Polymer, resin particles including said polymer, aqueous dispersion, ink, method for producing printed object using said ink, article with fixed image, 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

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

[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.

[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 containing a binder resin composition for aqueous inkjet inks, characterized by containing specific core-shell resin microparticles, and a specific moisturizing solvent. Patent Document 2 describes an ink composition containing a pigment, specific self-dispersing resin particles, at least two nonionic surfactants having HLBs in different specific ranges, a water-soluble organic solvent, and water. 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.

[0004] JP 2012-201692 A JP 2013-18951 A JP 2016-222754 A

[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.

[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): [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. 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, and n is an integer of 3 to 100. １ represents a group having an ethylenically unsaturated double bond.] [2] The A １ is any one of groups represented by the following formulas (1-a) to (1-f): [In the formula, R １ and R ２ R each independently represents a hydrogen atom or a monovalent aliphatic hydrocarbon group. ３ , R ５ , R ６ , and R ８R each independently represents a monovalent aliphatic hydrocarbon group. 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. * represents "(OA ２ ) ｎ represents a 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): (E Ｍ +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, and 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), and each zero-point energy is a zero-point energy obtained by a calculation method using the Gaussian 16 program manufactured by Gaussian Corporation, 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 formula (1-1), A １ and A ２ are A in the formula (1), respectively. １ and A ２The same as above.] [4] Resin particles comprising the polymer according to any one of [1] to [3]. [5] Resin particles according to [4], wherein the resin particles are single-layer particles comprising the polymer or particles with a core-shell structure comprising the polymer in the shell layer. [6] A water-based dispersion comprising the resin particles according to [4] or [5]. [7] An ink comprising a binder and a solvent, wherein the binder comprises the polymer according to any one of [1] to [3]. [8] The ink according to [7], wherein the binder is resin particles comprising the polymer. [9] A method for producing a printed matter, comprising an image forming step of forming an image by depositing the ink according to [7] or [8] on a substrate.

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

[11] A compound represented by the following formula (2): [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. 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, and m is an integer of 3 to 100. 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 ) <-80 kJ / 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 ＭＰis the absolute value of the zero-point energy of the association of the structural molecule (I) and the propylene octamer, and when the compound is represented by the formula (2), the structural molecule (I) has a structure represented by the following formula (2-1), and each zero-point energy is a zero-point energy obtained by a calculation method using the Gaussian 16 program manufactured by Gaussian Corporation, 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 formula (2-1), A ３ and A ４ are the A in the formula (2), ３ and A ４

[13] The above-mentioned A ３ is any one of groups represented by the following formulas (1-a) to (1-f): [In the formula, R １ and R ２ R each independently represents a hydrogen atom or a monovalent aliphatic hydrocarbon group. ３ , R ５ , R ６ , and R ８ R each independently represents a monovalent aliphatic hydrocarbon group. 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. * represents "(OA ４ ) ｍ represents the bonding site with the terminal O (oxygen atom) in

[0008] Due to the above-mentioned configuration, 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.

[0009] The present invention will be described in detail below. Note that 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. Furthermore, in this specification, "(meth)acrylate" means "acrylate" or "methacrylate", "(meth)acrylic" means "acrylic" or "methacrylic", and "(meth)acryloyl" means "acryloyl" or "methacryloyl". Furthermore, (meth)acrylate is sometimes referred to as a (meth)acrylic acid ester. Furthermore, unless otherwise specified in this specification, "A to B" representing a numerical range means "greater than or equal to A and less than or equal to B".

[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]

[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. 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, and n is an integer of 3 to 100. １ represents a group having an ethylenically unsaturated double bond.

[0013] <Polymerizable Monomer (M)> The polymerizable monomer (M) will be explained. The polymerizable monomer (M) is represented by the above formula (1). In the above formula (1), １ represents a polycyclic phenyl group, and the polycyclic phenyl group means 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 monocyclic aromatic hydrocarbons 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 monocyclic aromatic hydrocarbon skeletons such as a benzene ring (i.e., an unsaturated hydrocarbon ring that exhibits aromaticity by itself), or containing at least one aromatic hydrocarbon skeleton of a fused ring structure (i.e., a fused 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 only of the aromatic ring skeleton (i.e., a hydrocarbon group consisting only of 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. Among 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, and specific examples include alkylene groups having a chain structure such as methylene, ethylene-1,1-diyl, ethylene-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, and hexane-1,6-diyl. The number of carbon atoms in the monovalent or divalent or higher saturated aliphatic hydrocarbon group having a chain structure (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 even more preferably 1 to 3.

[0018] Examples of monovalent saturated aliphatic hydrocarbon groups 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. Examples of n-valent (n = an integer of 2 or more) saturated aliphatic hydrocarbon groups 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 monovalent unsaturated aliphatic hydrocarbon groups having a chain structure include alkenyl groups having a chain structure such as vinyl, n-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 1-pentenyl, 2-pentenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, and 3-methyl-1-butenyl; and alkynyl groups having a chain structure such as ethynyl, 2-propynyl, 3-butynyl, 4-pentynyl, 1-methyl-3-butynyl, 1,1-dimethyl-2-propynyl, and 6-heptynyl. Examples of n-valent (n = an integer of 2 or more) unsaturated aliphatic hydrocarbon groups having a chain structure include groups in which (n-1) hydrogen atoms constituting the monovalent unsaturated aliphatic hydrocarbon group having a chain structure are 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 monovalent cyclic unsaturated aliphatic hydrocarbon groups include cyclic alkenyl groups (i.e., cycloalkenyl groups) such as cyclohexenyl, cycloheptenyl, and cyclooctenyl. Examples of n-valent (n = an integer of 2 or greater) cyclic unsaturated aliphatic hydrocarbon groups include groups in which (n-1) hydrogen atoms constituting the monovalent cyclic unsaturated aliphatic hydrocarbon group are replaced with bonds. The number of carbon atoms in the monovalent or divalent or higher cyclic unsaturated aliphatic hydrocarbon group is preferably 3 to 18, more preferably 4 to 12, and even more preferably 5 to 8.

[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 includes 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 exhibit aromaticity independently), there are no particular limitations on the type of the polycyclic phenyl group, as long as it does not form a fused-ring aromatic hydrocarbon skeleton (i.e., as long as two or more unsaturated hydrocarbon rings are not fused). Typically, in a configuration having two or more monocyclic aromatic hydrocarbon skeletons, the monocyclic aromatic hydrocarbon skeletons (i.e., unsaturated hydrocarbon rings that exhibit aromaticity independently) 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 an embodiment in which the polycyclic phenyl group has two or more aromatic hydrocarbon skeletons of a monocyclic structure (i.e., unsaturated hydrocarbon rings that are independently aromatic), 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 a monocyclic aromatic hydrocarbon ring is fused, more preferably a structure derived from a fused ring aromatic hydrocarbon in which a 4- to 7-membered monocyclic aromatic hydrocarbon ring is 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. Examples of the fused ring aromatic hydrocarbon (i.e., an aromatic hydrocarbon skeleton of a fused ring structure) include, for example, a structure in which only a 6-membered aromatic hydrocarbon ring is fused, such as naphthalene, anthracene, pentacene, benzopyrene, chrysene, pyrene, triphenylene, corannulene, coronene, ovalene, and kekulene; and a structure 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. Among these, 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 of a fused ring structure (i.e., a structure exhibiting aromaticity formed by the fusion of two or more unsaturated hydrocarbon rings), the number of aromatic hydrocarbon skeletons of the 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) via 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) via 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 groups such as phenoxy group and naphthoxy group (preferably C ６－１５ aryloxy groups); acyl groups such as acetyl and benzoyl groups (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);

[0025] The nonionic substituent may be directly bonded to the aromatic ring skeleton constituting the polycyclic phenyl group (i.e., the unsaturated hydrocarbon ring exhibiting 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 an 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, and more preferably a halogen atom, a hydroxyl group, a C １－４ Alkoxy group, C ６－１５ More 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 １The polycyclic phenyl group represented by the formula (I) is preferably a hydrocarbon group A1 having two or more benzene rings which may have a monovalent aliphatic hydrocarbon group, each benzene ring being linked by a single bond or a divalent aliphatic hydrocarbon group, and any one of the benzene rings being bonded to an oxygen atom in formula (1) directly or via a divalent aliphatic hydrocarbon group, or a hydrocarbon group B1 having 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 being bonded to an oxygen atom in formula (1) directly or via a divalent aliphatic hydrocarbon group; It is more preferred that 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 that the hydrocarbon group B2 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; More preferably, the hydrocarbon group A3 has two to six 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 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 the hydrocarbon group B3 has one fused ring in which two to five 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. Note that the hydrocarbon group A1, hydrocarbon group B1, hydrocarbon group A2, hydrocarbon group B2, hydrocarbon group A3, and hydrocarbon group B3 may each have a nonionic substituent as exemplified above, but preferably do not have such a substituent.

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

[0028]

[0029] In the above formula (1-a), R １ and R ２ each independently represents a hydrogen atom or a monovalent aliphatic hydrocarbon group, R ３ Each independently represents a monovalent 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. * 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 or 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); 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; １ is a hydrogen atom, and R ２ is C １－３ is an alkyl group, and R ３ is C１－１２ It is more preferred that the alkyl group is an alkyl group, k is an integer of 1 to 3, and p is an integer of 0 to 1.

[0032]

[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 ４ Examples of the divalent aliphatic hydrocarbon group represented by the formula (I) include the divalent aliphatic hydrocarbon groups explained above (for example, an alkylene group, a divalent saturated alicyclic hydrocarbon group, etc.), and among these, an alkylene group is preferred, an alkylene group having 1 to 18 carbon atoms is more preferred, an alkylene group having 1 to 12 carbon atoms is even more preferred, an alkylene group having 1 to 6 carbon atoms is still more preferred, and an alkylene group having 1 to 3 carbon atoms is 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); 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, more preferably, R １ is a hydrogen atom, and R ２ is C １－３ is an alkyl group, and R ３ is C １－１２ is an alkyl group, and R ４ is C １－１２It 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]

[0037] In the above formula (1-c), R ５ and R ６ Each of the symbols 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] The above R ５ and R ６ 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 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; ５ and R ６ However, each independently, C １－１２ It is more preferred that the group is an alkyl group, q is 0 or 1, and r is 0 or 1.

[0040]

[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] R ７ Examples of the divalent aliphatic hydrocarbon group represented by the formula (I) include the divalent aliphatic hydrocarbon groups explained above (for example, an alkylene group, a divalent saturated alicyclic hydrocarbon group, etc.), and among these, an alkylene group is preferred, an alkylene group having 1 to 18 carbon atoms is more preferred, an alkylene group having 1 to 12 carbon atoms is even more preferred, an alkylene group having 1 to 6 carbon atoms is still more preferred, and an alkylene group having 1 to 3 carbon atoms is particularly preferred.

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

[0045] In the above formula (1-e), R ８ Each of the groups 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 the "(OA ２ ) ｎ " represents the bonding site with the terminal O (oxygen atom) in ".

[0046] The above R ８Examples 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, more preferably an alkyl group having 1 to 18 carbon atoms, even more preferably an alkyl group having 1 to 12 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an alkyl group 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); ８ is an alkyl group, s is 0 or 1, and j is an integer of 1 to 3; ８ is C １－１２ It is more preferred that the alkyl group is an alkyl group, s is 0 or 1, and j is an integer of 1 to 3.

[0048]

[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 ９ Examples of the divalent aliphatic hydrocarbon group represented by the formula (I) include the divalent aliphatic hydrocarbon groups explained above (for example, an alkylene group, a divalent saturated alicyclic hydrocarbon group, etc.), and among these, an alkylene group is preferred, an alkylene group having 1 to 18 carbon atoms is more preferred, an alkylene group having 1 to 12 carbon atoms is even more preferred, an alkylene group having 1 to 6 carbon atoms is still more preferred, and an alkylene group having 1 to 3 carbon atoms is 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); 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, more preferably, R ８ is C １－１２ is an alkyl group, and R ９ is 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 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, i.e., A １ - (OA ２ ) ｎ Therefore, the polymer of the present disclosure has excellent adhesion to polyolefin substrates. In particular, the adhesion to substrates 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 terminal structure) is thought to contribute significantly. As a method for estimating the adhesion of a polymer to a substrate, the present inventors focused on a calculation method using the Gaussian16 program manufactured by Gaussian Corporation, 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 structural molecule (Ip)), and it has been 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]

[0055] In the above formula, A １ and A ２ are A in formula (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 ) <-80 kJ / mol (f1-1) In the above 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.

[0057] Here, the structural molecule (Ip) has a structure represented by the formula (1-1). １ is A in the above formula (1). １and (OA ２ ) ２ is A in the above formula (1). １ (OA ２ ) ２ That is, (OA ２ ) ２ is expressed as A １ - (OA ２ ) ２ - (OA ２ ) ｎ－２ -OX １ When I rewrote it as (OA ２ ) ２ It is preferable that it is the same as. The zero-point energy of the above-mentioned aggregate means the zero-point energy when the structural molecule (Ip) (structural molecule represented by the above formula (1-1)) and the above propylene octamer are in the same space. Each zero-point energy in formula (f1-1) is a zero-point energy obtained by a calculation method using the Gaussian16 program manufactured by Gaussian Corporation, applying B3LYP as the functional of the density functional theory, 6-31G(d,p) as the basis function, and dispersion force correction (GD3BJ keyword). Since each zero-point energy obtained by this calculation method is a negative value, the absolute value of each zero-point energy is used in the above formula (f1-1). The same applies to each zero-point energy in formulas (f1-2), (f2-1), and (f2-2) described below.

[0058] The above formula (f1-1) 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 (Ip) and the propylene octamer (E ＭＰ ) is less than −80 kJ / mol.

[0059] The absolute value of the zero-point energy of the structural molecule (Ip) (E ＭWhen the difference d1 satisfies the 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 E in the above formula (f1-1), respectively. Ｍ , E Ｐ８ , and E ＭＰ 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) 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 (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 (larger with a negative value) than the difference d2.

[0062] In the polymer of the present disclosure, the absolute value of the zero-point energy (E Ｍ When the difference d1 and the difference d2 satisfy the above-mentioned relational formula (f1-2), a polymer 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. In the above-mentioned relational formula (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 (I) include the groups described 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 halogen atoms; polar functional groups; alkoxy groups; and thioalkoxy groups. Examples of the halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Of these, chlorine atoms, bromine atoms, and fluorine atoms are preferred, and fluorine atoms are more preferred. Examples of the polar functional groups include hydroxyl groups, carboxy groups, amino groups, and mercapto groups. Examples of the alkoxy groups include preferably alkoxy groups having 1 to 10 carbon atoms, more preferably alkoxy groups having 1 to 4 carbon atoms, and even more preferably alkoxy groups having 1 carbon atom, i.e., methoxy groups. Examples of the thioalkoxy groups include preferably thioalkoxy groups having 1 to 10 carbon atoms, more preferably thioalkoxy groups having 1 to 4 carbon atoms, and even more preferably thioalkoxy groups having 1 carbon atom, i.e., thiomethoxy groups.

[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 formulas (1-a) to (1-f), and in addition, 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, 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 following formula (I) 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" described later. 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 therefore will not be repeated here.

[0071] <Composition, properties, etc. of polymer (Pm)> The polymer (Pm) of the present disclosure may be a polymer containing only the structure (M) as a structural unit, or may be a polymer containing a structure other than the structure (M) as a structural 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 structural 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 (meth)acrylic monomers and styrene-based monomers. 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 structural units. That is, the polymer (Pm) of the present disclosure is preferably a (meth)acrylic polymer containing the structure (M) and a structure derived from a (meth)acrylic monomer as structural units (but not a structure derived from a styrene-based monomer); a styrene-based polymer containing the structure (M) and a structure derived from a styrene-based monomer as structural units (but not a structure derived from a (meth)acrylic monomer); or a (meth)acrylic-styrene-based polymer containing the structure (M), a structure derived from a (meth)acrylic monomer, and a structure derived from a styrene-based monomer as structural units, with a (meth)acrylic polymer being more preferred.

[0073] The polymer (Pm) of the present disclosure contains the structure (M) as a structural unit, and preferably contains a plurality of the structure (M) as a structural unit, and more preferably contains a plurality of the structure (M) as a repeating structural unit. Note that 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 the structure (M) in the polymer (Pm) of the present disclosure is not particularly limited, but the content of the structure (M) in 100% by mass of the 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 still more preferably 5 to 50% by mass.

[0075] The (meth)acrylic monomer is not particularly limited, and one or more of conventionally known (meth)acrylic acid esters and (meth)acrylic acids can be selected and used. The total content of the structure (M) and the structure derived from the (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 later, the structure derived from a branched (meth)acrylic acid ester described later, the structure derived from a (meth)acrylic acid ester having a cyclic aliphatic hydrocarbon group described later, and the structure derived from an acid group-containing monomer described later, within the above range, and 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 later, the structure derived from a (meth)acrylic acid ester having a cyclic aliphatic hydrocarbon group described later, and the structure derived from an acid group-containing monomer described later, 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 (meth)acrylic acid 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; and amino group-containing linear (meth)acrylic acid esters 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; and the like.

[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, with cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate being more preferred, cyclohexyl (meth)acrylate and isobornyl (meth)acrylate being even more preferred, and cyclohexyl methacrylate and isobornyl acrylate being even more preferred.

[0080] Examples of (meth)acrylic acid esters having a branched alkyl group include branched alkyl (meth)esters 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)esters such as 3-methoxybutyl (meth)acrylate and methoxytripropylene glycol (meth)acrylate; and halogen atom-containing branched alkyl (meth)esters such as hexafluoroisopropyl (meth)acrylate. Among these, branched alkyl (meth)esters 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, may be 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, a value (when multiple Tg values ​​are listed, the lowest value) described in "POLYMER HANDBOOK THIRD EDITION" (by J. BRANDRUP and E. H. IMMERGUT, 1989, published by John Wiley & Sons, Inc., pp. VI / 209 to VI / 277). For compounds not described in "POLYMER HANDBOOK THIRD EDITION," a value (calculated value) determined by a computer using commercially available glass transition temperature calculation software (for example, "MATERIALS STUDIO" manufactured by Accelrys Software Inc., version: 4.0.0.0, module: Synthia, conditions: calculation with a weight average molecular weight of 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%, relative to 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 a 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 the 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 the 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 (for example, methoxy group, ethoxy group, etc.) １－４alkoxyl 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 suitable styrene-based monomers include styrenes that 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. Divinylbenzene is a preferred example of a polyfunctional styrene-based monomer. These styrene-based monomers may be used alone or in combination of two or more. Styrene is preferred as the styrene-based monomer 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 when it is 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] Furthermore, the polymer (Pm) of the present disclosure may contain a structural unit derived from a monomer other than the polymerizable monomer (M), the (meth)acrylic acid ester, the acid group-containing monomer, and the styrene-based monomer (hereinafter, sometimes referred to as "monomer Q"). Examples of the monomer (Q) include: 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 monomers such as maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide; Examples of the monomer include 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 N-n-propyl(meth)acrylamide; vinyl-based monomers such as vinyl acetate, vinyl chloride, and vinyl benzoate; and olefin-based monomers such as ethylene and propylene.

[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 １is 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. The upper limit of the weight average molecular weight is preferably 5,000,000 or less from the viewpoint of viscosity and film-forming properties. The weight average molecular weight refers to the weight average molecular weight (polystyrene equivalent) measured using gel permeation chromatography (manufactured by 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] It is also preferable that the glass transition temperature (Tg) of the polymer (Pm) of the present disclosure is 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, if the glass transition temperature is -40°C or higher, the resulting image is likely to have excellent thermal stability, while if the glass transition temperature is 50°C or lower, the ink is likely to have 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. On the other hand, 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). Preferably, the value obtained by differential scanning calorimetry (DSC) is used. 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) measuring devices include Seiko Instruments Inc.'s DSC220C. Furthermore, when measuring differential scanning calorimetry, there are no particular limitations on the method for plotting a differential scanning calorimetry (DSC) curve, the method for obtaining a first-order derivative curve from a differential scanning calorimetry (DSC) curve, the method for performing smoothing processing, the method for determining the target peak temperature, and the like. For example, when using the above-mentioned measuring device, a graph may be drawn from data obtained using the measuring device. In this case, analytical software capable of performing mathematical processing may be used. Examples of the analysis software include analysis software (manufactured by 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. In addition, the glass transition onset temperature, intermediate temperature, inflection point temperature, and end temperature are observed in the above measurement, and the intermediate 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 a polymerizable monomer (M) represented by the above formula (1). Examples of monomers other than the polymerizable monomer (M) include the aforementioned (meth)acrylic monomers, styrene-based monomers, acid group-containing monomers, and monomer (Q), among others. (Meth)acrylic monomers and / or styrene-based monomers are preferred. The content (charge amount) and blending ratio of each polymerizable monomer in the polymerizable monomer composition may be appropriately selected so as to achieve the content of the structure derived from each monomer in the target polymer. The polymerization method is not particularly limited, and a conventionally known polymerization method can be used. For example, solution polymerization, suspension polymerization, emulsion polymerization, UV curing, and the like can be employed.

[0100] 2. Resin Particles The resin particles of the present disclosure include the polymer (Pm) of the present disclosure described above. The resin particles of the present disclosure are sometimes 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 referred to as polymer (Pm2)). In addition, 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, in which one or more layers are composed of the polymer (Pm) and the remaining layers are 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 its preferred embodiments, is the same as the polymer (Pm) described in "1. Polymer," and the description 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 diameter 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, from the viewpoint of easily obtaining a dispersion system with uniform dispersion and excellent dispersion stability, it is more preferably 10 nm or more and 1 μm or less. From the viewpoint of easily blending the resin particles (Pp) at a high concentration while maintaining the viscosity of the dispersion system within 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. In this specification, the average particle diameter of the resin particles is the average particle diameter (hydrodynamic diameter) obtained by cumulant analysis using a particle size distribution analyzer (manufactured by Otsuka Electronics Co., Ltd., product number: nanoSAQLA) using a dynamic light scattering method to determine the autocorrelation function using a photon correlation method.

[0103] The structure of the resin particles (Pp) of the present disclosure is not particularly limited. The particles may have a uniform composition throughout, or may have 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 have 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). This structure allows inks containing the resin particles (Pp) to exhibit superior 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) are particles with a core-shell structure, the polymer constituting the layer other than the outermost shell (for example, the core portion) may be the polymer (Pm) or the polymer (Pm2), but is preferably the polymer (Pm2). When both the core and the shell are composed of the polymer (Pm), it is preferable that the mass ratio of the structure derived from the polymerizable monomer (M) in the polymer (Pm) in the shell portion is larger than the mass ratio 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, phenolic 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 structural units 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 (meth)acrylic monomer-derived structure 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). It is particularly preferred to adjust the total content of the low-Tg (meth)acrylic acid alkyl ester-derived structure, the (meth)acrylic acid ester-derived structure having a cyclic aliphatic hydrocarbon group, and the acid group-containing monomer-derived structure 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 form. 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 its preferred forms. 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 cycloalkyl (meth)acrylate-derived structure and the isobornyl (meth)acrylate-derived structure 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 the 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. The styrene-based monomer is the same as the styrene-based monomer described above, including its preferred form. 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 a structure (M), but preferably does not contain one. The structure (M) is the same as the structure (M) described above, including its preferred form. 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 other than the (meth)acrylic monomer, styrene monomer, acid group-containing monomer, and 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, and 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)) to fall 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 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 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 having excellent thermal stability, while a glass transition temperature of 50°C or lower tends to result in an ink having excellent film-forming ability at low temperatures. The upper limit of the Tg is more preferably 45°C or lower, and even more preferably 40°C or lower. On the other hand, 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 conventional 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, the method for producing the resin particles (Pp) of the present disclosure is preferably an emulsion polymerization method or a suspension polymerization method carried out in an aqueous medium. 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 referred to as aqueous emulsion particles. In the above emulsion polymerization method, polymerization may be carried out in a single stage or multiple stages. For example, in the first step, a polymerizable monomer composition comprising 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 comprising monomers constituting the polymer (Pm) is polymerized to synthesize the shell (i.e., the polymer (Pm)). This allows resin particles having a core-shell structure to be produced. Resin particles having a core-shell structure can also be produced by a method (seed emulsion polymerization) in which particles obtained by a suspension polymerization method, an emulsion polymerization method, or the like are used as seed particles and the seed particles are subjected to emulsion polymerization in the presence of the seed particles. The content (charge amount) and blending ratio of each polymerizable monomer in the polymerizable monomer composition may be appropriately selected so as to achieve 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 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, the preferred aspects of their particle shape, average particle size, particle structure, particle composition, glass transition temperature, etc. are the same as the preferred aspects 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 organic solvents described above may be used alone or in combination of two or more thereof.

[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) described in "2. Resin Particles," and the description 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 two or more types in the aqueous dispersion (preferably the aqueous emulsion). Among the surfactants, nonionic surfactants and / or anionic surfactants are preferred. Furthermore, surfactants containing polymerizable groups in their molecules are also preferred. Examples of polymerizable groups include groups having ethylenically unsaturated double bonds. Among the surfactants, nonionic surfactants containing polymerizable groups and / or anionic surfactants containing polymerizable groups are particularly preferred. Surfactants containing polymerizable groups 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; sulphate salts; dialkylsulphosuccinate salts; arylsulphonic acid-formalin condensates; fatty acid salts such as ammonium laurate and sodium stearylate; allyl group-containing sulphuric acid esters or salts thereof such as bis(polyoxyethylene polycyclic phenyl ether) methacrylate sulphonate salts, propenyl-alkylsulphosuccinate ester salts, (meth)acrylic acid polyoxyethylene sulphonate salts, (meth)acrylic acid polyoxyethylene phosphonate salts and sulphonate salts of allyloxymethyl alkyloxy polyoxyethylene; sulphuric acid ester salts of allyloxymethyl alkoxyethyl polyoxyethylene, polyoxyalkylene alkenyl ether ammonium sulphate salts, and the like.

[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 polymer 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.), allyloxymethyl alkyloxy polyoxyethylene sulfonate salts (e.g., Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon KH-10, etc.), polyoxyethylene styrenated propenyl phenyl ether sulfate ammonium salts, 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 allyloxymethylnonylphenoxyethyl hydroxypolyoxyethylene (e.g., trade name: Adeka Reasoap SE-10, manufactured by ADEKA Corporation), allyloxymethylalkoxyethyl 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.); and 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, per 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 incorporating the resin particles at a high concentration while maintaining the viscosity of the dispersion within 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 dispersed particle size of the 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 a dynamic light scattering method. In either measurement method, the aqueous dispersion may be appropriately diluted with ion-exchanged water and used as a sample. In particular, it is preferable to use a particle size distribution analyzer (manufactured by Otsuka Electronics Co., Ltd., product number: nanoSAQLA) using the dynamic light scattering method, determine the autocorrelation function by photon correlation analysis, and then use the average particle size (hydrodynamic diameter) determined by cumulant analysis.

[0139] From the viewpoint of the stability of the aqueous dispersion, 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. Any pH adjuster can be used to adjust the pH of the aqueous dispersion of the present disclosure to the above-mentioned 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 of mixing resin particle (Pp) powder with an aqueous solvent and dispersing the mixture can be employed. 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 a portion of the solvent, thereby adjusting the content of aqueous emulsion particles, to produce the aqueous dispersion of the present disclosure. The aqueous dispersion of the present disclosure can also be produced by adding water, an organic solvent, or an aqueous solvent to the 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, wherein the binder contains the polymer (Pm) of the present disclosure and / or the resin particles (Pp) of the present disclosure. Therefore, use of the ink of the present disclosure tends to facilitate the production of printed matter with excellent adhesion to the substrate. In particular, when the substrate is made of polyolefin, it is easy to obtain a printed matter with excellent adhesion to the substrate.

[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, with an aqueous solvent being 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, solvents other than water (i.e., organic solvents) that can be used in the aqueous solvent can also be organic solvents similar to the organic solvents in the aqueous solvent constituting the aqueous dispersion of the present disclosure described above, and the preferred embodiments are also the same. An ink of the present disclosure in which the solvent is an aqueous solvent is also referred to as an aqueous ink.

[0143] The polymer (Pm) and resin particles (Pp) contained as a binder in the ink of the present disclosure, including their respective preferred embodiments, are similar to the polymer (Pm) and resin particles (Pp) and their preferred embodiments explained in "1. Polymer" and "2. Resin Particles," and the explanations 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 has a glass transition temperature of 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. For the same reasons as in the case of the polymer (Pm), the resin particles (Pp) also preferably have a glass transition temperature in the same range.

[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. On the other hand, 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 polymers (Pm), one or more resin particles (Pp), or one or more polymers (Pm) and one or more resin particles (Pp). Among 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. Examples of materials that can be used as the other binder components 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 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 the content is less than 1% by mass, there is a risk of performance such as reduced adhesion, while if it exceeds 70% by mass, there is a risk of high viscosity and reduced workability. The content is more preferably 5% by mass or more and 65% by mass or less. Furthermore, 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. Furthermore, when the ink of the present disclosure is a clear ink that does not contain a 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 still more preferably 70 to 98% by mass. In this specification, the solid content refers to the 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] Preferably, the ink of the present disclosure further contains a pigment. The inclusion of a pigment allows the hue of the ink to 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 colors of subtractive color mixing, magenta, yellow, and cyan, as well as colors of different shades, such as light cyan, dark yellow, light magenta, and light black. Furthermore, the ink may contain one or more hues selected from red, blue, orange, green, and violet. In this specification, a pigment that exhibits a white hue may be referred to as a white pigment, and a pigment that exhibits 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 the pigment 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 C.I. Pigment Yellow, C.I. Pigment Red, C.I. Pigment Orange, C.I. Pigment Violet, C.I. Pigment Blue, and C.I. Pigment Green. When using a polypropylene substrate such as a polypropylene fabric, it is preferable to use a metal-free organic pigment so as not to promote thermal decomposition of the polypropylene. Specifically, C.I. Pigment Blue 16 or the like can be selected.

[0157] Examples of inorganic pigments include titanium dioxide, antimony trioxide, zinc oxide 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. Furthermore, 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] Preferred color pigments include the above organic pigments, red iron oxide, black iron oxide, chromium oxide green, carbon black, yellow lead, molybdenum red, ferric ferrocyanide (Prussian blue), ultramarine, and lead chromate.

[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 preferred to use a particle size distribution analyzer using dynamic light scattering (Otsuka Electronics Co., Ltd., product number: nanoSAQLA) to determine an 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 a measurement method 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 per 100 parts by mass of the pigment.

[0163] When the ink of the present disclosure contains a pigment, the content of the pigment is not particularly limited, but is preferably 1 to 40% by mass per 100% by mass of ink. If the content is less than 1% by mass, there is a risk that the color development will be insufficient, and if the content is more than 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 per 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, if a pigment is included, the pigment, 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 refers to 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 the oxazoline group-containing polymer 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, from the viewpoint of excellent crosslinking performance. The oxazoline group-containing polymer can be produced by a conventionally known production method. 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 monomer exemplified as a monomer constituting the polymer (Pm)) that does not have a functional group reactive with the oxazoline group can be exemplified. Examples thereof 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 EPOCROS WS-500 and EPOCROS WS-700, manufactured by Nippon Shokubai Co., Ltd., and emulsion polymers such as EPOCROS K-2010, EPOCROS K-2020, and EPOCROS K-2030. Of these, water-soluble polymers such as EPOCROS WS-500 and EPOCROS 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 parts by mass or more and 20 parts by mass or less. 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 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 crosslinker, and additives, if necessary. In a preferred embodiment, an aqueous dispersion containing resin particles (Pp) (preferably an aqueous emulsion containing aqueous emulsion particles) is prepared in advance, and the aqueous dispersion (preferably the aqueous emulsion) is mixed with other components. Furthermore, in preparing an ink containing a pigment, a pigment dispersion containing the pigment is prepared in advance, and the aqueous dispersion (preferably the aqueous emulsion) is mixed with other components such as a crosslinker. Below, an example of the production of an aqueous ink using aqueous emulsion particles as a binder is shown.

[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] Furthermore, when 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 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 a solution diluted with a solvent may be used. The method and order of mixing the components are not particularly limited. For example, when a pigment dispersion and a crosslinking agent are used as other components, the aqueous emulsion and the pigment dispersion may be mixed together, and then the crosslinking agent may be mixed; the pigment dispersion and the crosslinking agent may be mixed together, and then the aqueous emulsion may be mixed; the aqueous emulsion and the crosslinking agent may be mixed together, and then the pigment dispersion may be mixed; or the pigment dispersion, the aqueous 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. Examples of the solvent include water, organic solvents such as glycols, and mixtures of water and organic solvents. Components such as additives other than those described above may also be added. The timing of mixing these solvents (adjustment solvents), additives, etc. may be selected appropriately. After mixing the components, centrifugation or filtration may be performed as needed. The above-described production method can be used to produce an aqueous ink containing aqueous emulsion particles and an aqueous solvent (e.g., an aqueous ink containing a pigment, aqueous emulsion particles, a crosslinker, and an aqueous solvent). While an example of the ink production method of the present disclosure has been shown, the method is not limited to the above.

[0179] 5. Method for Producing Printed Material A method for producing a printed material according to the present disclosure will be described. The method for producing a printed material according to the present disclosure uses the ink according to the present disclosure. That is, the method for producing a printed material according to the present disclosure is a method for producing a printed material having an image printed on a substrate, the method including an image formation step of forming an image by applying the ink according to the present disclosure to a substrate. Therefore, the printed material obtained by the method for producing a printed material according to the present disclosure has excellent adhesion to the substrate. In particular, when the substrate is made of polyolefin, a printed material having excellent adhesion to the substrate is easily obtained.

[0180] The ink used in the method for producing a printed matter of the present disclosure is an ink containing a binder and a solvent, wherein the binder contains the polymer (Pm) and / or resin particles (Pp) of the present disclosure (preferably resin particles (Pp) of the present disclosure). The specific composition 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 composition of the ink (e.g., the type and amount of solvent and binder contained in the ink), including preferred embodiments thereof, described in "4. Ink," and the description thereof can be applied mutatis mutandis. From the perspective of low environmental impact, the ink used in the method for producing a 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 a substrate may be referred to as a "printed item."

[0182] Preferred examples of the natural fibers include silk, cotton, and wool. Preferred examples of 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 polyester films 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] The ink of the present invention is particularly suitable for use with 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 and polypropylene fibers); films made of polyolefins (e.g., polyethylene and polypropylene); and molded products of polyolefins such as polyolefin plates (e.g., polyethylene plates and polypropylene plates). Among the polyolefin substrates, fabrics made of polyolefin fibers and films made of polyolefins 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 depositing the ink of the present disclosure on the substrate to form an image 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 the image formation step of depositing the ink of the present disclosure on a substrate, a substrate on which the image has been 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 printer, a thermal printer, or a charge change control printer (continuous ejection printer), can be used. Among these, a piezoelectric inkjet printer is preferred. When using a piezoelectric 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), and each is preferably 5 minutes or less.

[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] The image-fixed article of the present disclosure will be described below. 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 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) containing, as a structural unit, a structure derived from the polymerizable monomer (M) represented by the formula (1). The polymer (Pm) contained in the resin, including preferred embodiments thereof, 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 resin components other than the polymer (Pm). Resin components other than the polymer (Pm) of the present disclosure 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-based 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, based on 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 all of the substrate. The 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 thickness can be 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. Furthermore, to achieve the desired effect, the content is preferably 0.01% by weight or more, 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 those described in "5. Method for Manufacturing Printed Matter," including their preferred aspects, and the explanation 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, or nonwoven fabric made of polyolefin, or a fabric made of fiber), 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]

[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. 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, and m is an integer of 3 to 100. X ２ represents a group having an ethylenically unsaturated double bond.

[0208] The above compound, including preferred embodiments thereof, is similar to the compound represented by formula (1) (i.e., polymerizable monomer (M)) described in "1. Polymer," and the description given for 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 a polyolefin substrate. Therefore, by applying the compound of the present disclosure to a polymer for an ink, an image having excellent adhesion to a polyolefin substrate can be printed.

[0209] For example, A in the above formula (2) ３ , A４ , X ２ Specific and preferred embodiments of each of A and m in the above formula (1) are １ , A ２ , X １ , and n are the same as the specific and preferred embodiments of each of them, 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 of the hydrocarbon group having two or more aromatic ring skeletons (i.e., polycyclic phenyl group), and more preferably the structure represented by the formula (1-a).

[0211] The compound of the present disclosure is represented by the formula (2) X ２ Structures other than, i.e., A ３ - (OA ４ ) ｍ 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 - (OA ４ ) ｍ -O- structure), particularly A ３ - (OA ４ ) ２- structure (terminal structure), resulting in excellent adhesion to substrates made of polyolefins. As a method for estimating the adhesion of a polymer using a 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, and the density functional function is B3LYP, the basis function is 6-31G (d, p), and dispersion force correction (GD3BJ keyword) is applied. In this calculation method, the zero-point energy of the terminal structure possessed by 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 sum of the absolute value of the zero-point energy of the structural molecule (I) and the absolute value of the zero-point energy of the base molecule, obtained by this calculation method, and the magnitude of the difference between the absolute value of the zero-point energy of the aggregate of the structural molecule (I) and the base molecule, and the adhesion of a polymer using a compound of the present disclosure to a substrate have been found to be correlated.

[0212]

[0213] In the above formula, A ３ and A ４ are the A in formula (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 (OA ４ ) ２ It is preferably the same as

[0215] Specifically, the compound of the present disclosure preferably satisfies the following formula (f2-1): (E Ｍ +E Ｐ８ )-(E ＭＰ ) <-80 kJ / 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), EＰ８ 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 The zero-point energy of the aggregate means the zero-point energy when the structural molecule (I) and the propylene octamer are 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 When the difference d10 satisfies the 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 a polyolefin substrate, particularly a polypropylene substrate. The difference d10 is preferably −85 kJ / mol or less, and 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 )-(E ＭＰ ) < (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.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.

[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 (larger with a negative value) than the difference d20.

[0220] In the compound of the present disclosure, the absolute value of the zero-point energy of the structural molecule (I) (E Ｍ When the formula (f2-2) 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 for producing compound> The method for producing the compound is not particularly limited, but a preferred method will be described. The method for producing the compound described here can also be used as a method for producing the 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]

[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). ５ is A in the compound represented by the above formula (2). ３ Similarly, A in the above formula (1) including its specific embodiments and preferred embodiments １ The specific embodiments and preferred embodiments are the same as those of the above A １ The explanation regarding the above can be applied mutatis mutandis. 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 of z are the same as those of n in the general formula (1), including specific and preferred embodiments thereof, as with m in the compound represented by formula (2), and the explanation for n above 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 Dai-ichi 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 has 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, for example, 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) is preferably a compound having a group reactive with a hydroxyl group and the group having the X ２ In the production of the polymerizable monomer (M), it is preferable to use a compound (B) 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, an ester group, etc. Among these, anhydrous carboxyl group is preferred because it easily reacts with the hydroxyl group of compound (A) even under mild conditions to form an ester bond. Economically, transesterification with methyl ester or acid esterification of methacrylic acid is preferred. The group having an ethylenically unsaturated double bond and the group reactive with a hydroxyl group may be a combination in which they share a part of each group. For example, acrylic acid, which is an example of compound (B), contains an acryloyl group "CH ２ It has a carboxy group "-C(=O)OH" which is a group that can react with a hydroxyl group, and the "-C(=O)" portion exists overlappingly in each group.

[0229] The compound (B) may be, for example, (meth)acrylic acid, (meth)acrylic anhydride, 2-(meth)acryloyloxyethyl isocyanate, methyl (meth)acrylate, or other (meth)acrylic acid esters (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 a transesterification 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)acrylate 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 a transesterification catalyst in the transesterification 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, and examples thereof include 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. In the case of using a (meth)acrylation reaction, it is preferable to use a solvent that forms an azeotrope with water produced by the reaction, and in the case of using a transesterification reaction, it is preferable to use a solvent that forms an azeotrope with alcohol produced by the reaction.

[0235] When the heating is carried out, the heating temperature is not particularly limited and may be appropriately selected depending on the compounds (A) and (B) used; however, from the viewpoints of inhibiting discoloration, inhibiting 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 carried out, the heating time is not particularly limited; however, from the viewpoints of inhibiting discoloration, inhibiting polymerization, and improving productivity, the time from the time when the total amounts of compounds (A) and (B) are mixed to the completion of the reaction is preferably within 24 hours, more preferably within 12 hours, and even more preferably within 8 hours. The reaction may be carried out 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 compounds (A) and (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-described production method, the compound of the present disclosure can be efficiently obtained. The obtained compound can be used, for example, as a polymerizable monomer (M), which is a raw material for the polymer (Pm), resin particles (Pp), etc. 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.

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

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

[0240] <Ink Viscosity> The viscosity of each ink obtained in each example and comparative example was measured using an E-type viscometer TPE-100 (manufactured by Toki Sangyo Co., Ltd.) with rotor A24, at 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 grid cross-cut was made on the test specimen, and Cellotape (registered trademark) manufactured by Nichiban Co., Ltd. was attached to the test specimen while removing air, and the test specimen was pressed back and forth at 500 g 10 times. After 1 minute, the tape was peeled off at 100 mm / sec, and the peeled area was evaluated using an N5 average.

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

[0243] <Monomer Production Examples> [Example 1-1] A 300 ml separable flask equipped with a thermometer, a condenser, and a stirrer was charged with 40 parts of methacrylic anhydride, 120 parts of Newcol 704 (manufactured by Nippon Nyukazai Co., Ltd., an emulsifier having a polycyclic phenyl group and a polyethylene oxide group and no ionic group), 0.9 parts of N,N-dimethylaminopyridine, 26 parts of triethylamine, 18 parts of toluene, and 0.005 parts of phenothiazine as a polymerization inhibitor. The resulting solution was then stirred at 120°C for 3 hours to react. 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. Low-boiling components were distilled off from the resulting organic phase to obtain 122 parts of a pale yellow, transparent liquid of Monomer (1), i.e., 122 parts of Monomer (1) as a pale yellow, transparent liquid.

[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 Nyukazai 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 Dai-ichi Kogyo Seiyaku Co., Ltd., an emulsifier having a polycyclic phenyl group and a polyethylene oxide group and no ionic group).

[0246] [Example 1-4] Monomer (4) was obtained by producing in the same manner as in Example 1-1, except that 120 parts of Newcol 704 was replaced with 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, and having no ionic group). In addition, using the Gaussian 16 program manufactured by Gaussian Corporation, 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 associated complex of the structural molecule (4) and the propylene octamer were each calculated using a calculation method applying 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 of the structural molecule (4) and the propylene octamer (5,925,708 kJ / mol) from the sum of 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) was −91 kJ / mol.

[0247]

[0248] [Comparative Example 1-1] Monomer (5) was obtained by producing 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 and no ionic group). In addition, using the Gaussian 16 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 associated complex of the structural molecule (5) and the propylene octamer were each calculated using a calculation method in which B3LYP was used as the functional of the density functional theory, 6-31G (d, p) as the basis function, and dispersion force correction (GD3BJ keyword) were applied. 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]

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

[0251] Comparative Examples 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 Production Examples> [Example 2-1] 355 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser. A pre-emulsion for first-stage dropping was prepared in the dropping funnel, consisting of 98 parts of deionized water, 32 parts of a 25% aqueous solution of an emulsifier [manufactured by 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 amount of the 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. Thereafter, the remainder of the pre-emulsion for dropping was uniformly added dropwise to the flask over 120 minutes. After completion of the dropwise addition, the contents of the flask were maintained at 70°C for 60 minutes. Subsequently, a second-stage pre-emulsion consisting of 98 parts of deionized water, 32 parts of a 25% aqueous solution of an emulsifier [manufactured by 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 completion of the dropwise addition, the contents of the flask were maintained at 70°C for 60 minutes, and the pH was adjusted to 8 by adding 25% aqueous ammonia, thereby terminating the polymerization. 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 resulting aqueous dispersion contained a polymer, which 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 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, which are nonvolatile matter, was 20%, and the proportion of structural units derived from monomer (1) in the polymer constituting the outer layer was 40%.

[0253] Example 2-2: Emulsion (2) was obtained by production in the same manner as in Example 2-1, except that 8 parts of monomer (1) and 72 parts of cyclohexyl methacrylate were used instead of 80 parts of 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: Emulsion (3) was obtained in the same manner as in Example 2-1, except that 80 parts of monomer (2) was used instead of 80 parts of 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: Emulsion (4) was obtained by production in the same manner as in Example 2-1, except that 80 parts of monomer (3) was used instead of 80 parts of monomer (1). The obtained emulsion (4) 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 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, which were nonvolatile components, 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: Emulsion (5) was obtained by production in the same manner as in Example 2-1, except that 80 parts of monomer (4) was used instead of 80 parts of monomer (1). The obtained emulsion (5) 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 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, which were nonvolatile components, was 20%, and the proportion of structural units derived from monomer (4) in the polymer constituting the outer layer was 40%.

[0257] Comparative Example 2-1: 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 Monomer (1). The obtained emulsion (6) 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 nonvolatile content in emulsion (6) was 40%, and the average particle size of the resin emulsion particles was 200 nm.

[0258] Comparative Example 2-2: Emulsion (7) was obtained in the same manner as in Example 2-1, except that 80 parts of monomer (5) was used instead of 80 parts of monomer (1). The obtained emulsion (7) 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 nonvolatile content in emulsion (7) was 40%, and the average particle size of the resin emulsion particles was 200 nm.

[0259] Comparative Example 2-3: Emulsion (8) was obtained in the same manner as in Example 2-1, except that 80 parts of monomer (6) was used instead of 80 parts of monomer (1). The obtained emulsion (8) 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 nonvolatile content in emulsion (8) was 40%, and the average particle size of the resin emulsion particles was 200 nm.

[0260] Comparative Example 2-4: 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. The resin emulsion particles had 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 Production Example> 5 parts of a dispersant, Discoat N-14 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), 6 parts of propylene glycol, 70 parts of deionized water, 100 parts of titanium oxide, CR-95 (manufactured by Ishihara Sangyo Kaisha), 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 a pigment dispersion (1) containing 55% pigment. The average particle size of the pigment was 330 nm.

[0262] <Ink Production Examples> [Example 3-1] (Ink Preparation) 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 (manufactured by Shin-Etsu Chemical Co., Ltd.), and 30.4 parts of deionized water were mixed and filtered through a 1 μm pore size filter (manufactured by Advantec Co., Ltd., MCP-1-C10S) to prepare ink (1). 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 nozzle check printing (a total of 180 nozzles were ejected in sequence to print ruled lines) was performed to confirm that the ink was being ejected from all nozzles. Next, an image was formed on each substrate by performing solid printing of 50 mm x 50 mm at 1440 dpi x 1440 dpi, printing speed setting 1, on the substrate. The substrate on which the image was formed was subjected to a heat treatment for 10 minutes in a hot air dryer at 80°C to obtain a test specimen on which the image was printed. 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 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, except that 25 parts of an emulsion shown in Table 1 was used instead of 25 parts of Emulsion (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]

[0266] Reference Example 1 Using the Gaussian16 program manufactured by Gaussian Corporation, a calculation method was performed in which B3LYP was used as the functional of the density functional theory, 6-31G(d,p) as the basis function, and dispersion force correction (GD3BJ keyword) was applied. The difference obtained by subtracting the absolute value of the zero-point energy of the association of the propylene hexamer and the propylene octamer from the sum of the absolute value of the zero-point energy of the propylene hexamer and the absolute value of the zero-point energy of the propylene octamer was found to be −65 kJ / mol.

[0267] Reference Example 2 Using the Gaussian 16 program manufactured by Gaussian Corporation, a calculation method was performed in which B3LYP was used as the functional in the density functional theory, 6-31G(d,p) as the basis function, and dispersion force correction (GD3BJ keyword) was applied. The difference obtained by subtracting the absolute value of the zero-point energy of the association of dodecane and the propylene octamer from the sum of the absolute value of the zero-point energy of dodecane and the absolute value of the zero-point energy of the propylene octamer was found to be −51 kJ / mol.

[0268] The polymer of the present invention has excellent adhesion to polyolefin substrates, and therefore can be suitably used 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 structural unit, a structure derived from a polymerizable monomer (M) represented by the following formula (1). 【Chemical 1】 [In formula (1), A 1 is any one of the 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. A plurality of A 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. [Chemical Formula 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 from 1 to 5, and p represents an integer from 0 to 4. k + p is an integer from 1 to 5. q represents an integer from 0 to 3, and r represents an integer from 0 to 4. s represents an integer from 0 to 4, j1 represents an integer from 2 to 5, and j2 represents an integer from 1 to 5. s + j1 is an integer from 2 to 5, and s + j2 is an integer from 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) contains a compound in which A 1 in formula (1) is a group represented by formula (1-a).

3. 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 kJ / 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 octameric propylene, E MP is the absolute value of the zero-point energy of the complex of the above structural molecule (Ip) and the above octameric propylene, and When the above structural molecule (Ip) is when the above polymerizable monomer (M) is represented by the above formula (1), it has a structure represented by the following formula (1-1), Each zero-point energy is the zero-point energy obtained by a calculation method in which the B3LYP functional and the 6-31G(d,p) basis function are applied to the functional of the density functional method and the dispersion force correction (GD3BJ keyword) is used using the Gaussian16 program manufactured by Gaussian, Inc.] 【Chemical Formula 3】 [In formula (1-1), A 1 and A 2 are respectively the same as A 1 and A 2 in the said formula (1).]

4. The polymer according to claim 1, further comprising, as a structural unit, at least one structure selected from a structure derived from a low Tg (meth) acrylic acid alkyl ester having a glass transition temperature of the homopolymer of -20°C or lower and a structure derived from a (meth) acrylic acid ester having a cycloaliphatic hydrocarbon group.

5. The polymer according to claim 1, further comprising, as a structural unit, a structure derived from a (meth) acrylic monomer other than the polymerizable monomer (M) (provided that the polymer does not contain a structure derived from a styrene monomer).

6. The polymer according to claim 1, having a weight average molecular weight of 100,000 or more.

7. Resin particles characterized by containing 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 core-shell structured particles containing the polymer in the shell layer.

9. An aqueous dispersion characterized by containing the resin particles according to claim 7.

10. An ink containing a binder and a solvent, wherein the binder contains the polymer according to claim 1.

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

12. The ink according to claim 10, wherein the solvent is an aqueous solvent.

13. A method for manufacturing a printed matter having an image printed on the substrate, including an image forming step of forming an image by attaching the ink according to claim 10 to the substrate.

14. An image-fixing article in which an image containing a pigment and a resin is fixed to 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). 【Chemical 4】 [In formula (2), A 3 is any one of the 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. A plurality of A 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. [Chemical Formula 5] [In the formula, R1 and R2 each independently represent a hydrogen atom or a monovalent aliphatic hydrocarbon group. R3, R5, R6, and R8 each independently represent a monovalent aliphatic hydrocarbon group. R4, R7, and R9 each independently represent a divalent aliphatic hydrocarbon group. k represents an integer from 1 to 5, and p represents an integer from 0 to 4. k + p is an integer from 1 to 5. q represents an integer from 0 to 3, and r represents an integer from 0 to 4. s represents an integer from 0 to 4, j1 represents an integer from 2 to 5, and j2 represents an integer from 1 to 5. s + j1 is an integer from 2 to 5, and s + j2 is an integer from 1 to 5. * represents the bonding site with the terminal O (oxygen atom) in “(OA4)m” in formula (2). ]

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

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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