acrylic acid alkyl ester, the glass transition temperature of which of the homopolymer is -20°C or lower, and a structure derived from a (meth)acrylic acid ester having a cyclic aliphatic hydrocarbon group.

5. The polymer described in claim 1, wherein the polymer further contains a structure derived from a (meth)acrylic monomer other than the polymerizable monomer (M) as a constituent unit (however, the polymer does not contain a structure derived from a styrene-based monomer).

6. A polymer described in claim 1 having a weight average molecular weight of 100,000 or more.

7. Resin particles comprising the polymer according to claim 1.

8. The resin particles according to claim 7 , wherein the resin particles are single-layer particles containing the polymer, or particles having a core-shell structure containing the polymer in a shell layer.

9. An aqueous dispersion comprising the resin particles according to claim 7.

10. An ink comprising a binder and a solvent, wherein the binder comprises the polymer of claim 1.

11. The ink according to claim 10, wherein the binder is resin particles containing the polymer.

12. The ink described in claim 10, wherein the solvent is an aqueous solvent.

13. A method for producing a printed matter having an image printed on a substrate, the method comprising: an image forming step of depositing the ink according to claim 10 onto the substrate to form the image.

14. 10. An image-fixed article comprising an image containing a pigment and a resin fixed to a part or all of a substrate, wherein the resin contains the polymer according to claim 1.

15. A compound represented by the following formula (2): 【Chemistry 4】 [In formula (2), A 3 is any one of groups represented by the following formulas (1-a), (1-b), (1-d), (1-e), and (1-f). A 4 represents an alkylene chain having 1 to 10 carbon atoms, and the alkylene chain may have a substituent. 4 may be the same or different. m is an integer from 3 to 100. X 2 represents a group having an ethylenically unsaturated double bond. 【Transformation 5】 [In the formula, R 1 and R 2 each independently represent a hydrogen atom or a monovalent aliphatic hydrocarbon group. R 3 , R 5 , R 6 , and R 8 each independently represent a monovalent aliphatic hydrocarbon group. R 4 , R 7 , and R 9 each independently represent a divalent aliphatic hydrocarbon group. k represents an integer of 1 to 5, and p represents an integer of 0 to 4. k+p is an integer of 1 to 5. q represents an integer of 0 to 3; r represents an integer of 0 to 4; s represents an integer of 0 to 4, j1 represents an integer of 2 to 5, and j2 represents an integer of 1 to 5. s+j1 is an integer of 2 to 5, and s+j2 is an integer of 1 to 5. * represents the bonding site with the terminal O (oxygen atom) in "(OA 4 ) m " in formula (2).]

16. The compound according to claim 15, which satisfies the following formula (f2-1): (E M +E P8 )-(E MP )<-80+ / / / mol (f2-1) [In the above formula (f2-1), E M is the absolute value of the zero-point energy of the structural molecule (I), E P8 is the absolute value of the zero-point energy of the propylene octamer, E MP is the absolute value of the zero-point energy of the association of the structural molecule (I) and the propylene octamer, When the compound is represented by the formula (2), the structural molecule (I) has a structure represented by the following formula (2-1): Each zero-point energy is obtained by a calculation method using the Gaussian16 program manufactured by Gaussian, applying B3LYP as the functional of the density functional theory, 6-31G(d,p) as the basis function, and dispersion force correction (GD3BJ keyword).] 【Transformation 6】 [In formula (2-1), A 3 and A 4 are the A in the formula (2), 3 and A 4 is the same as 17. The compound according to claim 15, wherein A 3 in formula (2) is a group represented by formula (1-a).

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