Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks
  • C09D11/32—Inkjet printing inks characterised by colouring agents
  • C09D11/322—Pigment inks

Definitions

• 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 fixing article, and a polymerizable monomer.
• polyolefins such as polypropylene have been excellent in workability and inexpensive compared to other polymeric materials, they have been processed into films and fibers and used as flexible packaging films and nonwoven fabrics.
• Flexible packaging films are generally used after undergoing printing processes such as front printing and back printing. Flexible packaging films that have been printed on the back and laminated are widely used from the viewpoints of beautiful printing, ink bleeding prevention, and durability of the printed film.
• a shift to front printing is desired from the viewpoints of improving work efficiency and reducing the environmental and economic burden by not using adhesives or solvents used in lamination.
• inkjet printing which can handle small quantities of a wide variety of products, is beginning to be adopted.
• the inks used in these printing processes are shifting from solvent-based to water-based in order to reduce the burden on the environment, and various water-based ink compositions that can form printed images on flexible packaging films by inkjet printing have been proposed.
• Patent Document 1 describes an aqueous inkjet ink composition that contains a binder resin composition for aqueous inkjet ink, characterized by containing specific core-shell type resin particles, and a specific moisturizing solvent.
• Patent Document 2 describes an ink composition containing a pigment, specific self-dispersing resin particles, at least two types of 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-based surfactant, a specific silicone-based surfactant, a water-soluble solvent, and water.
• an object of the present invention is to provide a polymer that has excellent adhesion to substrates made of polyolefins, and a compound that constitutes this polymer.
• a polymer comprising, as a constituent unit, a structure derived from a polymerizable monomer (M) represented by the following 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.
• A2 represents an alkylene chain having 1 to 10 carbon atoms, and the alkylene chain may have a substituent. Note that, multiple A2 may be the same or different.
• n is an integer from 3 to 100.
• X1 represents a group having an ethylenically unsaturated double bond.
• a 1 is any one of groups represented by the following formulas (1-a) to (1-f): [Wherein, R 1 and R 2 each independently represent a hydrogen atom or a monovalent aliphatic hydrocarbon group. R 3 , R 5 , R 6 , and R 8 each independently represent a monovalent aliphatic hydrocarbon group. R 4 , R 7 , and R 9 each independently represent a divalent aliphatic hydrocarbon group. k represents an integer of 1 to 5, and p represents an integer of 0 to 4. k+p is an integer of 1 to 5.
• a 1 and A 2 are the same as A 1 and A 2 in formula (1), respectively.
• [4] Resin particles comprising the polymer according to any one of [1] to [3].
• [5] The resin particle according to [4], wherein the resin particle is a single-layer particle containing the polymer or a particle having a core-shell structure containing the polymer in a shell layer.
• An aqueous dispersion comprising the resin particles according to [4] or [5].
• [8] The ink according to [7], wherein the binder is resin particles containing the polymer.
• a method for producing a printed matter in which an image is printed on a substrate comprising: an image forming step of depositing the ink according to [7] or [8] on the substrate to form an image.
• An image-fixed article in which an image containing a pigment and a resin is fixed to a part or all of a substrate, the image-fixed article being characterized in that the resin contains the polymer according to any one of [1] to [3].
• a 4 represents an alkylene chain having 1 to 10 carbon atoms, and the alkylene chain may have a substituent. Note that, multiple A 4 's may be the same or different.
• m is an integer from 3 to 100.
• X2 represents a group having an ethylenically unsaturated double bond.
• A3 and A4 are the same as A3 and A4 in formula (2), respectively.]
• A3 is any one of groups represented by the following formulas (1-a) to (1-f): [Wherein, R 1 and R 2 each independently represent a hydrogen atom or a monovalent aliphatic hydrocarbon group. R 3 , R 5 , R 6 , and R 8 each independently represent a monovalent aliphatic hydrocarbon group. R 4 , R 7 , and R 9 each independently represent a divalent aliphatic hydrocarbon group. k represents an integer of 1 to 5, and p represents an integer of 0 to 4. k+p is an integer of 1 to 5.
• * represents a bonding site with the terminal O (oxygen atom) in "(OA 4 ) m " in formula (2).]
• the polymer of the present invention due to the above-mentioned configuration, has excellent adhesion to substrates made of polyolefin. 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 films made of polyolefin and fabrics made of polyolefin fibers. In particular, even in the case of aqueous ink, the use of the polymer of the present invention as a resin component can increase adhesion to polyolefin substrates.
• an ink preferably an aqueous ink
• (meth)acrylate means “acrylate” or “methacrylate”
• (meth)acrylic means “acrylic” or “methacrylic”
• (meth)acryloyl means “acryloyl” or “methacryloyl”.
• (Meth)acrylate is also sometimes referred to as (meth)acrylic acid ester.
• a to B expressing a numerical range means "A or more, B or less.”
• Polymer The polymer of the present disclosure is characterized by including a structure (M) derived from a polymerizable monomer (M) represented by the following formula (1) as a constituent unit.
• M polymerizable monomer
• the polymer of the present disclosure may also be referred to as a polymer (Pm).
• a 1 represents a hydrocarbon group containing two or more aromatic ring skeletons, the hydrocarbon group may have a substituent, and the substituent is a nonionic substituent.
• a 2 represents an alkylene chain having 1 to 10 carbon atoms, and the alkylene chain may have a substituent. Note that multiple A 2 's may be the same or different.
• n is an integer of 3 to 100.
• X 1 represents a group having an ethylenically unsaturated double bond.
• the polymerizable monomer (M) is represented by the above formula (1).
• a 1 represents a polycyclic phenyl group
• the polycyclic phenyl group means a hydrocarbon group containing two or more aromatic ring skeletons.
• the "hydrocarbon group containing two or more aromatic ring skeletons" may be referred to as a "polycyclic phenyl group”.
• a structure in which two aromatic hydrocarbons of a monocyclic structure are condensed is considered to contain two aromatic ring skeletons.
• containing two or more aromatic ring skeletons means that at least one of the following is satisfied: containing two or more aromatic hydrocarbon skeletons of a monocyclic structure such as a benzene ring (i.e., an unsaturated hydrocarbon ring that shows aromaticity by itself) or containing at least one aromatic hydrocarbon skeleton of a condensed ring structure (i.e., a condensed aromatic ring that shows aromaticity by condensing two or more unsaturated hydrocarbon rings).
• a monocyclic structure such as a benzene ring (i.e., an unsaturated hydrocarbon ring that shows aromaticity by itself) or containing at least one aromatic hydrocarbon skeleton of a condensed ring structure (i.e., a condensed aromatic ring that shows aromaticity by condensing two or more unsaturated hydrocarbon rings).
• the polycyclic phenyl group may have two or more aromatic hydrocarbon skeletons of a monocyclic structure, one or more aromatic hydrocarbon skeletons of a condensed ring structure, or one or more aromatic hydrocarbon skeletons of a monocyclic structure and one or more aromatic hydrocarbon skeletons of a condensed ring structure.
• the aromatic ring skeletons contained in the polycyclic phenyl group may be the same or different.
• 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).
• the other hydrocarbon group include monovalent or divalent or higher aliphatic hydrocarbon groups, such as alkyl groups, alkylene groups, alkenyl groups, alkenylene groups, alkynyl groups, etc., each having a chain structure or a cyclic structure. Among these, alkyl groups are preferred.
• the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group.
• the aliphatic hydrocarbon group may have a chain structure (aliphatic chain hydrocarbon group) or a cyclic structure (aliphatic cyclic hydrocarbon group).
• 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.
• linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-n
• Specific examples include alkylene groups having a chain structure such as a methylene group, an ethylene-1,1-diyl group, an ethylene-1,2-diyl group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group.
• the number of carbon atoms in the monovalent or divalent or higher chain-like saturated aliphatic hydrocarbon group is preferably 1 to 18, more preferably 1 to 12, even more preferably 1 to 6, and even more preferably 1 to 3.
• Examples of the monovalent saturated aliphatic hydrocarbon group having a cyclic structure include alkyl groups having a cyclic structure (i.e., cycloalkyl groups) such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a 3-methylcyclohexyl group, a 4-methylcyclohexyl group, a 4-ethylcyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
• alkyl groups having a cyclic structure i.e., cycloalkyl groups
• alkyl groups having a cyclic structure such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a 3-methylcyclohexyl group, a 4-methylcyclohexyl group, a 4-ethylcyclohexyl group,
• 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 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.).
• Examples of the monovalent unsaturated aliphatic hydrocarbon group having a chain structure include alkenyl groups having a chain structure, such as vinyl group, n-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, 2-pentenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, and 3-methyl-1-butenyl group; and alkynyl groups having a chain structure, such as ethynyl group, 2-propynyl group, 3-butynyl group, 4-pentynyl group, 1-methyl-3-butynyl group, 1,1-dimethyl-2-propynyl group, and 6-heptynyl group.
• alkenyl groups having a chain structure such as vinyl group, n-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, 2-
• 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.
• Examples of the monovalent unsaturated aliphatic hydrocarbon group having a cyclic structure include alkenyl groups having a cyclic structure (that is, cycloalkenyl groups), such as a cyclohexenyl group, a cycloheptenyl group, and a cyclooctenyl group.
• the monovalent or divalent or higher cyclic unsaturated aliphatic hydrocarbon group preferably has 3 to 18 carbon atoms, more preferably 4 to 12 carbon atoms, and even more preferably 5 to 8 carbon atoms.
• the aromatic hydrocarbon skeleton of the monocyclic structure is not particularly limited as long as it has a structure derived from an aromatic hydrocarbon of a monocyclic structure, but is preferably an aromatic hydrocarbon ring of 4 to 7 member rings, and more preferably an aromatic hydrocarbon ring of 6 member rings, i.e., a benzene ring.
• the aromatic hydrocarbon of the monocyclic structure is preferably an aromatic hydrocarbon of 4 to 7 member rings, and more preferably includes a 6 member ring, i.e., a benzene ring.
• the polycyclic phenyl group has two or more aromatic hydrocarbon skeletons of a monocyclic structure (i.e., an unsaturated hydrocarbon ring that shows aromaticity by itself), it is not particularly limited as long as it is not an aromatic hydrocarbon skeleton of a condensed ring structure (i.e., two or more unsaturated hydrocarbon rings are not condensed).
• the aromatic hydrocarbon skeletons of the monocyclic structure i.e., an unsaturated hydrocarbon ring that shows aromaticity by itself
• a single bond or another divalent or higher hydrocarbon group as mentioned above is preferred, a single bond or a divalent or higher aliphatic hydrocarbon group is more preferred, a single bond or a divalent aliphatic hydrocarbon group is even more preferred, a single bond or an alkylene group is even more preferred, and a single bond or a chain alkylene group is particularly preferred.
• the number of unsaturated hydrocarbon rings that the polycyclic phenyl group has independently exhibiting aromaticity is preferably 2 to 6, more preferably 2 to 4, and even more preferably 3 to 4.
• the aromatic hydrocarbon skeleton of the fused ring structure is not particularly limited as long as it is a structure exhibiting aromaticity formed by condensing two or more unsaturated hydrocarbon rings, but is preferably a structure derived from a fused ring aromatic hydrocarbon in which aromatic hydrocarbons of a monocyclic structure are condensed, more preferably a structure derived from a fused ring aromatic hydrocarbon in which aromatic hydrocarbon rings of a 4- to 7-membered ring structure are condensed, 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 condensed.
• condensed ring aromatic hydrocarbon i.e., aromatic hydrocarbon skeleton of condensed ring structure
• a structure in which only 6-membered aromatic hydrocarbon rings are condensed such as naphthalene, anthracene, pentacene, benzopyrene, chrysene, pyrene, triphenylene, corannulene, coronene, ovalene, kekulene, etc.
• a structure in which a 5-membered unsaturated hydrocarbon ring and a 7-membered unsaturated hydrocarbon ring are condensed such as azulene, etc.
• 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.
• 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.
• the polycyclic phenyl group represented by A 1 is preferably a monovalent group.
• the polycyclic phenyl group may be bonded to the oxygen atom in formula (1) through a carbon atom constituting the aromatic ring skeleton (i.e., an unsaturated hydrocarbon ring that exhibits aromaticity alone or by condensation), or may be bonded to the oxygen atom in formula (1) through a carbon atom constituting another hydrocarbon group other than the aromatic ring skeleton, such as an aliphatic hydrocarbon group such as an alkyl group or an alkylene group.
• the polycyclic phenyl group represented by A1 may have a substituent, but the substituent is a nonionic substituent, i.e., the polycyclic phenyl group does not have an anionic group.
• the nonionic substituent refers to a nonionic substituent, and specific examples thereof include polyalkylene glycol groups such as a polyethylene glycol group and a polypropylene glycol group; halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like; a hydroxyl group; alkyl ether groups such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and the like (preferably a C 1-4 alkoxy group); aryl ether groups such as a phenoxy group, a naphthoxy group, and the like (preferably a C 6-15 aryloxy group); acyl groups such as an acet
• the nonionic substituent may be directly bonded to the aromatic ring skeleton constituting the polycyclic phenyl group (i.e., an unsaturated hydrocarbon ring which exhibits aromaticity either alone or as a condensed ring), or may be bonded to a hydrocarbon group other than the aromatic ring skeleton (for example, the aliphatic hydrocarbon group such as an alkyl group or an alkylene group).
• the nonionic substituent bonded to a hydrocarbon group other than the aromatic ring skeleton is preferably a halogen atom, a hydroxyl group, an alkyl ether group, an aryl ether group or an acyl group, more preferably a halogen atom, a hydroxyl group, a C 1-4 alkoxy group, a C 6-15 aryloxy group, an alkylcarbonyl group in which the alkyl group has 1 to 4 carbon atoms, or an arylcarbonyl group in which the aryl group has 6 to 15 carbon atoms.
• halogen atoms a chlorine atom, a bromine atom or a fluorine atom is preferred, and a chlorine atom is more preferred.
• the polycyclic phenyl group represented by A1 is It is preferred that the hydrocarbon group A1 has 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 is bonded to an oxygen atom in formula (1) directly or via a divalent aliphatic hydrocarbon group, or that the hydrocarbon group B1 has one fused ring in which 2 to 12 benzene rings are condensed, the fused ring may have a monovalent aliphatic hydrocarbon group, and the fused ring is bonded to an oxygen atom in formula (1) directly or via a divalent aliphatic hydrocarbon group; It is more preferable 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
• hydrocarbon group A1, hydrocarbon group B1, hydrocarbon group A2, hydrocarbon group B2, hydrocarbon group A3, and hydrocarbon group B3 may each have the nonionic substituents exemplified above, but it is preferable that they do not have any of them.
• the polycyclic phenyl group represented by A1 above is more preferably at least one type selected from the group consisting of structures represented by the following formulas (1-a) to (1-f).
• R1 and R2 each independently represent a hydrogen atom or a monovalent aliphatic hydrocarbon group
• R3 each independently represent a monovalent aliphatic hydrocarbon group.
• k represents an integer of 1 to 5
• p represents an integer of 0 to 4.
• k+p is an integer of 1 to 5. * represents the bonding site with the terminal O (oxygen atom) in "( OA2 ) n " in formula (1).
• Examples of the monovalent aliphatic hydrocarbon group represented by R 1 , R 2 , and R 3 include the monovalent aliphatic hydrocarbon groups described above (for example, alkyl groups, alkenyl groups, alkynyl groups), and among these, an alkyl group is preferable, an alkyl group having 1 to 18 carbon atoms is more preferable, an alkyl group having 1 to 12 carbon atoms is even more preferable, an alkyl group having 1 to 6 carbon atoms is still more preferable, and an alkyl group having 1 to 3 carbon atoms is particularly preferable.
• the above k is preferably 1 to 3, more preferably 2 to 3.
• the above p is preferably 0 to 1.
• the above alkyl group is preferably an alkyl group having a chain structure, and the preferred range of the number of carbon atoms in the alkyl group having a chain structure is the same as the preferred range of the number of carbon atoms in the above alkyl group.
• R 1 and R 2 are a hydrogen atom or an alkyl group, R 3 is 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); More preferably, R 1 is a hydrogen atom, R 2 is an alkyl group, R 3 is an alkyl group, k is an integer of 1 to 3, and p is an integer of 0 to 1; It is more preferable that R 1 is a hydrogen atom, R 2 is a C 1-3 alkyl group, R 3 is a C 1-12 alkyl group, k is an integer of 1 to 3, and p is an integer of 0 to 1.
• R 1 , R 2 , R 3 , k, p, and * are the same as R 1 , R 2 , R 3 , k, p, and * in the above formula (1-a), including preferred embodiments.
• R 4 represents a divalent aliphatic hydrocarbon group.
• Examples of the divalent aliphatic hydrocarbon group represented by R4 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 preferable, an alkylene group having 1 to 18 carbon atoms is more preferable, an alkylene group having 1 to 12 carbon atoms is even more preferable, an alkylene group having 1 to 6 carbon atoms is still more preferable, and an alkylene group having 1 to 3 carbon atoms is particularly preferable.
• an alkylene group is preferable, an alkylene group having 1 to 18 carbon atoms is more preferable, an alkylene group having 1 to 12 carbon atoms is even more preferable, an alkylene group having 1 to 6 carbon atoms is still more preferable, and an alkylene group having 1 to 3 carbon atoms is particularly preferable.
• R 1 and R 2 are a hydrogen atom or an alkyl group, R 3 is an alkyl group, R 4 is 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); More preferably, R 1 is a hydrogen atom, R 2 is an alkyl group, R 3 is an alkyl group, R 4 is an alkylene group, k is an integer of 1 to 3, and p is an integer of 0 to 1; It is more preferable that R 1 is a hydrogen atom, R 2 is a C 1-3 alkyl group, R 3 is a C 1-12 alkyl group, R 4 is a C 1-12 alkylene group, k is an integer of 1 to 3, and p is an integer of 0 to 1.
• R5 and R6 each independently represent a monovalent aliphatic hydrocarbon group. Furthermore, q represents an integer of 0 to 3, and r represents an integer of 0 to 4. * represents the bonding site with the terminal O (oxygen atom) in "(OA 2 ) n " in formula (1).
• the monovalent aliphatic hydrocarbon group represented by R5 and R6 includes the monovalent aliphatic hydrocarbon groups described above (for example, alkyl groups, alkenyl groups, alkynyl groups), of which an alkyl group is preferable, an alkyl group having 1 to 18 carbon atoms is more preferable, an alkyl group having 1 to 12 carbon atoms is even more preferable, an alkyl group having 1 to 6 carbon atoms is still more preferable, and an alkyl group having 1 to 3 carbon atoms is particularly preferable.
• 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.
• R5 and R6 are each independently an alkyl group, q is an integer of 0 to 3, and r is an integer of 0 to 4; It is more preferable that R 5 and R 6 are each independently a C 1-12 alkyl group, q is 0 or 1, and r is 0 or 1.
• R 5 , R 6 , q, r, and * are the same as R 5 , R 6 , q, r, and * in the above formula (1-c), including preferred embodiments.
• R 7 represents a divalent aliphatic hydrocarbon group.
• Examples of the divalent aliphatic hydrocarbon group represented by R7 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 preferable, an alkylene group having 1 to 18 carbon atoms is more preferable, an alkylene group having 1 to 12 carbon atoms is even more preferable, an alkylene group having 1 to 6 carbon atoms is still more preferable, and an alkylene group having 1 to 3 carbon atoms is particularly preferable.
• an alkylene group is preferable, an alkylene group having 1 to 18 carbon atoms is more preferable, an alkylene group having 1 to 12 carbon atoms is even more preferable, an alkylene group having 1 to 6 carbon atoms is still more preferable, and an alkylene group having 1 to 3 carbon atoms is particularly preferable.
• R 5 and R 6 are each independently an alkyl group, R 7 is an alkylene group, q is an integer of 0 to 3, and r is an integer of 0 to 4; It is more preferable that R 5 and R 6 are each independently a C 1-12 alkyl group, R 7 is a C 1-12 alkylene group, q is 0 or 1, and r is 0 or 1.
• each R8 independently represents a monovalent aliphatic hydrocarbon group. Furthermore, 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 bonding site with the terminal O (oxygen atom) in "(OA 2 ) n " in formula (1).
• Examples of the monovalent aliphatic hydrocarbon group represented by R8 include the monovalent aliphatic hydrocarbon groups explained above (for example, an alkyl group, an alkenyl group, an alkynyl group), of which an alkyl group is preferable, an alkyl group having 1 to 18 carbon atoms is more preferable, an alkyl group having 1 to 12 carbon atoms is even more preferable, an alkyl group having 1 to 6 carbon atoms is still more preferable, and an alkyl group having 1 to 3 carbon atoms is particularly preferable.
• 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.
• R 8 is 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); More preferably, R 8 is an alkyl group, s is 0 or 1, and j is an integer from 1 to 3; It is more preferred that R 8 is a C 1-12 alkyl group, s is 0 or 1, and j is an integer from 1 to 3.
• R 8 , s, j, and * are the same as R 8 , s, j, and * in the above formula (1-e), including preferred embodiments, respectively.
• R 9 represents a divalent aliphatic hydrocarbon group.
• Examples of the divalent aliphatic hydrocarbon group represented by R9 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 preferable, an alkylene group having 1 to 18 carbon atoms is more preferable, an alkylene group having 1 to 12 carbon atoms is even more preferable, an alkylene group having 1 to 6 carbon atoms is still more preferable, and an alkylene group having 1 to 3 carbon atoms is particularly preferable.
• an alkylene group is preferable, an alkylene group having 1 to 18 carbon atoms is more preferable, an alkylene group having 1 to 12 carbon atoms is even more preferable, an alkylene group having 1 to 6 carbon atoms is still more preferable, and an alkylene group having 1 to 3 carbon atoms is particularly preferable.
• R 8 is an alkyl group
• R 9 is an alkylene group
• s is an integer of 0 to 4
• j is an integer of 1 to 5 (wherein s+j is an integer of 1 to 5); More preferably, R 8 is an alkyl group, R 9 is an alkylene group, s is 0 or 1, and j is an integer from 1 to 3; It is more preferable that R 8 is a C 1-12 alkyl group, R 9 is a C 1-12 alkylene group, s is 0 or 1, and j is an integer from 1 to 3.
• the polycyclic phenyl group represented by A1 is preferably at least one selected from the group consisting of structures represented by formulas (1-a) to (1-f) above, and more preferably the structure represented by formula (1-a) above.
• the polymer of the present disclosure has a structure other than X1 in formula (1), i.e., a structure A 1 -(OA 2 ) n -O-, in its side chain as a structure derived from the polymerizable monomer (M). Therefore, the polymer of the present disclosure has excellent adhesion to polyolefin substrates.
• the structure of the terminal portion of the side chain of the polymer particularly the structure represented by A 1 -(OA 2 ) 2 - (hereinafter also referred to as the terminal structure) contributes greatly to the adhesion to the substrate.
• the present inventors have focused on a calculation method in which, as a method for estimating the adhesion of a polymer to a substrate, the Gaussian 16 program manufactured by Gaussian Corporation is used to apply B3LYP to the functional of the density functional theory, 6-31G (d, p) to the basis function, and dispersion force correction (GD3BJ keyword).
• the zero-point energy of the terminal structure of the side chain of the polymer of the present disclosure is substituted with the zero-point energy of a molecule having a structure similar to the terminal structure, specifically, a molecule represented by the following formula (1-1) (hereinafter also referred to as the structure molecule (Ip)), and the magnitude of the difference between the absolute value of the zero-point energy of the structure molecule (Ip) and the absolute value of the zero-point energy of the substrate molecule, obtained by the calculation method, and the absolute value of the zero-point energy of the association between the structure molecule (Ip) and the substrate molecule, and the adhesion of the polymer of the present disclosure to the substrate is found to be correlated.
• a molecule having a structure similar to the terminal structure specifically, a molecule represented by the following formula (1-1) (hereinafter also referred to as the structure molecule (Ip))
• a 1 and A 2 are the same as A 1 and A 2 in formula (1), respectively.
• 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 is the absolute value of the zero-point energy of the structural molecule (Ip)
• E P8 is the absolute value of the zero-point energy of the propylene octamer
• E MP is the absolute value of the zero-point energy of the association of the structural molecule (Ip) and the propylene octamer.
• the structural molecule (Ip) has a structure represented by the above formula (1-1).
• a 1 in the above formula (1-1) is preferably the same as A 1 in the above formula (1)
• (OA 2 ) 2 in the above formula (1-1) is preferably the same as the consecutive (OA 2 ) 2 directly bonded to A 1 in the above formula (1). That is, (OA 2 ) 2 in the formula (1-1) is preferably the same as (OA 2 ) 2 when the formula (1) is rewritten as A 1 -(OA 2 ) 2 -(OA 2 ) n-2 -OX 1 .
• the zero-point energy of the association means the zero-point energy when the structure molecule (Ip) (the structure molecule represented by the above formula (1-1)) and the 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, 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.
• the above formula (f1-1) means that the difference d1 between the sum of the absolute value of the zero-point energy (E M ) of the structure molecule (Ip) and the absolute value of the zero-point energy (E P8 ) of the propylene octamer and the absolute value of the zero-point energy (E MP ) of the association of the structure molecule (Ip) and the propylene octamer is less than ⁇ 80 kJ/mol.
• the polymer (Pm) having a structure derived from the polymerizable monomer (M) having the corresponding terminal structure as a structural unit tends to have better adhesion to a polyolefin substrate, particularly a polypropylene substrate.
• the difference d1 is preferably -85 kJ/mol or less, more preferably -90 kJ/mol or less.
• E M , E P8 , and E MP have the same meanings as E M , E P8 , and E MP in the above formula (f1-1), respectively, and are values calculated in the same manner.
• 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 of the propylene octamer and the propylene hexamer.
• the zero-point energy of the association of the propylene octamer and the propylene hexamer means the zero-point energy when the propylene octamer and the propylene hexamer are in the same space.
• the above formula (f1-2) means that the difference d1 between the sum of the absolute value of the zero-point energy (E M ) of the structure molecule (Ip) and the absolute value of the zero-point energy (E P8 ) of the propylene octamer and the absolute value of the zero-point energy (E MP ) of the association of the structure molecule (Ip) and the propylene octamer is smaller (larger in a negative value) than the difference d2 between the sum of the absolute value of the zero-point energy (E P6 ) of the propylene hexamer and the absolute value of the zero-point energy (E P8 ) of the propylene octamer and the absolute value of the zero-point energy (E PP ) of the association of the propylene hexamer and the propylene octamer.
• 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.
• the group having an ethylenically unsaturated double bond represented by X1 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.
• a (meth)acryloyl group is preferred from the viewpoint of increasing the polymerization rate.
• A2 in the above formula (1) represents an alkylene chain having 1 to 10 carbon atoms, and the alkylene chain may have a substituent. Note that, although the multiple A2s in formula (1) may be the same or different, they are preferably the same.
• Examples of the alkylene chain represented by A2 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.
• the alkylene chain is preferably an ethylene-1,1-diyl group.
• the substituent that the alkylene chain may have is not particularly limited, and examples thereof include a halogen atom, a polar functional group, an alkoxy group, and a thioalkoxy group.
• the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a chlorine atom, a bromine atom, and a fluorine atom are preferred, and a fluorine atom is more preferred.
• Preferred examples of the polar functional group include a hydroxyl group, a carboxyl group, an amino group, and a mercapto group.
• the alkoxy group is, for example, preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, and even more preferably an alkoxy group having 1 carbon atom, that is, a methoxy group.
• the above thioalkoxy group is, for example, preferably a thioalkoxy group having 1 to 10 carbon atoms, more preferably a thioalkoxy group having 1 to 4 carbon atoms, and even more preferably a thioalkoxy group having 1 carbon atom, that is, a thiomethoxy group.
• n is not particularly limited as long as it is an integer between 3 and 100, but is preferably between 4 and 30.
• the polymerizable monomer (M) is preferably one in which the polycyclic phenyl group represented by A1 has any of the structures represented by formulas (1-a) to (1-f), more preferably one in which the alkylene chain represented by A2 is an alkylene chain having 1 to 3 carbon atoms, and particularly preferably one in which the group having an ethylenically unsaturated double bond represented by X1 is a (meth)acryloyl group.
• the polymerizable monomer (M) is preferably one in which the terminal structure containing the polycyclic phenyl group represented by A 1 satisfies the relationship represented by formula (f1-1) and/or formula (f1-2), more preferably one in which the alkylene chain represented by A 2 is an alkylene chain having 1 to 3 carbon atoms, and particularly preferably one in which the group having an ethylenically unsaturated double bond represented by X 1 is a (meth)acryloyl group.
• 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), it is preferable that the polymer (Pm) is a polymer containing the structure (M) and a structure other than the structure (M) as a structural unit.
• 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 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 monomer as a constituent unit.
• 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 constituent units (but not containing a structure derived from a styrene monomer); a styrene polymer containing the structure (M) and a structure derived from a styrene monomer as constituent units (but not containing a structure derived from a (meth)acrylic monomer); or a (meth)acrylic-styrene polymer containing the structure (M), a structure derived from a (meth)acrylic monomer, and a structure derived from a styrene monomer as constituent units, and a (meth)acrylic polymer is more preferable.
• the polymer (Pm) of the present disclosure contains the above structure (M) as a constituent unit, and preferably contains a plurality of the above structure (M) as a constituent unit, and more preferably contains a plurality of the above structure (M) as a repeating constituent unit.
• the polymer (Pm) contains a plurality of structures (M) as constituent units, the plurality of structures (M) may be the same or different.
• the content of structure (M) in polymer (Pm) of the present disclosure is not particularly limited, but the content of structure (M) in 100% by mass of polymer (Pm) is preferably 1 to 100% by mass, more preferably 2 to 80% by mass, even more preferably 4 to 50% by mass, and even more preferably 5 to 50% by mass.
• the (meth)acrylic monomer is not particularly limited, and one or more types may be selected from conventionally known (meth)acrylic acid esters and (meth)acrylic acids.
• 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, in 100% by mass of the polymer (Pm).
• the above (meth)acrylic acid esters 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 these, (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. In addition, the (meth)acrylic acid esters may be either monofunctional (meth)acrylic acid esters or polyfunctional (meth)acrylic acid esters, but monofunctional (meth)acrylic acid esters are preferred.
• Examples of the (meth)acrylic acid ester having a linear alkyl group include (meth)acrylic acid linear alkyl 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 car
• the (meth)acrylic acid ester having the 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-
• 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.
• 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)acryl
• cycloalkyl (meth)acrylate and isobornyl (meth)acrylate are preferred, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate and isobornyl (meth)acrylate are more preferred, cyclohexyl (meth)acrylate and isobornyl (meth)acrylate are even more preferred, and cyclohexyl methacrylate and isobornyl acrylate are even more preferred.
• Examples of the (meth)acrylic acid ester having a branched alkyl group include (meth)acrylic acid branched alkyl 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)acrylates, such as 3-methoxybutyl (meth)acrylate and methoxytripropylene glycol (meth)acrylate; Halogen atom-containing branched alkyl (meth)acrylates such as hexafluoroisopropyl (meth)acrylate; and the like.
• branched alkyl (meth)acrylates are preferred.
• 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.
• 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.
• These (meth)acrylic acid esters may be used alone or in combination of two or more kinds.
• the above-mentioned (meth)acrylic acid ester preferably includes a (meth)acrylic acid alkyl ester having a homopolymer glass transition temperature (Tg) of -20°C or lower (hereinafter, sometimes referred to as a low Tg (meth)acrylic acid alkyl ester) and/or a (meth)acrylic acid ester having a cyclic aliphatic hydrocarbon group, and more preferably includes a low Tg (meth)acrylic acid alkyl ester and a (meth)acrylic acid ester having a cyclic aliphatic hydrocarbon group.
• Tg homopolymer glass transition temperature
• the "glass transition temperature of a homopolymer” may be, for example, a value listed in "POLYMER HANDBOOK THIRD EDITION” (written by J. BRANDRUP and E. H. IMMERGUT, published by John Wiley & Sons, Inc., 1989, pages VI/209 to VI/277) (if multiple Tg values are listed, the lowest value).
• values calculated by 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 polymerization average molecular weight of 100,000 may be used.
• 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, isononyl acrylate, and the like, with n-butyl acrylate, 2-octyl acrylate, and 2-ethylhexyl acrylate being particularly preferred.
• 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) is in the range described below.
• 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% in 100 mass% of the polymer (Pm), more preferably 10 to 50 mass%, and even more preferably 15 to 30 mass%.
• the content of the structure derived from the (meth)acrylic acid ester having the cyclic aliphatic hydrocarbon group is preferably 5 to 90 mass% in 100 mass% of the polymer (Pm), more preferably 15 to 85 mass%, even more preferably 30 to 80 mass%, and particularly preferably 50 to 80 mass%.
• (meth)acrylic acid can be preferably used as an acid group-containing monomer, but an acid group-containing monomer 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.
• the polymer (Pm) containing a structure derived from an acid group-containing monomer as a constituent unit the dispersion stability of the resin particles containing the polymer (Pm) in the 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 monomethyl maleate, monobutyl maleate, monomethyl itaconic acid and monobutyl itaconic acid; and carboxyl group-containing aliphatic monomers such as vinyl benzoic acid.
• 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 monomethyl maleate
• 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, preferred are unsaturated monocarboxylic acids and unsaturated dicarboxylic acids, more preferred are acrylic acid, methacrylic acid, and itaconic acid, and even more preferred are acrylic acid and methacrylic acid.
• the content of structures derived from acid group-containing monomers (particularly (meth)acrylic acid) in the polymer (Pm) of the present disclosure is preferably 0.5 to 10 mass% in 100 mass% of the polymer (Pm), more preferably 1 to 8 mass%, and even more preferably 3 to 5 mass%.
• the styrene-based monomer is not particularly limited, but examples thereof include styrenes which may have functional groups such as alkyl groups (for example, C 1-4 alkyl groups such as methyl and tert-butyl), nitro groups, nitrile groups, alkoxy groups (for example, C 1-4 alkoxy groups such as methoxy and ethoxy), acyl groups (for example, alkylcarbonyl groups having an alkyl group of 1 to 4 carbon atoms such as acetyl), sulfone groups, hydroxyl groups, halogen atoms (for example, fluorine atoms, chlorine atoms, bromine atoms), vinyl groups, and alkoxysilyl groups (for example, tri-C 1-4 alkoxysilyl groups such as trimethoxysilyl and triethoxysilyl).
• alkyl groups for example, C 1-4 alkyl groups such as methyl and tert-butyl
• nitro groups for example
• the position of the functional group is not particularly limited, but it is preferably directly bonded to the benzene ring.
• the styrene-based monomer include monofunctional styrene-based monomers such as styrene, ⁇ -methylstyrene, vinyltoluene (e.g., p-methylstyrene), tert-methylstyrene, chlorostyrene, and 2-styrylethyltrimethoxysilane.
• polyfunctional styrene-based monomers can also be used as the styrene-based monomer.
• a preferred example of the polyfunctional styrene-based monomer is divinylbenzene. These styrene-based monomers may be used alone or in combination of two or more kinds. As the styrene-based monomer, styrene is preferred from the viewpoint of enhancing water resistance.
• the polymer (Pm) of the present disclosure contains a structure derived from a styrene-based monomer (preferably a (meth)acrylic-styrene-based polymer)
• the content of the structure derived from a styrene-based monomer is not particularly limited, but is preferably 1 to 70 mass%, more preferably 5 to 50 mass%, and even more preferably 10 to 30 mass%, of 100 mass% of the polymer (Pm).
• the polymer (Pm) of the present disclosure may also 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).
• 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; Addition-polymerizable oxazolines such as 2-viny
• 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).
• the polymerizable monomer (M) constituting the polymer (Pm) is preferably a (meth)acrylic monomer (M1) in which X1 is a (meth)acryloyl group, and the polymer (Pm) is more preferably a copolymer of the monomer (M1) with a (meth)acrylic monomer and/or a styrene-based monomer, and further preferably a copolymer of the monomer (M1), a (meth)acrylic monomer, and a styrene-based monomer.
• the weight average molecular weight of the polymer (Pm) of the present disclosure is not particularly limited, but from the viewpoint of adhesion, it is preferably 50,000 or more, more preferably 100,000 or more, even more preferably 200,000 or more, and particularly preferably 600,000 or more. From the viewpoint of viscosity and film-forming properties, the upper limit of the weight average molecular weight is preferably 5,000,000 or less.
• the weight average molecular weight refers to the weight average molecular weight (polystyrene equivalent) measured using gel permeation chromatography [Tosoh Corporation, product number: HLC-8120GPC, columns: TSKgel G-5000HXL and TSKgel GMHXL-L used in series].
• 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 conformity to the substrate.
• the lower limit of the Tg is more preferably -65°C or higher, and even more preferably -60°C or higher.
• 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 polymer (Pm) of the present disclosure is in the range of -40 to 50°C.
• 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 image obtained 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 above Tg is more preferably 45°C or lower, and even more preferably 40°C or lower. Meanwhile, the lower limit of the above Tg is more preferably -35°C or higher, and even more preferably -30°C or higher.
• the above glass transition temperature can be a value obtained by any of differential scanning calorimetry (DSC), differential thermal analysis (DTA), and thermomechanical analysis (TMA), but it is preferable to use a value obtained by differential scanning calorimetry (DSC), and unless otherwise specified, the glass transition temperature in this specification means a value obtained by differential scanning calorimetry (DSC).
• DSC differential scanning calorimetry
• DTA differential thermal analysis
• TMA thermomechanical analysis
• differential scanning calorimetry there is no particular limitation on the method of drawing a differential scanning calorimetry (DSC) curve, the method of obtaining a first derivative curve from a differential scanning calorimetry (DSC) curve, the method of performing smoothing processing, the method of obtaining the target peak temperature, etc.
• DSC differential scanning calorimetry
• analysis software capable of performing mathematical processing can be used.
• the analysis software may be, for example, analysis software (Seiko Instruments, product number: EXSTAA6000).
• the measurement conditions are preferably a temperature rise rate of 15°C/min and a temperature fall rate of 15°C/min, and the values obtained under these conditions are adopted.
• the glass transition start temperature, intermediate temperature, bending 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.
• the polymer (Pm) of the present disclosure can be produced by polymerizing a polymerizable monomer composition containing the polymerizable monomer (M) represented by the above formula (1).
• the monomer other than the polymerizable monomer (M) include the above-mentioned (meth)acrylic monomer, styrene-based monomer, acid group-containing monomer, monomer (Q), etc., and preferably the (meth)acrylic monomer and/or the styrene-based monomer.
• the content (charge amount) and blending ratio of each polymerizable monomer in the polymerizable monomer composition may be appropriately selected so as to obtain the content of the structure derived from each monomer in the target polymer.
• the polymerization method is not particularly limited, and any conventionally known polymerization method can be used, such as a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, or a UV curing method.
• Resin particles include the polymer (Pm) of the present disclosure described above.
• the resin particles of the present disclosure may also be referred to as resin particles (Pp).
• the resin particles (Pp) may contain only the polymer (Pm) as a resin component, or may contain the polymer (Pm) and a polymer different from the polymer (Pm) (hereinafter, polymer (Pm2)).
• the resin particles (Pp) contain the polymer (Pm) and the polymer (Pm2)
• the resin particles (Pp) are particles having a multilayer structure, and one or more layers are composed of the polymer (Pm), and the remaining layers are composed of the polymer (Pm2); the resin particles (Pp) are composed of a polymer alloy of the polymer (Pm) and the polymer (Pm2); and the like, but the form A is preferable.
• the polymer (Pm) constituting the resin particles of the present disclosure is the same as the polymer (Pm) explained in "1. Polymer", and the explanation therefor can be applied mutatis mutandis.
• the shape of the resin particles (Pp) of the present disclosure is not particularly limited, but examples include spherical, plate-like, and needle-like shapes.
• the shape is preferably spherical.
• the shape can be measured using a transmission electron microscope or a scanning electron microscope.
• the average particle size of the resin particles (Pp) of the present disclosure is not particularly limited, but is preferably 10 nm or more and 1000 nm or less.
• a dispersion system e.g., ink
• it is more preferably 10 nm or more and 1 ⁇ m or less from the viewpoint of easily obtaining a dispersion system that is easily dispersed uniformly and has excellent dispersion stability.
• the average particle diameter of the resin particles is the average particle diameter (hydrodynamic diameter) obtained by calculating the autocorrelation function by the photon correlation method using a particle size distribution measuring device (manufactured by Otsuka Electronics Co., Ltd., product number: nanoSAQLA) using a dynamic light scattering method, and then performing cumulant analysis.
• the structure of the resin particles (Pp) of the present disclosure is not particularly limited, and may be a form in which the composition of the entire particle is uniform, or may be a core-shell structure consisting of a core part and a shell part having different compositions and/or physical properties.
• the core-shell structure is not limited to two layers, and may be three or more layers. That is, the resin particles (Pp) may be particles having a single-layer structure in which the entire particle is composed of the polymer (Pm), or may be particles having a multilayer structure composed of a polymer (Pm) and a polymer (Pm2).
• the entire particle is preferably composed of the polymer (Pm), and when the resin particles (Pp) have a multilayer structure, the outermost shell layer (i.e., the shell part) is preferably composed of the polymer (Pm).
• the ink containing the resin particles (Pp) can exhibit better adhesion to a substrate made of polyolefin.
• the resin particles (Pp) are preferably in a form of a core-shell structure of two or more layers, which can improve the balance between the elongation and hardness of the coating film.
• 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).
• the polymer constituting the layers other than the outermost shell may be either polymer (Pm) or polymer (Pm2), but is preferably polymer (Pm2).
• the mass proportion of the structure derived from the polymerizable monomer (M) in the polymer (Pm) in the shell portion is greater than the mass proportion of the structure derived from the polymerizable monomer (M) in the polymer (Pm) in the core portion.
• the polymer (Pm2) is not particularly limited, but examples thereof include vinyl resins, (meth)acrylic resins, olefin resins, urethane resins, fluorine resins, silicone resins, epoxy resins, phenoxy resins, phenol resins, xylene resins, and blocked isocyanates.
• the polymer (Pm2) is preferably a (meth)acrylic resin (hereinafter, (meth)acrylic polymer (2)).
• the polymer (Pm2) is preferably an olefin resin from the viewpoint of adhesion, and particularly when the resin particles (Pp) are of the above-mentioned form B, the polymer (Pm2) is preferably an olefin resin.
• the (meth)acrylic polymer (2) is a polymer containing a structural unit derived from a (meth)acrylic monomer.
• examples of the (meth)acrylic monomer include the compounds exemplified above as the (meth)acrylic monomer. These (meth)acrylic monomers may be used alone or in combination of two or more.
• the content of the structure derived from a (meth)acrylic monomer in the (meth)acrylic polymer (2) is not particularly limited, but is, for example, 30 to 100 mass%, preferably 50 mass% or more, more preferably 70 mass% or more, even more preferably 80 mass% or more, still more preferably 90 mass% or more, and particularly preferably 95 mass% or more, based on 100 mass% of the (meth)acrylic polymer (2).
• the total content of the structure derived from a low Tg (meth)acrylic acid alkyl ester, the structure derived from a (meth)acrylic acid ester having a cyclic aliphatic hydrocarbon group, and the structure derived from an acid group-containing monomer is more preferable to adjust the total content of the structure derived from a low Tg (meth)acrylic acid alkyl ester, the structure derived from a (meth)acrylic acid ester having a cyclic aliphatic hydrocarbon group, and the structure derived from an acid group-containing monomer to be within the above range.
• the (meth)acrylic polymer (2) preferably contains at least a low Tg (meth)acrylic acid alkyl ester.
• the low Tg (meth)acrylic acid alkyl ester is the same as the low Tg (meth)acrylic acid alkyl ester described above, including its preferred forms.
• the content of the structure derived from the low Tg (meth)acrylic acid alkyl ester in the (meth)acrylic polymer (2) is preferably adjusted so that the Tg of the (meth)acrylic polymer (2) falls within the range described below.
• 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%, relative to 100 mass% of the (meth)acrylic polymer (2).
• 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 the preferred forms thereof.
• the content of the structure derived from the (meth)acrylic 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).
• 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 the preferred forms thereof.
• the content of the structure derived from an acid group-containing monomer (particularly (meth)acrylic acid) in the (meth)acrylic polymer (2) is preferably 0.5 to 10 mass%, more preferably 1 to 8 mass%, and further preferably 3 to 5 mass%, based on 100 mass% of the (meth)acrylic polymer (2).
• 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 preferred forms thereof.
• the content of the structure derived from a styrene-based monomer (particularly styrene) in the (meth)acrylic polymer (2) is preferably 30 mass% or less, more preferably 10 mass% or less, and even more preferably 5 mass% or less, based on 100 mass% of the (meth)acrylic polymer (2).
• the (meth)acrylic polymer (2) may further contain a structure (M), but it is preferable that the (meth)acrylic polymer (2) does not contain the structure (M).
• the structure (M) is the same as the structure (M) described above, including the preferred forms thereof.
• 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).
• the (meth)acrylic polymer (2) may further contain, but preferably does not contain, a structural unit derived from a monomer other than the (meth)acrylic monomer, the styrene monomer, the acid group-containing monomer, and the polymerizable monomer (M).
• the other monomer 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 mass% or less, more preferably 10 mass% or less, and even more preferably 5 mass% or less, based on 100 mass% of the (meth)acrylic polymer (2).
• 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).
• 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 the weight average molecular weight of the polymer (Pm).
• the content ratio of the polymer (Pm) to the polymer (Pm2) is preferably 5:95 to 95:5 by mass, and more preferably 30:70 to 70:30.
• 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 the 100% by mass of the resin components contained in the resin particles (Pp) of the present disclosure.
• the resin particles (Pp) are particles with a single layer structure, it is preferable to adjust the content of the polymer (Pm) contained in the resin particles (Pp) to within the above range, and when the resin particles (Pp) are particles with a multilayer structure, it is preferable to adjust the content of the polymer (Pm) in 100% by mass of the resin components contained in the outermost layer (i.e., the shell portion) to within the above range.
• 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.
• the resin particles (Pp) of the present disclosure may contain components other than the resin component.
• components other than the resin component include an emulsifier (surfactant), etc.
• 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 properties and adhesion.
• the lower limit of the Tg is more preferably ⁇ 65° C. or higher, and even more preferably ⁇ 60° C. or higher.
• the upper limit of the Tg is more preferably 80° C. or lower, and even more preferably 60° C. or lower. It is also preferable that the glass transition temperature (Tg) of the resin particles (Pp) of the present disclosure is in the range of -40 to 50°C.
• 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 properties at low temperatures.
• the upper limit of the Tg is more preferably 45°C or lower, and even more preferably 40°C or lower. Meanwhile, the lower limit of the Tg is more preferably -35°C or higher, and even more preferably -30°C or higher.
• the glass transition temperature of the resin particles (Pp) of the present disclosure is a value obtained by the same measurement method as that for the glass transition temperature of the polymer (Pm).
• the method for producing the resin particles (Pp) of the present disclosure is not particularly limited.
• the resin particles (Pp) can be produced using a conventionally known emulsion polymerization method, suspension polymerization method, or bulk polymerization grinding method using a polymerizable monomer composition containing a polymerizable monomer (M) represented by the above formula (1) as a raw material.
• 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 can obtain 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.
• the resin particles obtained by the emulsion polymerization method carried out in an aqueous medium are particularly excellent in dispersion stability.
• the resin particles obtained by the emulsion polymerization method carried out in an aqueous medium are also called aqueous emulsion particles.
• the polymerization may be carried out in one step or multiple steps.
• a polymerizable monomer composition made of the monomers constituting the polymer (Pm2) is polymerized in an aqueous medium to synthesize seed particles that become the core (i.e., the polymer (Pm2)), and then a polymerizable monomer composition made of the monomers constituting the polymer (Pm) is polymerized to synthesize the shell (i.e., the polymer (Pm)), thereby producing resin particles having a core-shell structure.
• resin particles having a core-shell structure can be produced by a method of carrying out emulsion polymerization in the presence of seed particles obtained by a suspension polymerization method, an emulsion polymerization method or the like (seed emulsion polymerization method).
• the content (charge amount) and compounding ratio of each polymerizable monomer in the polymerizable monomer composition may be appropriately selected so as to obtain the content of the structure derived from each polymerizable monomer in the target polymer (Pm) or polymer (Pm2).
• aqueous emulsion particles are preferred among the resin particles (Pp) of the present disclosure, resin particles obtained by emulsion polymerization or suspension polymerization carried out in an aqueous medium are preferred, and aqueous emulsion particles are more preferred.
• the above-mentioned aqueous medium means a solvent containing 50% by mass or more of water.
• the content of water 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, in 100% by mass of the aqueous medium.
• a solvent compatible with water is preferable, and examples thereof include alcohol, ether, ketone, ester, etc., and specifically, examples of the solvents exemplified as the organic solvent contained in the aqueous dispersion described later are solvents.
• the resin particles (Pp) of the present disclosure are aqueous emulsion particles, the preferred aspects of the particle shape, average particle size, particle structure, particle composition, glass transition temperature, etc. are the same as the preferred aspects described in the resin particles (Pp) of the present disclosure.
• the water-based dispersion of the present disclosure is characterized by containing the resin particles (Pp) of the present disclosure. More specifically, the water-based dispersion of the present disclosure is obtained by dispersing the resin particles (Pp) in a water-based solvent.
• the aqueous solvent means 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.
• the organic solvent is preferably an organic solvent that is compatible with water, and examples of the organic solvent include monohydric alcohols, polyhydric alcohols, polyhydric alcohol derivatives, ethers, ketones, esters, etc. Among these, monohydric alcohols, polyhydric alcohols, and polyhydric alcohol derivatives are preferred.
• the monohydric alcohols mentioned above are preferably monohydric alcohols having 1 to 3 carbon atoms, such as methanol, ethanol, and 2-propanol.
• polyhydric alcohols include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, and glycerin.
• Glycol derivatives are more preferred as the polyhydric alcohol derivatives, and examples of the glycol derivatives include monoalkyl ethers of glycol 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; monocarboxylic acid esters of glycol such as ethylene glycol monoacetate; dialkyl ethers of glycol such as ethylene glycol dimethyl ether; dicarboxylic acid esters of glycol such as ethylene glycol diacetate; and monoalkyl ether monocarboxylic acid esters of glycol such as ethylene glycol monomethyl ether acetate.
• monoalkyl ethers of glycol such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl
• the organic solvent is preferably a glycol or a monoalkyl ether of a glycol, more preferably a mono-, di-, or tri- C2-3 alkylene glycol or a di- C2-3 alkylene glycol mono- C1-4 alkyl ether, and further preferably propylene glycol, diethylene glycol, triethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, or diethylene glycol monoisobutyl ether.
• the organic solvents may be used alone or in combination of two or more kinds.
• the resin particles (Pp) contained in the aqueous dispersion of the present disclosure are similar to the resin particles (Pp) explained in "2. Resin Particles", and the explanation therefor can be applied mutatis mutandis.
• the resin particles (Pp) contained in the aqueous dispersion of the present disclosure are preferably the aqueous emulsion particles. That is, an aqueous dispersion in which the aqueous emulsion particles are dispersed in an aqueous solvent is one of the preferred embodiments of the aqueous dispersion of the present disclosure.
• An aqueous dispersion in which the aqueous emulsion particles are dispersed in an aqueous solvent is also called an aqueous emulsion.
• the aqueous dispersion of the present disclosure may contain, in addition to the resin particles (Pp) and the aqueous solvent, a dispersant for the purpose of improving the dispersion stability of the resin particles (Pp).
• a dispersant include a surfactant and a water-soluble polymer.
• the resin particles (Pp) are preferably stabilized in dispersion in the aqueous dispersion by a surfactant
• the aqueous emulsion particles are preferably stabilized in dispersion in the aqueous emulsion by a surfactant.
• the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and the like, and include conventionally known surfactants. These surfactants may be contained alone or in combination of two or more in the aqueous dispersion (preferably the aqueous emulsion).
• nonionic surfactants and/or anionic surfactants are preferred.
• surfactants containing a polymerizable group in the molecule are also preferred.
• the polymerizable group include groups having an ethylenically unsaturated double bond.
• nonionic surfactants containing a polymerizable group and/or anionic surfactants containing a polymerizable group are particularly preferred.
• Surfactants containing a polymerizable group are also referred to as reactive emulsifiers.
• polymeric emulsifiers can also be used as the surfactant.
• the anionic surfactants include, for example, 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 Examples include sulfate salts; dialkyl s
• nonionic surfactant examples include polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, condensation products of polyethylene glycol and polypropylene glycol, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid monoglycerides, condensation products of ethylene oxide and aliphatic amines, polyoxyalkylene alkenyl ethers, etc.
• polymeric emulsifiers examples include poly(meth)acrylates such as sodium polyacrylate; polyvinyl alcohol; polyvinylpyrrolidone; polyhydroxyalkyl(meth)acrylates such as polyhydroxyethyl acrylate; and copolymers in which one or more of the monomers constituting these polymers are copolymerized components.
• 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., product name: ELEMINOL RS-30, etc.), polyoxyethylene alkylpropenyl phenyl ether sulfonate salts (e.g., Daiichi Kogyo Seiyaku Co., Ltd., product name: AQUALON HS-10, etc.), allyloxymethyl alkyloxy polyoxyethylene sulfonate salts (e.g., Daiichi Kogyo Seiyaku Co., Ltd., product name: AQUALON KH-10, etc.), polyoxyethylene styrenated propenyl phenyl ether sulfate ammonium salts, anionic surfactants containing a polyme
• the content of the dispersant is preferably 0.5 to 10 parts by mass, and more preferably 1.0 to 5 parts by mass, per 100 parts by mass of the resin particles (Pp).
• the resin particles (Pp) obtained by emulsion polymerization in an aqueous medium are called aqueous emulsion particles, and the aqueous dispersion in which the aqueous emulsion particles are dispersed in the aqueous solvent is called an aqueous emulsion.
• the polymerization liquid obtained by emulsion polymerization 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.
• the content of the resin particles (Pp) contained in the aqueous dispersion is not particularly limited, but it is preferable that the content of the resin particles (Pp) relative to 100% by mass of the aqueous dispersion is 10 to 70% by mass. If it is 10% by mass or more, excellent film-forming properties are obtained, and if it is 70% by mass or less, low viscosity and excellent workability tend to be obtained. More preferably, it is 20% by mass or more and 65% by mass or less, and even more preferably, it is 30% by mass or more and 60% by mass or less.
• the average 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 ⁇ m or less from the viewpoint of excellent dispersion stability. From the viewpoint of easily blending the resin particles at a high concentration while keeping the viscosity of the dispersion in an appropriate range, it is more preferably 50 nm or more and 500 nm or less, even more preferably 100 nm or more and 400 nm or less, and particularly preferably 150 nm or more and 350 nm or less.
• the dispersion average 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 type particle size distribution meter or a dynamic light scattering method.
• the aqueous dispersion can be appropriately diluted with ion-exchanged water and used as a sample.
• the pH of the aqueous dispersion of the present disclosure is preferably from 5 to 10, more preferably from 6 to 9.5, and even more preferably from 7 to 9.5, from the viewpoint of the stability of the aqueous dispersion.
• Any pH adjuster can be used to adjust the pH of the aqueous dispersion of the present disclosure to the above range.
• 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; 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.
• 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 the resin particle (Pp) powder with an aqueous solvent and dispersing it can be adopted. If necessary, the above-mentioned dispersant or the like can be mixed. 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 it is as the aqueous dispersion of the present disclosure.
• 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 part of the solvent and adjust the content of the aqueous emulsion particles, etc., to be the aqueous dispersion of the present disclosure.
• the aqueous dispersion of the present disclosure can be prepared by adding water, an organic solvent, or an aqueous solvent to an aqueous emulsion obtained by emulsion polymerization of a polymerizable monomer composition containing a polymerizable monomer (M) in an aqueous medium.
• the ink of the present disclosure is an ink containing a binder and a solvent, and is characterized in that the binder contains the polymer (Pm) of the present disclosure and/or the resin particles (Pp) of the present disclosure. Therefore, by using the ink of the present disclosure, it is easy to obtain a printed matter having excellent adhesion to a substrate, particularly when the substrate is made of polyolefin.
• the solvent constituting the ink of the present disclosure is not particularly limited.
• it may be water, an organic solvent, or a combination of these. Among them, water or a combination of water and an organic solvent is preferable, and an aqueous solvent is more preferable.
• the aqueous solvent is synonymous with 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.
• an organic solvent similar to the organic solvent in the aqueous solvent constituting the aqueous dispersion of the present disclosure described above can be used, and the preferred aspects are also the same.
• an ink in which the solvent is a water-based solvent is also referred to as a water-based ink.
• polymer (Pm) and resin particles (Pp) contained as a binder in the ink of the present disclosure are the same as those described in "1. Polymer” and “2. Resin Particles" and their preferred embodiments, including their respective preferred embodiments, and the descriptions therefor can be applied mutatis mutandis.
• the polymer (Pm) 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.
• the glass transition temperature is more preferably 45° C. or lower, and even more preferably 40° C. or lower.
• 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.
• the glass transition temperature of the polymer (Pm) contained in the ink of the present disclosure is preferably ⁇ 40 to 50° C., more preferably ⁇ 35 to 45° C., and even more preferably ⁇ 30 to 40° C.
• the resin particles (Pp) also preferably have a glass transition temperature in the same range as that of the polymer (Pm) for the same reasons.
• 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 ⁇ m or less.
• the lower limit is more preferably 50 nm or more, and even more preferably 150 nm or more.
• 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.
• the binder may contain one or more types of polymers (Pm), may contain one or more types of resin particles (Pp), or may contain one or more types of polymers (Pm) and one or more types of resin particles (Pp). Of these, it is preferable for the binder to contain at least resin particles (Pp), and it is even more preferable for the resin particles (Pp) to be aqueous emulsion particles.
• 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.
• the binder components other than the polymer (Pm) and the resin particles (Pp) are not particularly limited, and conventionally known materials can be used.
• materials that can be used as the other binder components include vinyl resins, (meth)acrylic resins, olefin resins, urethane resins, fluorine 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).
• the binder preferably contains at least resin particles (Rp), and more preferably contains the aqueous emulsion particles. That is, an ink containing a binder and a solvent, the solvent being aqueous, and the binder containing the 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 aqueous emulsion particles is one of the more preferred embodiments of the ink of the present disclosure.
• the content of each component contained in the ink of the present disclosure is not particularly limited.
• the content of the binder in the ink of the present disclosure is preferably 1 to 70% by mass per 100% by mass of the ink. If it is less than 1% by mass, there is a risk that performance such as adhesion will decrease, and if it exceeds 70% by mass, there is a risk that the viscosity will be high and workability will decrease. More preferably, it is 5% by mass or more and 65% by mass or less.
• the content of the binder in the solid content of the ink of the present disclosure is preferably 4 to 100% by mass, more preferably 20 to 99% by mass, and even more preferably 30 to 98% by mass.
• 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.
• the content of the binder in the solid content of the ink is preferably 4 to 100% by mass, more preferably 50 to 99% by mass, even more preferably 60 to 98% by mass, and even more preferably 70 to 98% by mass.
• the solid content refers to the components excluding the solvent.
• 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.
• the ink of the present disclosure may contain pigments, crosslinking agents, other components, etc., as described below, as necessary.
• the ink of the present disclosure preferably further contains a pigment.
• a pigment By containing a pigment, the hue of the ink can be adjusted.
• an ink containing a pigment may be referred to as a "colored ink.”
• the ink of the present disclosure may 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 subtractive primary colors of magenta, yellow, and cyan, as well as colors of different densities such as light cyan, dark yellow, light magenta, and light black.
• the pigment may have one or more hues selected from red, blue, orange, green, and violet.
• a pigment that exhibits a white hue may be referred to as a white pigment
• a pigment that exhibits a hue other than white (chromatic color or black) may be referred to as a colored pigment.
• the pigment may be any pigment known in the art.
• pigments include organic pigments and inorganic pigments, which may be used alone or in combination of two or more types. If necessary, they may also be used in combination with an extender pigment.
• organic pigments examples 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.
• azo pigments such as benzidine and Hansa Yellow
• diazo pigments such as benzidine
• 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 products with product numbers such as 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.
• organic pigments that do not contain metals so as not to promote thermal decomposition of polypropylene. Specifically, Pigment Blue 16, etc. can be selected.
• inorganic pigments include titanium dioxide, antimony trioxide, zinc oxide such as zinc oxide, lithopone, white lead, red iron oxide, black iron oxide, chromium oxide green, carbon black, yellow lead, molybdenum red, ferric ferrocyanide (Prussian blue), ultramarine, lead chromate, etc.
• inorganic pigments include flat pigments such as mica, clay, aluminum powder, talc, and aluminum silicate, and extender pigments such as calcium carbonate, magnesium hydroxide, aluminum hydroxide, barium sulfate, and magnesium carbonate.
• carbon black include furnace black, thermal lamp black, acetylene black, and channel black.
• preferred white pigments are titanium dioxide, antimony trioxide, zinc oxide such as zinc oxide, lithopone, white lead, calcium carbonate, magnesium hydroxide, aluminum hydroxide, barium sulfate, magnesium carbonate, clay, talc, and aluminum silicate.
• titanium dioxide is preferred from the viewpoint of its high refractive index and excellent hiding power.
• titanium dioxide with a rutile crystal structure is preferred.
• 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, lead chromate, etc.
• the average particle size of the pigment is preferably 10 to 1000 nm, more preferably 20 to 500 nm, from the viewpoint of dispersion stability and color development or hiding power.
• 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.
• the average particle size is preferably 20 to 200 nm, particularly from the viewpoint of color development, more preferably 40 to 150 nm, and even more preferably 50 to 100 nm.
• the above average particle size is preferably the average particle size of the pigment dispersed in the ink of the present disclosure.
• the average particle size of the pigment dispersed can be measured by a measurement method using a laser diffraction scattering type particle size distribution meter or a dynamic light scattering method, similar to the average particle size of the resin particles (Pp) in the aqueous dispersion of the present disclosure.
• a particle size distribution meter using the dynamic light scattering method (Otsuka Electronics Co., Ltd., product number: nanoSAQLA) to determine the autocorrelation function by the photon correlation method and to adopt the average particle size (hydrodynamic diameter) determined by cumulant analysis.
• the 50% particle size in the volume-based particle size distribution obtained by a measurement method using a laser diffraction scattering type particle size distribution meter can be adopted as the average particle size.
• the pigment is preferably stabilized in dispersion by a dispersant in the ink of the present disclosure. That is, the ink of the present disclosure preferably contains a dispersant together with the pigment.
• 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 with respect to 100 parts by mass of the pigment.
• the pigment content is not particularly limited, but is preferably 1 to 40% by mass per 100% by mass of the ink. If it is less than 1% by mass, there is a risk that the color development is insufficient, and if it exceeds 40% by mass, there is a risk that the coating film becomes brittle. More preferably, it is 2% by mass or more and 35% by mass or less. Furthermore, when the ink of the present disclosure contains a pigment, the content of the pigment relative to 100 parts by mass of the binder is preferably 10 to 400 parts by mass, more preferably 20 to 300 parts by mass, and even more preferably 30 to 200 parts by mass.
• the ink of the present disclosure may further contain a crosslinking agent.
• a crosslinking agent By containing a crosslinking agent, a crosslinking effect is exerted through interaction with the components contained in the ink of the present disclosure, such as the polymer (Pm) and/or resin particles (Pp), or the pigment, dispersant, etc., if a pigment is contained, or through a chemical reaction, making it easier to form a tough coating film.
• 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, and the like. These crosslinking agents may be used alone or in combination of two or more types.
• oxazoline group-containing compounds are preferred from the viewpoint of excellent crosslinking performance.
• the above oxazoline group-containing compounds refer to compounds having two or more oxazoline groups in the molecule.
• examples of the above oxazoline group-containing compounds 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), 2,2'-ethylene-bis (4,4'-dimethyl-2-oxazoline), 2,2'-p-phenylene-bis(2-oxazoline), 2,2'-m-phenylene-bis(2-oxazoline), 2,2'-m-phenylene-bis(4,4'
• oxazoline group-containing compounds from the viewpoint of excellent crosslinking performance, water-soluble oxazoline group-containing compounds and/or oxazoline group-containing polymers are preferred, and water-soluble oxazoline group-containing polymers are more preferred.
• the above oxazoline group-containing polymers can be produced by a conventionally known production method. For example, a method of polymerizing a monomer component containing one or more types of addition polymerizable oxazolines, or an addition polymerizable oxazoline and a monomer copolymerizable with the addition polymerizable oxazoline, can be mentioned.
• a monomer that does not have a functional group that reacts with the oxazoline group and is copolymerizable with the addition polymerizable oxazoline is preferred.
• a monomer that does not have a functional group that reacts with the oxazoline group in the above ethylenically unsaturated double bond-containing monomer specifically, the monomer exemplified as the monomer that constitutes the polymer (Pm)
• Pm polymer that constitutes the polymer
• 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, ⁇ -methylstyrene, and chloromethylstyrene; olefin monomers such as ethylene and propylene; and the like.
• (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, ⁇ -methylstyrene, and chloromethylstyrene
• Examples of the above-mentioned 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.
• water-soluble oxazoline group-containing polymers are preferred, and can be produced by the same method as the above-mentioned method for producing oxazoline group-containing polymers.
• water-soluble oxazoline group-containing polymers include polymers that have an acrylic polymer, an acrylic-styrene polymer, or the like as the main chain and contain oxazoline groups in the side chains.
• oxazoline group-containing polymers examples include water-soluble polymers such as Epocross WS-500 and Epocross WS-700 manufactured by Nippon Shokubai Co., Ltd., and emulsion-type polymers such as Epocross K-2010, Epocross K-2020, and Epocross K-2030. Of these, the water-soluble polymers Epocross WS-500 and Epocross WS-700 manufactured by Nippon Shokubai Co., Ltd. are preferred.
• 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 it is less than 0.1 part by mass, there is a risk that the coating strength will be difficult to improve, and if it exceeds 30 parts by mass, there is a risk that the water resistance will decrease. 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 strength, it is preferably 0.5 to 10 parts by mass relative to 100 parts by mass of the binder, and more preferably 5 parts by mass or less.
• 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.
• the ink of the present disclosure may further contain other components in addition to the above-mentioned binder component, solvent, pigment, and crosslinking agent, so long as the object of the present invention is not impaired.
• the ink may contain additives such as surfactants, dispersants, leveling agents, UV absorbers, UV stabilizers, thickeners, wetting agents, plasticizers, stabilizers, defoamers, dyes, antioxidants, crosslinking accelerators, pH adjusters, and preservatives in appropriate amounts.
• the leveling agent for example, acetylene glycol-based, silicone-based, and fluorine-based surfactants are preferably used, and among them, polyether-modified silicone compounds are preferred.
• the 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.
• the content is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more.
• the method for producing the ink of the present disclosure is not particularly limited.
• the ink can be produced by mixing a binder and a solvent, as well as a pigment, a crosslinking agent, and additives that are used as needed.
• an ink containing a pigment it is preferable to prepare a pigment dispersion containing the pigment in advance, and mix the aqueous dispersion (preferably the aqueous emulsion), the pigment dispersion, and other components such as a crosslinking agent.
• aqueous dispersion preferably the aqueous emulsion
• other components such as a crosslinking agent.
• an emulsion containing aqueous emulsion particles is prepared.
• the emulsion containing aqueous emulsion particles can be produced by a conventional emulsion polymerization method as described above.
• an aqueous emulsion is prepared in which aqueous emulsion particles containing the polymer (Pm) (preferably the resin (Pp)) of the present disclosure are dispersed in an aqueous solvent at a predetermined ratio by performing emulsion polymerization in an aqueous medium using a polymerizable monomer composition containing a polymerizable monomer (M) as a raw material.
• 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.
• the aqueous emulsion obtained by the emulsion polymerization method usually contains an emulsifier such as a surfactant used in the emulsification, but the aqueous emulsion may be used as it is as the aqueous emulsion for preparing the ink of the present disclosure.
• a pigment dispersion when preparing an ink containing a pigment, it is preferable to prepare a pigment dispersion.
• the pigment dispersion can be produced by mixing the pigment and dispersant in water or an aqueous solvent, and carrying out a dispersion process using a bead mill or the like.
• the pigment content in the pigment dispersion is not particularly limited, but is preferably 15 to 65 mass% relative to 100 mass% of the pigment dispersion.
• the dispersant content is also not particularly limited, but is preferably 1 to 10 mass parts relative to 100 mass parts of pigment in the pigment dispersion.
• the above-mentioned aqueous emulsion and other components such as the above-mentioned pigment dispersion and crosslinking agent, which are used as necessary, are mixed to prepare a mixture.
• the above-mentioned 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 above-mentioned components are not particularly limited.
• the water-based emulsion and the pigment dispersion may be mixed together, and then the crosslinking agent may be mixed therewith; the pigment dispersion and the crosslinking agent may be mixed together and then the water-based emulsion may be mixed therewith; the water-based emulsion and the crosslinking agent may be mixed together and then the pigment dispersion may be mixed therewith; or the pigment dispersion, the water-based emulsion, and the crosslinking agent may be mixed together at approximately the same time.
• a solvent can be further added to the mixture.
• the solvent water, an organic solvent such as glycols, or a mixture of water and an organic solvent can be used.
• Components such as additives other than the above may be further mixed. The timing of mixing these solvents (adjustment solvents), additives, etc. may be appropriately selected. After mixing the components, centrifugation, filtration, etc. can be performed as necessary.
• an aqueous ink containing aqueous emulsion particles and an aqueous solvent for example, an aqueous ink containing a pigment, aqueous emulsion particles, a crosslinking agent, and an aqueous solvent, etc.
• an aqueous ink containing a pigment, aqueous emulsion particles, a crosslinking agent, and an aqueous solvent, etc. for example, an aqueous ink containing a pigment, aqueous emulsion particles, a crosslinking agent, and an aqueous solvent, etc.
• the method for producing a printed matter according to the present disclosure uses the ink according to the present disclosure, that is, the method for producing a printed matter according to the present disclosure is a method for producing a printed matter having an image printed on a substrate, the method including an image forming step of applying the ink according to the present disclosure to a substrate to form an image. Therefore, the printed matter obtained by the method for producing a printed matter according to the present disclosure has excellent adhesion to the substrate, and in particular, when the substrate is made of polyolefin, the printed matter having excellent adhesion to the substrate is easily obtained.
• the ink used in the method for producing a printed matter of the present disclosure is an ink containing a binder and a solvent, characterized in that the binder contains the polymer (Pm) of the present disclosure and/or the resin particles (Pp) of the present disclosure (preferably contains the resin particles (Pp) of the present disclosure).
• the specific configuration of the ink e.g., the solvent contained in the ink, the type and amount of binder, etc.
• is similar to the specific configuration of the ink e.g., the solvent contained in the ink, the type and amount of binder, etc.
• the ink used in the manufacturing method of the printed matter of the present disclosure is a water-based ink.
• the substrate is not particularly limited, but is preferably a fabric, a polymer film, a polymer molded body, or the like.
• the fabric includes all textile products such as cloth and textiles made from natural and/or synthetic fibers. Examples of the 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 of these.
• a printed matter obtained using a fabric as the substrate may be referred to as a "printed material".
• Preferred examples of the natural fibers include silk, cotton, and wool.
• the chemical fibers include synthetic fibers, regenerated fibers, and semi-synthetic fibers.
• Preferred examples of synthetic fibers include polyester fibers, nylon fibers, acrylic fibers, polyurethane fibers, polyolefin fibers such as polyethylene fibers and polypropylene fibers, and vinylon fibers.
• Preferred examples of regenerated fibers include rayon.
• Preferred examples of semi-synthetic fibers include acetate and triacetate.
• the fabric is preferably a fabric containing at least one type of 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.
• the fabric used as the substrate is a nonwoven fabric
• examples of the material include polyolefins such as polyethylene and polypropylene, rayon, cotton, and celluloses, with polyolefins being preferred, and polypropylene being particularly preferred.
• 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.
• the substrate is preferably a polyolefin film or a polyester film.
• Preferred examples of the polyolefin film include polyethylene film and polypropylene film
• preferred examples of the polypropylene film include CPP (non-oriented polypropylene) and OPP (biaxially oriented polypropylene), with OPP being particularly preferred.
• the polyester film is preferably a polyethylene terephthalate film.
• the above-mentioned polymer molded body may be a polyolefin plate such as an SBR (styrene butadiene rubber) plate, a polyethylene plate, or a polypropylene plate, with a polyolefin plate being preferred, and a polypropylene plate being particularly preferred.
• a polyolefin plate such as an SBR (styrene butadiene rubber) plate, a polyethylene plate, or a polypropylene plate, with a polyolefin plate being preferred, and a polypropylene plate being particularly preferred.
• the ink of the present invention is suitably used for substrates made of polyolefin.
• a substrate made of polyolefin may be referred to as a polyolefin substrate.
• the polyolefin substrate include fabrics such as woven fabrics, nonwoven fabrics, knitted fabrics, etc., made of polyolefin fibers (e.g., polyethylene fibers, polypropylene fibers); films made of polyolefins (e.g., polyethylene, polypropylene); and molded products of polyolefins such as polyolefin plates (e.g., polyethylene plates, polypropylene plates).
• a fabric made of polyolefin fibers and a film made of polyolefin are preferred, and a fabric made of polyethylene fibers, a fabric made of polypropylene fibers, a polyethylene film, and a polypropylene film are more preferred.
• the substrate may have a surface onto which the ink of the present invention is printed that has been chemically or physically modified by corona treatment, anchor coat treatment, or the like. This provides better adhesion to the image formed from the ink of the present invention.
• Specific examples include corona-treated polyolefin films.
• the method of applying the ink of the present disclosure to 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.
• a substrate on which the image is formed can be obtained.
• the inkjet printing method 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.
• the inkjet printer can be of any type, such as a piezoelectric type, a thermal type, or a charge change control type (continuous ejection type). Among them, a piezoelectric type inkjet printer is preferred.
• the piezoelectric type inkjet printer there are no particular limitations on the ink ejection conditions. 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.
• the viscosity of the ink of the present disclosure is preferably in the range of 2 to 20 mPa/s.
• the surface tension of the ink of the present disclosure is preferably in the range of 25 to 45 mN/m.
• the ink ejected from the nozzle openings of the inkjet printer head adheres to the surface of the substrate to form an image.
• the substrate on which an image has been formed by the inkjet printing method is preferably heat-treated as described below.
• the heating method, timing of the heat treatment, heating temperature, etc., including preferred embodiments of each, are as described below.
• the method for producing a printed matter disclosed herein preferably includes a heating step (also referred to as a heat treatment step). That is, it is preferable to heat treat the substrate on which an image has been formed by the above-mentioned method.
• the heat treatment can promote the removal of volatile components, such as the ink-derived aqueous solvent, contained in the image formed on the substrate, and can also promote fixation of the image by melting the binder components contained in the ink.
• the heat treatment step may be performed simultaneously with the image formation step or after the image formation step.
• the two may also be combined.
• a method of performing the heat treatment step simultaneously with the image formation step is to perform the image formation step while heating the substrate.
• Preferred heat treatment methods when the heat treatment step is performed after the image formation step include, for example, a heating method using a heating and drying oven, a heating method using a heat press, a heating method using an infrared lamp, an electric hot plate method, and a method using steam such as normal pressure steam or high pressure steam.
• it is preferable to perform the heat treatment step after the image formation step since there is a risk of disturbing the air flow if the two are performed simultaneously.
• the heating temperature is not particularly limited, but is preferably 60 to 180°C.
• the upper limit is more preferably 150°C or less, and even more preferably 110°C or less, and the lower limit is more preferably 70°C or more, and even more preferably 80°C or more.
• the heating time is not particularly limited, but is preferably 0.5 to 30 minutes.
• the upper limit is more preferably 20 minutes or less, and even more preferably 10 minutes or less, and the lower limit is more preferably 1 minute or more, and even more preferably 2 minutes or more.
• the heating temperature and time in the heat treatment process differ depending on the material of the fabric.
• 120 to 190°C is preferred for cotton, 70 to 130°C (preferably 125°C) for polypropylene, and 110 to 170°C (preferably 110°C) for polyester, each of which is preferably within 5 minutes.
• the printed matter (printed matter) on which an image is formed on the fabric obtained after the above heat treatment process may be washed with water and dried.
• the above-mentioned method for producing printed matter makes it possible to produce printed matter with excellent adhesion of the printed image in an energy-saving and environmentally friendly manner. In particular, it is possible to obtain printed matter with excellent adhesion of the image even when the substrate is polyolefin.
• the image fixing article of the present disclosure is an image fixing article in which an image containing a pigment and a resin is fixed to a part or all of a substrate, and is characterized in that the resin contains a polymer (Pm) containing a structure derived from the polymerizable monomer (M) represented by the above formula (1) as a constituent unit.
• Pm polymer
• M polymerizable monomer
• the resin contains a polymer (Pm) that contains, as a constituent unit, a structure derived from the polymerizable monomer (M) represented by the above formula (1).
• the polymer (Pm) contained in the above resin is similar to the polymer (Pm) described in "1. Polymer”, and the description in "1. Polymer” can be applied mutatis mutandis as is.
• the resin may be a resin particle containing only the polymer (Pm) as a resin component, or may be a resin particle containing a resin component other than the polymer (Pm).
• the resin component other than the polymer (Pm) of the present disclosure is also referred to as the other resin component.
• the other resin component is not particularly limited, and examples thereof include vinyl resins, (meth)acrylic resins, olefin resins, urethane resins, fluorine resins, silicone resins, epoxy resins, phenoxy resins, phenol resins, xylene resins, and blocked isocyanates.
• the other resin component is preferably a polymer (Pm2), and the polymer (Pm2) is the same as the polymer (Pm2) described in "2.
• Resin Particles including its preferred embodiments, and the description in "2. Resin Particles” can be applied mutatis mutandis.
• an olefin resin is preferable as the other resin component from the viewpoint of adhesion.
• the content of the polymer (Pm) contained in the resin is not particularly limited, but is preferably 50% by mass or more, more preferably 80% by mass or more, even more preferably 95% by mass or more, and particularly preferably 100% by mass, of 100% by mass of the resin.
• the image contains the resin and the pigment.
• the total content of the resin and pigment in the image is preferably 70-100% by mass, more preferably 90-100% by mass, and even more preferably 95-100% by mass, relative to 100% by mass of the image.
• the resin content in the image is preferably 20% by mass or more and less than 100% by mass, more preferably 25-90% by mass, and even more preferably 30-85% by mass, relative to 100% by mass of the total content of the resin and pigment in the image.
• the image may be fixed to a part or the whole of the substrate.
• the film thickness of the image is not particularly limited, but is preferably 0.1 to 1000 ⁇ m, more preferably 0.3 to 500 ⁇ m, and even more preferably 0.5 to 100 ⁇ m.
• the film thickness may be, for example, a value measured by observation using a laser microscope or the like.
• the image may contain other components in addition to the resin and pigment.
• it may contain an appropriate amount of additives such as a crosslinking agent, a surfactant, a dispersant, a leveling agent, an ultraviolet absorber, an ultraviolet stabilizer, a thickener, a wetting agent, a plasticizer, a stabilizer, an antifoaming agent, a dye, an antioxidant, a crosslinking promoter, a pH adjuster, and a preservative.
• the content of the other components is not particularly limited, but is preferably 30% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, relative to 100% by mass of the image. In order to exert the effect of the addition, it is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more.
• the above substrate including its preferred embodiments, is the same as the substrate that is 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.
• the method for producing the image-fixed article of the present disclosure is not particularly limited, and for example, the method for producing the printed matter of the present disclosure described above can be used.
• a preferred embodiment of the method is the same as the method for producing the printed matter described in "5. Method for producing the printed matter” and its preferred embodiment, and the description in "5. Method for producing the 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 adhesion to the image.
• the substrate is a polyolefin substrate (for example, a film, molded body, or nonwoven fabric made of polyolefin, or a cloth made of fiber), the image is an article having excellent adhesion to the substrate.
• the compound of the present disclosure is characterized by being represented by the following formula (2).
• A3 represents a hydrocarbon group containing two or more aromatic ring skeletons, and the hydrocarbon group may have a substituent, and the substituent is a nonionic substituent.
• a 4 represents an alkylene chain having 1 to 10 carbon atoms, and the alkylene chain may have a substituent. Note that, multiple A 4 's may be the same or different.
• m is an integer from 3 to 100.
• X2 represents a group having an ethylenically unsaturated double bond.
• the above compounds are similar to the compounds represented by formula (1) (i.e., polymerizable monomer (M)) described in "1.
• Polymer and the description of the polymerizable monomer (M) can be applied mutatis mutandis. That is, the compounds of the present disclosure can be suitably used as polymerizable monomers, and polymers containing structural units derived from the compounds of the present disclosure have excellent adhesion to polyolefin substrates. Therefore, by applying the compounds of the present disclosure to polymers for inks, images with excellent adhesion to polyolefin substrates can be printed.
• the "hydrocarbon group containing two or more aromatic ring skeletons" represented by A3 above is preferably at least one type selected from the group consisting of structures represented by formulas (1- a ) to (1-f) shown as preferred structures of the hydrocarbon group containing two or more aromatic ring skeletons (i.e., polycyclic phenyl group) represented by A1 in formula (1) above, and more preferably the structure represented by formula (1-a).
• the compound of the present disclosure has a structure other than X2 in formula (2), i.e., a structure of A 3 -(OA 4 ) m -O-, the compound itself tends to have excellent adhesion to a polyolefin substrate.
• a polymer polymerized using the compound of the present disclosure as a polymerizable monomer component has the above structure (a structure of A 3 -(OA 4 ) m -O-) as its side chain, particularly the structure represented by A 3 -(OA 4 ) 2 - (terminal structure), and therefore has excellent adhesion to a polyolefin substrate.
• a calculation method can be adopted in which the Gaussian16 program manufactured by Gaussian Corporation is used to apply B3LYP to the functional of the density functional theory, 6-31G (d, p) to the basis function, and dispersion force correction (GD3BJ keyword).
• the zero-point energy of the above-mentioned terminal structure of the compound of the present disclosure is substituted with the zero-point energy of a molecule having a structure similar to that of the above-mentioned terminal structure, specifically, a molecule represented by the following formula (2-1) (hereinafter also referred to as the structure molecule (I)), and the sum of the absolute value of the zero-point energy of the structure molecule (I) and the absolute value of the zero-point energy of the substrate molecule obtained by the calculation method, and the magnitude of the difference between the absolute value of the zero-point energy of the association between the structure molecule (I) and the substrate molecule, and the adhesion of a polymer using the compound of the present disclosure to a substrate are found to be correlated.
• a molecule represented by the following formula (2-1) hereinafter also referred to as the structure molecule (I)
• A3 and A4 are the same as A3 and A4 in formula (2), respectively.
• a 3 in the above formula (2-1) is the same as A 3 in the above formula (2), and (OA 4 ) 2 in the above formula (2-1) is the same as the adjacent (OA 4 ) 2 directly bonded to A 3 in the above formula (2).
• the compound of the present disclosure preferably satisfies the following formula (f2-1): ( EM +E P8 ) - (E MP ) ⁇ -80kJ/mol (f2-1)
• E M is the absolute value of the zero-point energy of the structural molecule (I)
• E P8 is the absolute value of the zero-point energy of the propylene octamer
• E MP is the absolute value of the zero-point energy of the association of the structural molecule (I) and the propylene octamer
• the structural molecule (I) has a structure represented by the above formula (2-1) when the compound is represented by the above formula (2).
• the above formula (f2-1) means that the difference d10 between the sum of the absolute value of the zero-point energy (E M ) of the structure molecule (I) and the absolute value of the zero-point energy (E P8 ) of the propylene octamer, and the absolute value of the zero-point energy (E MP ) of the association of the structure molecule (I) and the propylene octamer is less than ⁇ 80 kJ/mol.
• the zero-point energy of the association means the zero-point energy when the structural molecule (I) and the propylene octamer are present in the same space.
• a polymer having a structure derived from a compound having a corresponding terminal structure as a structural unit tends to have better adhesion to a polyolefin substrate, particularly a polypropylene substrate.
• the difference d10 is preferably -85 kJ/mol or less, more preferably -90 kJ/mol or less.
• E M , E P8 , and E MP have the same meanings as E M , E P8 , and E MP in the above formula (f2-1), respectively, and are values calculated in the same manner.
• E P6 is the absolute value of the zero-point energy of a propylene hexamer
• E PP is the absolute value of the zero-point energy of the association of the propylene octamer and the propylene hexamer.
• the zero-point energy of the association of the propylene octamer and the propylene hexamer means the zero-point energy when the propylene octamer and the propylene hexamer are in the same space.
• the above formula (f2-2) means that the difference d10 between the sum of the absolute value of the zero-point energy (E M ) of the structure molecule (I) and the absolute value of the zero-point energy (E P8 ) of the propylene octamer, and the absolute value of the zero-point energy (E MP ) of the association of the structure molecule (I) and the propylene octamer, is smaller (larger in a negative value) than the difference d20 between the sum of the absolute value of the zero-point energy (E P6 ) of the propylene hexamer and the absolute value of the zero-point energy (E P8 ) of the propylene octamer, and the absolute value of the zero-point energy (E PP ) of the association of the propylene hexamer and the propylene octamer.
• the absolute value (E M ) of the zero-point energy of the structural molecule (I) satisfies the above relational formula (f2-2)
• a polymer having a structure derived from a compound having a corresponding terminal structure as a constituent unit tends to have better adhesion to polyolefin substrates, particularly polypropylene substrates.
• 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.
• the method for producing the above compound is not particularly limited, but a preferred method will be described below.
• the method for producing the compound described here can also be used as a method for producing the above polymerizable monomer (M).
• 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 capable of reacting with a hydroxyl group.
• A5 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.
• A6 represents an alkylene chain having 1 to 10 carbon atoms, and the alkylene chain may have a substituent. Note that multiple A6s may be the same or different.
• z is an integer from 3 to 100.
• the compound (A) is not particularly limited as long as it is represented by the formula (3).
• the above A5 is the same as the specific and preferred aspects of A1 in the above formula (1), including specific and preferred aspects thereof, as A3 in the compound represented by the above formula (2), and the explanation regarding A1 can be applied mutatis mutandis as it is.
• the above A6 is the same as the specific and preferred embodiments of A2 in the above general formula (1), including specific and preferred embodiments thereof, as is the case with A4 in the compound represented by the above formula (2), and the explanation regarding A2 can be applied mutatis mutandis as is.
• n in the above general formula (1) is the same as the specific and preferred aspects of n in the above general formula (1), including specific and preferred aspects thereof, as is the case with m in the compound represented by the above formula (2), and the above explanation regarding n can be applied mutatis mutandis.
• Preferred commercially available products include, for example, Newcol 714, Newcol 707, and Newcol 704 manufactured by Nippon Nyukazai Co., Ltd., Noigen EA167 and Noigen EA137 manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and Emulgen A-60 and Emulgen A-90 manufactured by Kao Corporation.
• the compound (B) is not particularly limited as long as it is a compound having a group capable of reacting with a hydroxyl group and a group having an ethylenically unsaturated double bond.
• the group having an ethylenically unsaturated double bond is not particularly limited, but is preferably a radically polymerizable group, such as a (meth)acryloyl group, a vinyl group, a styryl group, an allyl group, etc.
• a (meth)acryloyl group is preferred from the viewpoint of copolymerizability.
• the compound (B) it is preferable to use, as the compound (B), a compound having a group capable of reacting with a hydroxyl group and the above-mentioned X 2.
• the compound (M) it is preferable to use, as the compound (B), a compound having a group capable of reacting with a hydroxyl group and the above-mentioned X 1 .
• Examples of the group capable of reacting with the hydroxyl group include a carboxyl group, anhydrous carboxyl group, an isocyanate group, and an ester group.
• anhydrous carboxyl group is preferred. This is because it easily reacts with the hydroxyl group of the compound (A) under mild conditions to form an ester bond. From an economical perspective, it is preferred to carry out an ester exchange reaction with a methyl ester or the like, or to convert methacrylic acid into an acid ester.
• the group having an ethylenically unsaturated double bond and the group capable of reacting with a hydroxyl group may be in a combination in which each group shares a part of the other group.
• acrylic acid which is an example of compound (B)
• Examples of the compound (B) include (meth)acrylic acid, (meth)acrylic acid anhydride, 2-(meth)acryloyloxyethyl isocyanate, and (meth)acrylic acid esters such as methyl (meth)acrylate (preferably (meth)acrylic acid C1-4 alkyl esters).
• (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.
• the method and conditions for reacting the compound (A) with the compound (B) are not particularly limited, but for example, a method of heating a mixture containing the compound (A) and the compound (B) or a method of obtaining the compound by an ester exchange reaction between the compound (A) and a (meth)acrylic acid ester such as methyl methacrylate is preferred.
• a catalyst can be present to promote the reaction.
• 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.
• catalyst or co-catalyst examples include sulfonic acid compounds such as paratoluenesulfonic acid, benzenesulfonic acid, xylenesulfonic acid, methanesulfonic acid, and sulfuric acid.
• ester exchange catalyst in the ester exchange reaction between compound (A) and the (meth)acrylic acid ester.
• the transesterification catalyst may be any known one without any particular limitation.
• the transesterification catalyst 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; carboxy
• alkoxy compounds include 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 di
• a solvent may be used, for example, aromatic compound solvents such as benzene, toluene, xylene, etc., aliphatic compound solvents such as hexane, heptane, etc., alicyclic compound solvents such as cyclohexane, etc., and ether compound solvents such as diisopropyl ether, dibutyl ether, etc. These solvents may be used alone or in combination of two or more.
• aromatic compound solvents such as benzene, toluene, xylene, etc.
• aliphatic compound solvents such as hexane, heptane, etc.
• alicyclic compound solvents such as cyclohexane, etc.
• ether compound solvents such as diisopropyl ether, dibutyl ether, etc.
• the heating temperature is not particularly limited and may be appropriately selected depending on the compounds (A) and (B) used. From the viewpoints of inhibiting discoloration and polymerization, and improving productivity, the heating temperature is preferably 50 to 150°C, more preferably 60 to 120°C, and even more preferably 70 to 100°C.
• the heating time is not particularly limited, but from the viewpoints of inhibiting discoloration and polymerization, and improving productivity, the time from the time when the entire 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 performed under normal pressure or under pressure.
• the reaction produces a reaction solution containing the compound of the present disclosure.
• the reaction solution contains the solvent used in the reaction, residues of compound (A) and compound (B), catalyst residues, etc., in addition to the compound of the present disclosure, but the compound of the present disclosure can be isolated by a conventionally known purification method.
• the purification method include washing with a basic aqueous solution or an acidic aqueous solution, or with Glauber's salt water, and distilling off low boiling points under reduced pressure. According to the above-mentioned 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) that is a raw material for the polymer (Pm), resin particles (Pp), etc. of the present disclosure.
• a particle size distribution measuring device manufactured by Otsuka Electronics Co., Ltd., product number: nanoSAQLA
• Base material Polypropylene (for automobiles) manufactured by Standard Test Piece. 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 applied to the test specimen so as to remove air, and the test specimen was pressed 10 times with 500 g. After 1 minute, the tape was peeled off at 100 mm/sec, and the peeled area was evaluated using an average of N5.
• ⁇ PP adhesion 2> The substrate was changed to a corona-treated OPP film (product number: FOR-AQ) manufactured by Futamura Chemical Co., Ltd., and the film was evaluated in the same manner as in PP adhesion 1, except that the 2 mm wide grid cross-cut was not performed.
• Peeling area exceeds 5%.
• Example 1-1 A 300 ml separable flask equipped with a thermometer, a cooling tube, 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.
• reaction solution was washed twice with 40 parts of a 5 wt % aqueous sodium hydroxide solution and twice with 40 parts of a 20 wt % aqueous sodium sulfate solution, and low boiling points 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) which is a pale yellow transparent liquid.
• 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).
• Examples 1-3 Monomer (3) was obtained in the same manner as in Example 1-1, except that 120 parts of Newcol 704 was changed to 120 parts of Noigen EA167 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., an emulsifier having a polycyclic phenyl group and a polyethylene oxide group and no ionic group).
• Noigen EA167 manufactured by Daiichi Kogyo Seiyaku Co., Ltd., an emulsifier having a polycyclic phenyl group and a polyethylene oxide group and no ionic group.
• Examples 1 to 4 Monomer (4) was obtained in the same manner as in Example 1-1, except that 120 parts of Newcol 704 was changed to 120 parts of Emulgen A-60 (manufactured by Kao Corporation, an emulsifier having a distyrenated phenol group, which is a polycyclic phenyl group, and a polyethylene oxide group, and having no ionic group).
• 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.
• the absolute value of the zero-point energy of the structure molecule (4) represented by the 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 association of the structure molecule (4) and the propylene octamer were obtained by a calculation method in which B3LYP is used as the functional of the density functional theory, 6-31G (d, p) as the basis function, and dispersion force correction (GD3BJ keyword).
• the absolute value of the zero-point energy of the structure molecule (4) (3,343,411 kJ/mol) and the absolute value of the zero-point energy of the propylene octamer (2,582,206 kJ/mol) were subtracted from the absolute value of the zero-point energy of the association of the structure molecule (4) and the propylene octamer (5,925,708 kJ/mol), which was -91 kJ/mol.
• 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 calculated by a calculation method using the Gaussian 16 program manufactured by Gaussian Corporation, in which B3LYP is used as the functional of the density functional theory, 6-31G (d, p) as the basis function, and dispersion force correction (GD3BJ keyword).
• Example 2-1 In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 355 parts of deionized water were charged.
• a pre-emulsion for the second dropwise addition 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 dropped into the flask over 120 minutes.
• aqueous dispersion contained a polymer, the polymer being a resin emulsion particle, and the resin emulsion particle was an emulsion particle having a two-layer structure having an inner layer and an outer layer.
• the content of non-volatile matter in this aqueous dispersion (emulsion (1)) was 40%, the average particle size of the resin emulsion particle was 200 nm, the proportion of the structural unit derived from monomer (1) in the total of all the polymers being the non-volatile matter was 20%, and the proportion of the structural unit derived from monomer (1) in the polymer constituting the outer layer was 40%.
• Example 2-2 An emulsion (2) was obtained 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, the polymer being a resin emulsion particle, and the resin emulsion particle was an emulsion particle having a two-layer structure having an inner layer and an outer layer.
• the content of non-volatile matter in the emulsion (2) was 40%, the average particle size of the resin emulsion particle was 200 nm, the proportion of the structural unit derived from monomer (1) in the total of all the polymers being the non-volatile matter was 2%, and the proportion of the structural unit derived from monomer (1) in the polymer constituting the outer layer was 4%.
• Example 2-3 An emulsion (3) was obtained in the same manner as in Example 2-1, except that 80 parts of the monomer (2) was used instead of 80 parts of the monomer (1).
• the obtained emulsion (3) contained a polymer, the polymer being a resin emulsion particle, and the resin emulsion particle was an emulsion particle having a two-layer structure having an inner layer and an outer layer.
• the content of non-volatile matter in the emulsion (3) was 40%, the average particle size of the resin emulsion particle was 200 nm, the proportion of the structural unit derived from the monomer (2) in the total of all the polymers being the non-volatile matter was 20%, and the proportion of the structural unit derived from the monomer (2) in the polymer constituting the outer layer was 40%.
• Example 2-4 An emulsion (4) was obtained in the same manner as in Example 2-1, except that 80 parts of the monomer (3) was used instead of 80 parts of the monomer (1).
• the obtained emulsion (4) contained a polymer, the polymer was a resin emulsion particle, and the resin emulsion particle was a two-layer structure emulsion particle having an inner layer and an outer layer.
• the content of non-volatile matter in the emulsion (4) was 40%, the average particle size of the resin emulsion particle was 200 nm, the proportion of the structural unit derived from monomer (3) in the total of all the polymers being the non-volatile matter was 20%, and the proportion of the structural unit derived from monomer (3) in the polymer constituting the outer layer was 40%.
• Example 2-5 An emulsion (5) was obtained in the same manner as in Example 2-1, except that 80 parts of the monomer (4) was used instead of 80 parts of the monomer (1).
• the obtained emulsion (5) contained a polymer, the polymer was a resin emulsion particle, and the resin emulsion particle was a two-layer structure emulsion particle having an inner layer and an outer layer.
• the content of non-volatile matter in the emulsion (5) was 40%, the average particle size of the resin emulsion particle was 200 nm, the proportion of the structural unit derived from the monomer (4) in the total of all the polymers being the non-volatile matter was 20%, and the proportion of the structural unit derived from the monomer (4) in the polymer constituting the outer layer was 40%.
• Example 2-1 An emulsion (6) was obtained in the same manner as in Example 2-1, except that 80 parts of cyclohexyl methacrylate was used instead of 80 parts of the monomer (1).
• the obtained emulsion (6) contained a polymer, and the polymer was a resin emulsion particle, and the resin emulsion particle was a two-layer structure emulsion particle having an inner layer and an outer layer.
• the content of non-volatile matter in the emulsion (6) was 40%, and the average particle size of the resin emulsion particle was 200 nm.
• Example 2-2 An emulsion (7) was obtained in the same manner as in Example 2-1, except that 80 parts of the monomer (5) was used instead of 80 parts of the monomer (1).
• the obtained emulsion (7) contained a polymer, and the polymer was a resin emulsion particle, and the resin emulsion particle was a two-layer structure emulsion particle having an inner layer and an outer layer.
• the content of non-volatile matter in the emulsion (7) was 40%, and the average particle size of the resin emulsion particle was 200 nm.
• Example 2-3 An emulsion (8) was obtained in the same manner as in Example 2-1, except that 80 parts of the monomer (6) was used instead of 80 parts of the monomer (1).
• the obtained emulsion (8) contained a polymer, and the polymer was a resin emulsion particle, and the resin emulsion particle was a two-layer structure emulsion particle having an inner layer and an outer layer.
• the content of non-volatile matter in the emulsion (8) was 40%, and the average particle size of the resin emulsion particle was 200 nm.
• Example 2-4 An emulsion (9) was obtained in the same manner as in Example 2-1, except that 80 parts of Antox MS-60 was used instead of 80 parts of Monomer (1).
• the obtained emulsion (9) contained a polymer, and the polymer was a resin emulsion particle, and the resin emulsion particle was a two-layer structure emulsion particle having an inner layer and an outer layer.
• the content of non-volatile matter in the emulsion (9) was 40%, and the average particle size of the resin emulsion particle was 200 nm.
• the average particle size of the pigment was 330 nm.
• Ink (1) was prepared by mixing 25 parts of emulsion (1) (10 parts as emulsion particles), 27.3 parts of pigment dispersion (1) (15 parts as pigment), 2 parts of diethylene glycol monobutyl ether, 15 parts of propylene glycol, 0.3 parts of a surfactant KF-6011 (manufactured by Shin-Etsu Chemical Co., Ltd.), and 30.4 parts of deionized water and filtering the mixture through a 1 ⁇ m pore size filter (MCP-1-C10S, manufactured by Advantec Co., Ltd.).
• the viscosity of ink (1) was 7 mPa ⁇ s.
• the ink (1) obtained above was introduced into a textile printer MMP-TX13 manufactured by Mastermind, 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 ejected from all nozzles.
• nozzle check printing a total of 180 nozzles were ejected in sequence to print ruled lines
• 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.
• Examples 3-2 to 3-5 and Comparative Examples 3-1 to 3-4 Except for using 25 parts of an emulsion shown in Table 1 instead of 25 parts of Emulsion (1), the inks of Examples 3-2 to 3-5 and Comparative Examples 3-1 to 3-4 were prepared and images were formed in the same manner as in Example 3-1, and PP adhesion evaluation 1 and PP adhesion evaluation 2 were performed. The results are shown in Table 1. The viscosity of the inks obtained in these Examples and Comparative Examples was all 7 mPa ⁇ s, and nozzle check printing confirmed that the inks were ejected from all nozzles.
• the polymer of the present invention has excellent adhesion to polyolefin substrates. Therefore, the polymer of the present invention 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; inks and primers used for printing on polyolefin molded products such as polyethylene plates and polypropylene plates; etc.

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