JP2010280830A - Binder resin composition for aqueous inkjet ink, and inkjet ink using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a binder resin composition for aqueous inkjet ink, from which the aqueous inkjet ink excellent in wear resistance and fixability and durable against rubbing between printed materials in continuous printing or against contact with an alcohol solvent or a gasoline solvent can be obtained. <P>SOLUTION: The binder resin composition for the aqueous inkjet ink contains functional group-containing resin fine particles obtained by emulsion polymerization of ethylenically unsaturated monomers containing at least one kind of monomer by 0.1-15 wt.% selected from a group consisting of amide group-containing ethylenically unsaturated monomers, hydroxy group-containing ethylenically unsaturated monomers and carboxy group-containing ethylenically unsaturated monomers. A coating film formed from the binder resin composition has tensile break strength of 10 to 30 N/mm<SP>2</SP>at 25°C and a percentage of tensile elongation at break of 100-1,000%, and a glass transition temperature of 10-100°C. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a binder resin composition for an aqueous inkjet ink that can be suitably used for an aqueous inkjet ink. More specifically, the present invention relates to a water-based inkjet ink binder composition having excellent friction resistance, water resistance, and solvent resistance.

  In recent years, inkjet recording systems have been improved in resolution and performance, and expectations for excellent water resistance and weather resistance are increasing. Furthermore, in recent years, the demand in the commercial printing field has increased, and inkjet inks that can handle various printing methods in small lots according to customer demands, especially from fine paper to art paper, coated paper, PP, PET, PVC, etc. There is a need for inks that can be printed on various substrates such as films. Furthermore, commercial printing is increasingly required to achieve high-speed printing, and there is a need for inkjet inks that satisfy these requirements.

  A water-based inkjet ink is generally composed of a pigment, a pigment dispersion resin, water, a humectant component, and a binder. Among these, a binder is used in order to improve the tolerance of a coating film. Many attempts have been made to use resin emulsions as binders for the purpose of providing stable ejection without clogging nozzles and ensuring water resistance and ink stability. For example, in Patent Document 1, a resin emulsion or the like is used as a binder, and the ink storage stability and clogging are reduced by setting the minimum ink forming temperature (MFT) to 40 ° C. or higher. However, methods that merely define the minimum film-forming temperature (MFT) of ink have not improved ink physical properties such as water resistance, solvent resistance, and further, friction resistance of the coating film. Furthermore, since the ink film-forming temperature (MFT) is high, the usable printing system is limited and the versatility is poor.

  Patent Document 2 is characterized in that the glass transition temperature (Tg) of the resin emulsion is 35 ° C. or more and the minimum film-forming temperature (MFT) is 20 ° C. or less. Further, in Patent Document 3, the glass transition temperature of the resin emulsion is used. The temperature (Tg) is 40 to 80 ° C. These also merely define the softening / film-forming temperature of the resin, and do not fully satisfy the resistance such as water resistance, solvent resistance, and friction resistance.

  Patent Documents 4 and 5 are characterized in that an acrylic silicon resin containing an alkoxysilyl group is used as a binder as a resin component. By using a resin component having an alkoxysilyl group having self-crosslinking properties as a binder, the coating film is strengthened and the friction resistance and the blocking property are improved. However, when this resin is used, alkoxysilyl groups that are not finally used for self-crosslinking also cause deterioration of water resistance and friction resistance, and in recent years, such as art paper and coated paper that require high fixability. The resistance on the osmotic substrate is not sufficient.

  Furthermore, resin emulsions impregnated with pigments or dyes have been studied so far, Patent Document 6 uses resin emulsions dyed with dyes, and Patent Document 7 uses vinyl polymer particles containing pigments. . However, these do not satisfy the balance between the dispersion stability and color development of the pigment and resin.

Japanese Patent No. 2867491 Japanese Patent No. 4079339 Japanese Patent No. 3937170 Japanese Patent No. 3011087 Japanese Patent No. 3982003 Japanese Patent Laid-Open No. 3-250069 Japanese Patent No. 3534395

  The present invention is a water-based ink jet ink that is excellent in friction resistance and fixability, and is capable of obtaining a water-based inkjet ink that can withstand rubbing between printed materials during continuous printing and contact with water, alcohol solvents, and gasoline solvents. It aims at providing the binder resin composition for inkjet inks.

The first invention of the present invention comprises an amide group-containing ethylenically unsaturated monomer (a), a hydroxyl group-containing ethylenically unsaturated monomer (b), and a carboxyl group-containing ethylenically unsaturated monomer (c). Binder resin for water-based inkjet inks containing functional group-containing resin fine particles obtained by emulsion polymerization of an ethylenically unsaturated monomer (A) containing 0.1 to 15% by weight of at least one monomer selected from the group consisting of A composition comprising:
The film formed from the binder resin composition has a tensile breaking strength at 25 ° C. of 10 to 30 N / mm ² , a tensile breaking elongation of 100 to 1000%, and
It is related with the binder resin composition for water-based inkjet inks whose glass transition temperature is 10-100 degreeC.

  Moreover, 2nd invention is 1st invention in which ethylenically unsaturated monomer (A) contains 0.1 to 10weight% of monomer (d) which has a 2 or more ethylenically unsaturated group. It relates to the binder resin composition for water-based inkjet inks.

In the third invention, the ethylenically unsaturated monomer (A) contains 0.5 to 10% by weight of the carbonyl group-containing ethylenically unsaturated monomer (e), and
The binder resin composition relates to the binder resin composition for an aqueous inkjet ink according to the first or second invention, which comprises the compound (f) having a functional group capable of reacting with a carbonyl group.

  Moreover, 4th invention is related with the inkjet ink containing the binder resin composition for water-based inkjet inks of the invention in any one of 1-3.

  According to the present invention, it is possible to obtain a water-based inkjet ink that has excellent friction resistance and fixability, and can withstand rubbing between printed matter at the time of continuous printing and contact with water, an alcohol solvent, or a gasoline solvent. A possible binder resin composition for water-based inkjet ink could be provided.

The binder resin composition for aqueous inkjet inks of the present invention comprises an amide group-containing ethylenically unsaturated monomer (a), a hydroxyl group-containing ethylenically unsaturated monomer (b), and a carboxyl group-containing ethylenically unsaturated monomer. Water-based inkjet containing functional group-containing resin fine particles obtained by emulsion polymerization of ethylenically unsaturated monomer (A) containing 0.1 to 15% by weight of at least one monomer selected from the group consisting of (c) A binder resin composition for ink,
The film formed from the binder resin composition has a tensile breaking strength at 25 ° C. of 10 to 30 N / mm ² , a tensile breaking elongation of 100 to 1000%, and
The glass transition temperature is 10 to 100 ° C.

  The functional group-containing resin fine particles are obtained from an amide group-containing ethylenically unsaturated monomer (a), a hydroxyl group-containing ethylenically unsaturated monomer (b), and a carboxyl group-containing ethylenically unsaturated monomer (c). It has at least one functional group selected from amide groups, hydroxyl groups, and carboxyl groups derived from at least one monomer selected from the group consisting of: The functional group-containing resin fine particles have the above functional groups to ensure the stability during synthesis or storage of the resin fine particles, and to improve the film formability when forming a binder resin composition for aqueous inkjet inks. Make good. However, when there are too many said functional groups, it will become the cause of reducing the water resistance, alcohol resistance, or friction resistance of a coating film. Therefore, the functional group-containing resin fine particles included in the present invention include an amide group-containing ethylenically unsaturated monomer (a), a hydroxyl group-containing ethylenically unsaturated monomer (b), and a carboxyl group-containing ethylenically unsaturated monomer. It is necessary to contain 0.1 to 15% by weight of at least one monomer selected from the group consisting of the body (c).

Moreover, the binder resin composition for water-based inkjet inks of the present invention has a tensile strength at break of 10 to 30 N / mm ² at 25 ° C. and a tensile elongation at break of 100 to 1000 of the film formed from the binder resin composition. %. When the tensile rupture strength and the tensile rupture elongation are within this range, the binder resin composition can ensure sufficient toughness to withstand rubbing between printed matter.

  Furthermore, the binder resin composition for water-based inkjet inks of the present invention has a glass transition temperature of 10 to 100 ° C. When the glass transition temperature is 10 ° C. or higher and relatively near room temperature or higher, the coating formed from the binder resin composition has good friction resistance. However, unless the functional group-containing resin fine particles contained in the binder resin composition are fused to form a film, the film does not exhibit good friction resistance and solvent resistance. The temperature needs to be 100 ° C. or lower.

  The functional group-containing resin fine particles contained in the binder resin composition for aqueous inkjet inks of the present invention are obtained by emulsion polymerization of an ethylenically unsaturated monomer (A) with a radical polymerization initiator in the presence of a surfactant in water. Resin fine particles obtained in this way. The functional group-containing resin fine particles in the present invention include an amide group-containing ethylenically unsaturated monomer (a), a hydroxyl group-containing ethylenically unsaturated monomer (b), and a carboxyl group-containing ethylenically unsaturated monomer (c). It can be obtained by emulsion polymerization of an ethylenically unsaturated monomer (A) containing 0.1 to 15% by weight of at least one monomer selected from the group consisting of: tensile rupture strength, tensile rupture It is necessary to appropriately select other ethylenically unsaturated monomers so that the elongation rate and the glass transition temperature are within the above-described ranges.

  At least one selected from the group consisting of an amide group-containing ethylenically unsaturated monomer (a), a hydroxyl group-containing ethylenically unsaturated monomer (b), and a carboxyl group-containing ethylenically unsaturated monomer (c). By copolymerizing the monomer, hydrophilic functional groups can be left in or on the surface of the functional group-containing resin fine particles, thereby ensuring stability during synthesis or storage of the resin fine particles. Can do. Moreover, the film-forming property at the time of forming into a coating film the binder resin composition for water-based inkjet inks containing a functional group containing resin fine particle can be improved. Even after the synthesis of the particles, the amide group, hydroxyl group, or carboxyl group is not used for crosslinking or the like and tends to remain inside or on the surface of the particle, and even a small amount has a great effect on particle stability and film-forming properties. In addition, some of them may be used for the crosslinking reaction, and by adjusting the degree of crosslinking of these functional groups, the tensile breaking strength, tensile breaking elongation, and glass transition temperature can be optimized, and the particle stability In addition, it is possible to balance the film formability and ink resistance.

Examples of the amide group-containing ethylenically unsaturated monomer (a) include a first amide group-containing ethylenically unsaturated monomer such as (meth) acrylamide;
Alkylol (meth) acrylamides such as N-methylolacrylamide, N, N-di (methylol) acrylamide, N-methylol-N-methoxymethyl (meth) acrylamide;
N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, N-propoxymethyl- (meth) acrylamide, N-butoxymethyl- (meth) acrylamide, N-pentoxymethyl- (meth) acrylamide Monoalkoxy (meth) acrylamides such as;
N, N-di (methoxymethyl) acrylamide, N-ethoxymethyl-N-methoxymethylmethacrylamide, N, N-di (ethoxymethyl) acrylamide, N-ethoxymethyl-N-propoxymethylmethacrylamide, N, N- Di (propoxymethyl) acrylamide, N-butoxymethyl-N- (propoxymethyl) methacrylamide, N, N-di (butoxymethyl) acrylamide, N-butoxymethyl-N- (methoxymethyl) methacrylamide, N, N- Dialkoxy (meth) acrylamides such as di (pentoxymethyl) acrylamide, N-methoxymethyl-N- (pentoxymethyl) methacrylamide;
Dialkylamino (meth) acrylamides such as N, N-dimethylaminopropylacrylamide, N, N-diethylaminopropylacrylamide;
Dialkyl (meth) acrylamides such as N, N-dimethylacrylamide and N, N-diethylacrylamide;
Examples include carbonyl group-containing (meth) acrylamides such as diacetone (meth) acrylamide.

  Examples of the hydroxyl group-containing ethylenically unsaturated monomer (b) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and glycerol mono (meth) acrylate. 4-hydroxyvinylbenzene, 1-ethynyl-1-cyclohexanol, allyl alcohol and the like.

  Examples of the carboxyl group-containing ethylenically unsaturated monomer (c) include maleic acid, fumaric acid, itaconic acid, citraconic acid, or alkyl or alkenyl monoesters thereof, and β- (meth) acryloxyethyl phthalate. Monoester, isophthalic acid β- (meth) acryloxyethyl monoester, terephthalic acid β- (meth) acryloxyethyl monoester, succinic acid β- (meth) acryloxyethyl monoester, acrylic acid, methacrylic acid, crotonic acid And cinnamic acid.

  In the present invention, the amide group-containing ethylenically unsaturated monomer (a), the hydroxyl group-containing ethylenically unsaturated monomer (b), and the carboxyl group-containing ethylenically unsaturated monomer (c) are selected. At least one monomer is used in an amount of 0.1 to 15% by weight in a total of 100% by weight of the whole ethylenically unsaturated monomer (A) used for emulsion polymerization. Preferably it is 0.5 to 8 weight%, More preferably, it is 0.5 to 5 weight%. When the above monomer containing functional groups of amide group, hydroxyl group and carboxyl group is less than 0.1% by weight, the amount of functional groups remaining in the interior of the particle or on the surface after polymerization is reduced, and synthesis is performed. The particle stability during storage or storage, and the film forming property of the binder resin composition containing the resin fine particles are deteriorated. Moreover, when it exceeds 15 weight%, the friction resistance and alcohol resistance of a binder resin composition will fall. Further, by reacting these functional groups with a crosslinking agent described later, the tensile strength at break, tensile elongation at break and glass transition temperature of the coating formed from the binder resin composition of the present invention can be adjusted.

  Further, among the amide group-containing ethylenically unsaturated monomers (a), alkylol (meth) acrylamides are self-crosslinking reactive functional groups, and the effect of forming internal cross-linking of resin fine particles during emulsion polymerization. This is preferable. Furthermore, by using alkylol (meth) acrylamides, the tensile strength at break, tensile elongation at break, and glass transition temperature of the coating formed from the binder resin composition of the present invention can be adjusted.

  Further, the functional group-containing resin fine particles may be expressed as a monomer (d) having two or more ethylenically unsaturated groups [hereinafter referred to as a monomer (d). ] Is preferably copolymerized. By copolymerizing the monomer (d), a crosslinked structure can be introduced into the fine particles, and a stronger binder coating film can be obtained. Thereby, the strength of the coating film obtained from the binder resin composition is increased, and the friction resistance is improved. Furthermore, by using the monomer (d), the tensile breaking strength, tensile breaking elongation, and glass transition temperature of the coating formed from the binder resin composition of the present invention can be adjusted.

Examples of the monomer (d) having two or more ethylenically unsaturated groups in one molecule include allyl (meth) acrylate, 1-methylallyl (meth) acrylate, and 2-methylallyl (meth) acrylate. 1-butenyl (meth) acrylate, 2-butenyl (meth) acrylate, 3-butenyl (meth) acrylate, 1,3-methyl-3-butenyl (meth) acrylate, 2- (meth) acrylate 2- Chloroallyl, 3-chloroallyl (meth) acrylate, o-allylphenyl (meth) acrylate, 2- (allyloxy) ethyl (meth) acrylate, allyl lactyl (meth) acrylate, citronellyl (meth) acrylate, (meth) Geranyl acrylate, rosinyl (meth) acrylate, cinnamyl (meth) acrylate, diallyl maleate, diallyl itaconic acid, Meth) vinyl acrylate, vinyl crotonate, vinyl oleate, vinyl linolenic acid, (meth) ethylenically unsaturated group-containing (meth) acrylic acid esters such as acrylic acid 2- (2'-vinyloxy ethoxy) ethyl;
Di (meth) acrylic acid ethylene glycol, di (meth) acrylic acid triethylene glycol, di (meth) acrylic acid tetraethylene glycol, tri (meth) acrylic acid trimethylolpropane, tri (meth) acrylic acid pentaerythritol, diacrylic acid Polyfunctional (meth) acrylic acid esters such as 1,1,1-trishydroxymethylethane, 1,1,1-trishydroxymethylethane triacrylate, 1,1,1-trishydroxymethylpropanetriacrylic acid;
Divinyls such as divinylbenzene and divinyl adipate;
Examples include diallyls such as diallyl isophthalate, diallyl phthalate, and diallyl maleate.

  Two or more ethylenically unsaturated groups contained in the monomer (d) can be mainly polymerized during polymerization to introduce a crosslinked structure into the resin fine particles, but some of the ethylenically unsaturated groups can be incorporated into the interior of the particle after polymerization. It may remain on the surface. The remaining ethylenically unsaturated groups contribute to the interparticle crosslinking of the binder resin composition, thereby improving the friction resistance of the resulting coating film.

  In the present invention, the monomer (d) is preferably used in an amount of 0.1 to 10% by weight in a total of 100% by weight of the entire ethylenically unsaturated monomer (A) used for emulsion polymerization. More preferably, it is 0.5-8 weight%, More preferably, it is 0.5-5 weight%. If the monomer (d) is less than 0.1% by weight, the resin fine particles may not be sufficiently crosslinked and may not contribute to the friction resistance of the coating film obtained from the binder resin composition. On the other hand, if it exceeds 10% by weight, there may be a problem in the polymerization stability at the time of emulsion polymerization, or even if it can be polymerized, there may be a problem in the storage stability.

  Furthermore, the functional group-containing resin fine particles are preferably copolymerized with a carbonyl group-containing ethylenically unsaturated monomer (e). In this case, the obtained resin fine particle aqueous dispersion has a functional group capable of reacting with a carbonyl group (f) [hereinafter sometimes referred to as a compound (f). ] As a cross-linking agent, and used as a binder resin composition to introduce a cross-linked structure upon drying, thereby improving the friction resistance of the coating film. Further, by using the resin fine particles copolymerized with the monomer (e) and the compound (f), the tensile breaking strength, tensile breaking elongation, and glass of the film formed from the binder resin composition of the present invention The transition temperature can be adjusted.

  Examples of the carbonyl group-containing ethylenically unsaturated monomer (e) include diacetone (meth) acrylamide, acrolein, N-vinylformamide, vinyl methyl ketone, vinyl ethyl ketone, acetoacetoxyethyl (meth) acrylate, acetoacetoxy Examples include propyl (meth) acrylate and acetoacetoxybutyl (meth) acrylate. In particular, diacetone (meth) acrylamide is more preferable because it has a function as the above-mentioned amide group-containing ethylenically unsaturated monomer (a).

  The carbonyl group-containing ethylenically unsaturated monomer (e) is preferably used in an amount of 0.5 to 10% by weight in a total of 100% by weight of the ethylenically unsaturated monomer (A) used for emulsion polymerization. More preferably, it is 1-8 weight%, More preferably, it is 1-6 weight%. If the monomer (e) is less than 0.5% by weight, the resin fine particles may not be sufficiently crosslinked and may not contribute to the friction resistance of the coating film. On the other hand, if it exceeds 10% by weight, the stability after adding the compound (f) having a functional group capable of reacting with a carbonyl group may be deteriorated.

  Examples of the compound (f) having a functional group capable of reacting with a carbonyl group used as a crosslinking agent include hydrazine derivatives having at least two hydrazide groups in one molecule, such as oxalic acid dihydrazide, malonic acid dihydrazide, and succinic acid. In addition to aliphatic dihydrazides such as acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, and sebacic acid dihydrazide, carbonic polyhydrazide, aliphatic, alicyclic, aromatic bissemicarbazide, aromatic dicarboxylic acid dihydrazide, polyhydrazide of polyacrylic acid And dihydrazides of unsaturated dicarboxylic acids such as dihydrazides of aromatic hydrocarbons, hydrazine-pyridine derivatives and maleic acid dihydrazides. These compounds (f) are preferably added in an amount of 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the solid content of the functional group-containing resin fine particles.

Other ethylenically unsaturated monomers are exemplified as the ethylenically unsaturated monomer (A) constituting the resin fine particles. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, hexyl ( (Meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate [alias: lauryl (meth) acrylate], tridecyl (meth) acrylate, tetradecyl (Meth) acrylate [alias: myristyl (meth) acrylate], pentadecyl (meth) acrylate, hexadecyl (meth) acrylate [alias: cetyl (meth) acrylate], heptadecyl ( Acrylate), octadecyl (meth) acrylate [alias: stearyl (meth) acrylate], nonadecyl (meth) acrylate, icosyl (meth) acrylate, heicosyl (meth) acrylate, docosyl (meth) acrylate, cyclohexyl (meth) acrylate, isobonyl (Meth) acrylates such as (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, (meth) acrylonitrile;
Tertiary butyl group-containing ethylenically unsaturated monomers such as tertiary butyl (meth) acrylate;
Epoxy group-containing ethylenically unsaturated monomers such as glycidyl (meth) acrylate and 3,4-epoxycyclohexyl (meth) acrylate;
Sulfonic acid group-containing ethylenically unsaturated monomers such as vinyl sulfonic acid and styrene sulfonic acid;
Phosphoric acid group-containing ethylenically unsaturated monomers such as (2-hydroxyethyl) methacrylate acid phosphate;
Dialkylamino group-containing ethylenically unsaturated compounds such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate methylethylaminoethyl (meth) acrylate, dimethylaminostyrene, diethylaminostyrene;
Perfluoromethylmethyl (meth) acrylate, perfluoroethylmethyl (meth) acrylate, 2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorooctylethyl (meth) acrylate , 2-perfluoroisononylethyl (meth) acrylate, 2-perfluorononylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, perfluoropropylpropyl (meth) acrylate, perfluorooctylpropyl (meta ) Perfluoroalkyl having a C 1-20 perfluoroalkyl group such as acrylate, perfluorooctyl amyl (meth) acrylate, perfluorooctyl undecyl (meth) acrylate, etc. (Meth) acrylate;
Perfluoroalkyl group-containing ethylenically unsaturated compounds such as perfluoroalkylethylene, perfluoroalkyl such as perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, and perfluorodecylethylene;
Polyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, propoxypolyethylene glycol (meth) acrylate, n-butoxypolyethylene glycol (meth) acrylate, n-pentoxypolyethylene glycol (meth) Acrylate, phenoxypolyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, propoxypolypropylene glycol (meth) acrylate, n-butoxypolypropylene glycol (meth) acrylate N-Pentoxypolypropylene Recall (meth) acrylate, phenoxypolypropylene glycol (meth) acrylate, polytetramethylene glycol (meth) acrylate, methoxypolytetramethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, hexaethylene glycol (meth) acrylate, Ethylenically unsaturated compounds having a polyether chain such as methoxyhexaethylene glycol (meth) acrylate;
Ethylenically unsaturated compounds having a polyester chain such as lactone-modified (meth) acrylate;
(Meth) acrylic acid dimethylaminoethyl methyl chloride salt, trimethyl-3- (1- (meth) acrylamide-1,1-dimethylpropyl) ammonium chloride, trimethyl-3- (1- (meth) acrylamidopropyl) ammonium chloride, And quaternary ammonium base-containing ethylenically unsaturated compounds such as trimethyl-3- (1- (meth) acrylamide-1,1-dimethylethyl) ammonium chloride;
Fatty acid vinyl compounds such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl hexanoate, vinyl caprylate, vinyl laurate, vinyl palmitate, vinyl stearate;
Vinyl ether compounds such as butyl vinyl ether and ethyl vinyl ether;
Α-olefin compounds such as 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene;
Allyl compounds such as allyl acetate, allylbenzene, allyl cyanide;
Vinyl compounds such as vinyl cyanide, vinylcyclohexane, vinylmethylketone, styrene, α-methylstyrene, 2-methylstyrene, chlorostyrene;
Ethynyl compounds such as acetylene, ethynylbenzene, ethynyltoluene;
γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltributoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-acryloxy Propyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-methacryloxymethyltrimethoxysilane, γ-acryloxymethyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane And alkoxysilyl group-containing ethylenically unsaturated monomers such as vinyltributoxysilane and vinylmethyldimethoxysilane.

  The other ethylenically unsaturated monomers described above are important for adjusting the tensile strength at break, tensile elongation at break, and glass transition temperature of the film formed from the binder resin composition. Two or more kinds can be used in combination in order to adjust the stability, film formability, and coating film properties.

  Further, among other ethylenically unsaturated monomers, the alkoxysilyl group-containing ethylenically unsaturated monomer has a self-crosslinking reactive functional group in the contained alkoxysilyl group, and the resin fine particles are formed during emulsion polymerization. Has the effect of forming internal crosslinks. On the other hand, silanol groups are formed in the alkoxysilyl group in the course of crosslinking, and this silanol group may reduce the physical properties of the coating film (friction resistance, alcohol resistance). Therefore, for the purpose of adjusting the physical property balance of the binder resin composition, it is preferably used to the extent that the coating film resistance is not lowered.

  Of the other ethylenically unsaturated monomers, tertiary butyl group-containing ethylenically unsaturated monomers undergo a desorption reaction (tertiary butanol is eliminated) when the contained tertiary butyl group is heated. To become a carboxyl group. This carboxyl group contributes to particle stability and coating film formability, like the carboxyl group contained in the monomer (c).

  It is preferable to introduce a crosslinked structure in order to adjust the tensile strength at break, tensile elongation at break and glass transition temperature of the film formed from the binder resin composition for water-based inkjet inks of the present invention. The introduction of the crosslinked structure can also be formed by the reaction between the functional group-containing resin fine particles constituting the binder resin composition and the crosslinking agent. That is, the binder resin composition of the present invention has a compound (g) having two or more functional groups capable of reacting with at least one functional group selected from an amide group, a hydroxyl group and a carboxyl group [hereinafter referred to as a compound (g). There is a case. ] May be used as a crosslinking agent.

  Examples of the functional group capable of reacting with the amide group include a carbonyl group. Examples of the functional group capable of reacting with a hydroxyl group include an acid anhydride group and an isocyanate group. Examples of the functional group capable of reacting with a carboxyl group include an amino group, an epoxy group, an aziridinyl group, a carbodiimide group, and an oxazoline group.

  The compound (g) that can be used in the present invention is exemplified below. Examples of the compound having a carbonyl group include aldehyde compounds such as formalin and paraformaldehyde. The amide group contained in the functional group-containing resin fine particles reacts to form a methylol group when formalin is added. The obtained methylol group can be used for forming a crosslinked structure.

  Examples of the compound having two or more acid anhydride groups include pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, oxydiphthalic dianhydride, and diphenylsulfonetetracarboxylic dianhydride. , Diphenyl sulfide tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, perylene tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, "Ricacid TMTA-C", "Ricacid MTA" manufactured by Shin Nippon Rika Co., Ltd. -10 "," Licacid MTA-15 "," Licacid TMEG series "," Licacid TDA "and the like.

  Examples of the compound having two or more isocyanate groups include aromatic polyisocyanate, aliphatic polyisocyanate, araliphatic polyisocyanate, and alicyclic polyisocyanate.

  Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6 -Tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, xylylene diisocyanate and the like can be mentioned.

  Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HMDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, and 1,3-butylene diisocyanate. , Dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and the like.

  Examples of the araliphatic polyisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene. 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.

  Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (also known as IPDI, isophorone diisocyanate), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1, Examples include 4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanate methyl) cyclohexane, and the like. .

  Moreover, the trimethylol propane adduct body of the said polyisocyanate, the trimer which has an isocyanurate ring, etc. can be used. Furthermore, polyphenylmethane polyisocyanate (also known as PAPI), naphthylene diisocyanate, modified polyisocyanate thereof, and the like can be used. In addition, as the polyisocyanate modified product, a carbodiimide group, a uretdione group, a uretoimine group, a burette group reacted with water, a group of isocyanurate groups, or a modified product having two or more of these groups is used. it can. A reaction product of polyol and diisocyanate can also be used as a polyfunctional isocyanate compound.

Examples of the compound having two or more amino groups include aliphatic diamines such as ethylenediamine and hexamethylenediamine;
Alicyclic diamines such as 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, 4,4′-diamino-3,3′-dimethyldicyclohexyl, diaminocyclohexane, isophoronediamine;
And araliphatic diamines such as xylylenediamine and α, α, α ′, α′-tetramethylxylylenediamine.

  Examples of the compound having two or more epoxy groups include bisphenol A-epichlorohydrin type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1, 6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidylaniline, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N′-di) Glycidylaminomethyl) cyclohexane and the like.

  Examples of the compound having two or more aziridinyl groups include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxite), N, N′-toluene-2,4-bis (1-aziridine). Carboxite), bisisophthaloyl-1- (2-methylaziridine), tri-1-aziridinylphosphine oxide, N, N′-hexamethylene-1,6-bis (1-aziridinecarboxite), tri Methylolpropane-tri-β-aziridinylpropionate, tetramethylolmethane-tri-β-aziridinylpropionate, tris-2,4,6- (1-aziridinyl) -1,3,5-triazine , Trimethylolpropane tris [3- (1-aziridinyl) propionate], trimethylolpropane tris [3- (1-azi Lysinyl) butyrate], trimethylolpropane tris [3- (1- (2-methyl) aziridinyl) propionate], trimethylolpropane tris [3- (1-aziridinyl) -2-methylpropionate], 2,2 ′ -Bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate], pentaerythritol tetra [3- (1-aziridinyl) propionate], diphenylmethane-4,4-bis-N, N′-ethyleneurea, 1,6 -Hexamethylenebis-N, N'-ethyleneurea, 2,4,6- (triethyleneimino) -Syn-triazine, bis [1- (2-ethyl) aziridinyl] benzene-1,3-carboxylic acid amide, etc. Is mentioned.

  Examples of the compound having two or more carbodiimide groups include Nisshinbo Co., Ltd. Carbodilite series. Among them, Carbodilite V-02, 04, 06, E-01, 02, 03A is an aqueous type or an aqueous emulsion type, and is therefore preferable because of its good compatibility with the resin fine particles of the present invention. Moreover, even if it is an oily type like Carbodilite V-05, it can be used for the binder resin composition of this invention by making a water-system dispersion using surfactant, for example.

  Examples of the compound having two or more oxazoline groups include 2'-methylenebis (2-oxazoline), 2,2'-ethylenebis (2-oxazoline), 2,2'-ethylenebis (4-methyl-2- Oxazoline), 2,2'-propylenebis (2-oxazoline), 2,2'-tetramethylenebis (2-oxazoline), 2,2'-hexamethylenebis (2-oxazoline), 2,2'-octa Methylenebis (2-oxazoline), 2,2′-p-phenylenebis (2-oxazoline), 2,2′-p-phenylenebis (4,4′-dimethyl-2-oxazoline), 2,2′- p-phenylenebis (4-methyl-2-oxazoline), 2,2′-p-phenylenebis (4-phenyl-2-oxazoline), 2,2′-m-phenylenebis ( -Oxazoline), 2,2'-m-phenylenebis (4-methyl-2-oxazoline), 2,2'-m-phenylenebis (4,4'-dimethyl-2-oxazoline), 2,2'- m-phenylenebis (4-phenylenebis-2-oxazoline), 2,2′-o-phenylenebis (2-oxazoline), 2,2′-o-phenylenebis (4-methyl-2-oxazoline), 2 , 2′-bis (2-oxazoline), 2,2′-bis (4-methyl-2-oxazoline), 2,2′-bis (4-ethyl-2-oxazoline), 2,2′-bis ( 4-phenyl-2-oxazoline) and the like.

  The compound (g) used as the crosslinking agent is preferably added in an amount of 0.1 to 50 parts by weight, more preferably 1 to 40 parts by weight, based on 100 parts by weight of the solid content of the functional group-containing resin fine particles. preferable. The addition amount of a crosslinking agent can be used to such an extent that it does not have a bad influence on the physical properties (friction resistance, alcohol resistance) of the coating film obtained by a binder resin composition.

  Furthermore, two or more kinds of compounds (g) in the binder resin composition can be used in combination.

  Crosslinking reaction between at least one functional group selected from amide groups, hydroxyl groups and carboxyl groups in these functional group-containing resin fine particles and functional groups in the compound (g) strengthens the crosslinking and adjusts the binder performance. For the purpose, heat treatment may be performed as necessary during printing. For example, the reaction between the carboxyl group in the functional group-containing resin fine particles and the epoxy group in the compound having two or more epoxy groups is preferably heat-treated at 160 ° C to 250 ° C.

  Furthermore, in addition to these compounds (g), a third component can be added to the binder resin composition for the purpose of strengthening the coating film or adjusting the mechanical strength. As an additive for adjusting the mechanical strength of the binder, for example, a resin such as a polyamide resin, a polyester resin, or a polyurethane resin can be blended. These 3rd components will not be restricted to this as long as the said objective is satisfy | filled.

  The functional group-containing resin fine particles of the present invention are synthesized by a conventionally known emulsion polymerization method.

  As the emulsifier used in the emulsion polymerization in the present invention, a conventionally known one such as a reactive emulsifier having an ethylenically unsaturated group or a non-reactive emulsifier having no ethylenically unsaturated group may be arbitrarily used. it can.

  Reactive emulsifiers having an ethylenically unsaturated group can be further roughly classified into anionic and nonionic nonionic ones. Especially when anionic reactive emulsifier or nonionic reactive emulsifier having an ethylenically unsaturated group is used, the dispersed particle size of the copolymer becomes fine and the particle size distribution becomes narrow, so it is used as a binder resin for aqueous inkjet ink. In this case, the friction resistance and alcohol resistance can be improved. This anionic reactive emulsifier or nonionic reactive emulsifier having an ethylenically unsaturated group may be used singly or in combination.

Specific examples of the anionic reactive emulsifier having an ethylenically unsaturated group are illustrated below, but the emulsifiers that can be used in the present invention are not limited to those described below. Examples of the emulsifier include alkyl ethers (commercially available products include, for example, Aqualon KH-05, KH-10, KH-20, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Adeka Soap SR-10N, SR-20N manufactured by ADEKA Corporation. Latemuru PD-104 manufactured by Kao Corporation);
Sulfosuccinic acid ester-based (for example, LATEMUL S-120, S-120A, S-180P, S-180A, Sanyo Chemical Co., Ltd., Elemiol JS-2, etc., manufactured by Kao Corporation);
Alkyl phenyl ether type or alkyl phenyl ester type (commercially available products include, for example, Aqualon H-2855A, H-3855B, H-3855C, H-3856, HS-05, HS-10, HS, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. -20, HS-30, Adeka Soap SDX-222, SDX-223, SDX-232, SDX-233, SDX-259, SE-10N, SE-20N, etc. manufactured by ADEKA Corporation);
(Meth) acrylate sulfate-based (commercially available products include, for example, Antox MS-60, MS-2N, Sanyo Chemical Industries Co., Ltd., Elemiol RS-30, manufactured by Nippon Emulsifier Co., Ltd.);
Examples of the phosphoric acid ester (commercially available products include H-3330PL manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Adeka Soap PP-70 manufactured by ADEKA Co., Ltd.), and the like.

Nonionic reactive emulsifiers that can be used in the present invention include, for example, alkyl ether-based (commercially available products such as Adeka Soap ER-10, ER-20, ER-30, ER-40, manufactured by ADEKA Corporation, Latemu PD-420, PD-430, PD-450, etc. manufactured by Kao Corporation);
Alkyl phenyl ether type or alkyl phenyl ester type (commercially available products include, for example, Aqualon RN-10, RN-20, RN-30, RN-50, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., ADEKA rear soap NE- manufactured by ADEKA Co., Ltd. 10, NE-20, NE-30, NE-40, etc.);
(Meth) acrylate sulfate esters (commercially available products include, for example, RMA-564, RMA-568, and RMA-1114 manufactured by Nippon Emulsifier Co., Ltd.).

  In obtaining the functional group-containing resin fine particles of the present invention by emulsion polymerization, a non-reactive emulsifier having no ethylenically unsaturated group may be used in combination with the above-described reactive emulsifier having an ethylenically unsaturated group, if necessary. it can. Non-reactive emulsifiers can be broadly classified into non-reactive anionic emulsifiers and non-reactive nonionic emulsifiers.

Examples of non-reactive nonionic emulsifiers include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether;
Polyoxyethylene alkylphenyl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether;
Sorbitan higher fatty acid esters such as sorbitan monolaurate, sorbitan monostearate, sorbitan trioleate;
Polyoxyethylene sorbitan higher fatty acid esters such as polyoxyethylene sorbitan monolaurate;
Polyoxyethylene higher fatty acid esters such as polyoxyethylene monolaurate and polyoxyethylene monostearate;
Glycerin higher fatty acid esters such as oleic acid monoglyceride and stearic acid monoglyceride;
Examples include polyoxyethylene / polyoxypropylene / block copolymer, polyoxyethylene distyrenated phenyl ether, and the like.

Examples of non-reactive anionic emulsifiers include higher fatty acid salts such as sodium oleate;
Alkylaryl sulfonates such as sodium dodecylbenzenesulfonate;
Alkyl sulfate salts such as sodium lauryl sulfate;
Polyoxyethylene alkyl ether sulfate esters such as sodium polyoxyethylene lauryl ether sulfate;
Polyoxyethylene alkylaryl ether sulfate salts such as sodium polyoxyethylene nonylphenyl ether sulfate;
Alkyl sulfosuccinic acid ester salts such as sodium monooctyl sulfosuccinate, sodium dioctyl sulfosuccinate, sodium polyoxyethylene lauryl sulfosuccinate and derivatives thereof;
Examples thereof include polyoxyethylene distyrenated phenyl ether sulfate salts.

  The usage-amount of the emulsifier used in this invention is not necessarily limited, According to the physical property calculated | required when a functional group containing resin fine particle is finally used as a binder resin composition, it can select suitably. For example, the emulsifier is usually preferably 0.1 to 30 parts by weight, more preferably 0.3 to 20 parts by weight with respect to 100 parts by weight of the total of the ethylenically unsaturated monomers (A). More preferably, it is in the range of 0.5 to 10 parts by weight.

In the emulsion polymerization of the functional group-containing resin fine particles of the present invention, a water-soluble protective colloid can be used in combination. Examples of the water-soluble protective colloid include polyvinyl alcohols such as partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, and modified polyvinyl alcohol;
Cellulose derivatives such as hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose salts;
Natural polysaccharides such as guar gum and the like can be mentioned, and these can be used either alone or in combination. The use amount of the water-soluble protective colloid is 0.1 to 5 parts by weight, more preferably 0.5 to 2 parts by weight with respect to 100 parts by weight of the total amount of the ethylenically unsaturated monomer (A). .

  Examples of the aqueous medium used in the emulsion polymerization of the functional group-containing resin fine particles of the present invention include water, and a hydrophilic organic solvent can be used as long as the object of the present invention is not impaired.

The polymerization initiator used in obtaining the functional group-containing resin fine particles of the present invention is not particularly limited as long as it has the ability to initiate radical polymerization, and a known oil-soluble polymerization initiator or water-soluble polymerization initiator is used. Can be used. The oil-soluble polymerization initiator is not particularly limited, and examples thereof include benzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl hydroperoxide, tert-butyl peroxy (2-ethylhexanoate), and tert-butyl peroxide. Organic peroxides such as oxy-3,5,5-trimethylhexanoate, di-tert-butyl peroxide;
2,2′-azobisisobutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1 Mention may be made of azobis compounds such as' -azobis-cyclohexane-1-carbonitrile. These can be used alone or in combination of two or more. These polymerization initiators are preferably used in an amount of 0.1 to 10.0 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer (A).

  In the present invention, it is preferable to use a water-soluble polymerization initiator. For example, ammonium persulfate, potassium persulfate, hydrogen peroxide, 2,2′-azobis (2-methylpropionamidine) dihydrochloride and the like are conventionally known. A thing can be used conveniently. Moreover, when performing emulsion polymerization, a reducing agent can be used together with a polymerization initiator if desired. Thereby, it becomes easy to accelerate the emulsion polymerization rate or to perform the emulsion polymerization at a low temperature. Examples of such a reducing agent include reducing organic compounds such as metal salts such as ascorbic acid, ersorbic acid, tartaric acid, citric acid, glucose, formaldehyde sulfoxylate, sodium thiosulfate, sodium sulfite, sodium bisulfite, Examples include reducing inorganic compounds such as sodium bisulfite, ferrous chloride, Rongalite, thiourea dioxide, and the like. These reducing agents are preferably used in an amount of 0.05 to 5.0 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer (A). In addition, it can superpose | polymerize also by a photochemical reaction, radiation irradiation, etc. irrespective of an above described polymerization initiator. The polymerization temperature is not less than the polymerization start temperature of each polymerization initiator. For example, in the case of a peroxide-based polymerization initiator, it may be usually about 70 ° C. The polymerization time is not particularly limited, but is usually 2 to 24 hours.

  Further, if necessary, sodium acetate, sodium citrate, sodium bicarbonate, etc. as a buffering agent, and octyl mercaptan, 2-ethylhexyl thioglycolate, octyl thioglycolate, stearyl mercaptan, lauryl mercaptan as a chain transfer agent A suitable amount of mercaptans such as t-dodecyl mercaptan can be used.

When a monomer having an acidic functional group such as a carboxyl group-containing ethylenically unsaturated monomer is used for the polymerization of the functional group-containing resin fine particles, it can be neutralized with a basic compound before or after the polymerization. When neutralizing, ammonia or alkylamines such as trimethylamine, triethylamine, butylamine;
Alcohol amines such as 2-dimethylaminoethanol, diethanolamine, triethanolamine, aminomethylpropanol;
It can be neutralized with a base such as morpholine. However, it is a highly volatile base that is highly effective in drying, and preferred bases are aminomethylpropanol and ammonia.

In the present invention, the film formed from the binder resin composition for aqueous inkjet ink containing functional group-containing resin fine particles has a tensile breaking strength at 25 ° C. of 10 to 30 N / mm ² and a tensile breaking elongation of 100 to 1000%. It is characterized by that. Further tensile strength is 12~28N / mm ^2, preferably a tensile elongation at break 150-800%, more tensile strength at break 12~25N / mm ^2, a tensile elongation at break 150-600% It is more preferable. When the breaking strength is less than 10 N / mm ² , the friction resistance of the coating film obtained from the binder resin composition deteriorates, and when the breaking strength exceeds 30 N / mm ² , the coating film becomes too brittle, Reduce friction. Furthermore, even if the elongation at break is less than 100%, the coating film is brittle and the friction resistance decreases. On the other hand, when the elongation at break exceeds 1000%, the coating film obtained from the binder resin composition is tacky, resulting in a decrease in friction resistance and alcohol resistance. The tensile rupture strength and tensile rupture elongation of the coating film in the present invention are the tensile rupture strength and tensile rupture elongation measured with Tensilon.

  The tensile rupture strength and tensile rupture elongation of the coating film with Tensilon can be measured by the following methods. The binder resin composition is dried to prepare a sheet having a thickness of about 0.5 mm. The measurement specimen is cut out to 5 mm × 60 mm, and the film thickness is measured accurately. The measurement is performed under a constant temperature and humidity condition of a temperature of 25 ° C. and a humidity of 50%, using a tensile tester [Tensilon manufactured by Orientec Co., Ltd.] with a chuck distance of 20 mm and a tensile speed of 50 mm / min. The tensile rupture strength and tensile rupture elongation calculated in consideration of the film thickness from the tensile rupture strength and tensile rupture elongation obtained by measurement are taken as the tensile rupture strength and tensile rupture elongation of the present invention.

  In addition, the present invention is characterized in that the binder resin composition containing functional group-containing resin fine particles has a glass transition temperature (hereinafter also referred to as Tg) of 10 to 100 ° C. Furthermore, 15-90 degreeC is preferable. When Tg is less than 10 ° C., the coating film obtained from the binder resin composition does not exhibit sufficient toughness and the friction resistance deteriorates. Moreover, when Tg exceeds 100 degreeC, a softness | flexibility will become scarce and friction resistance will deteriorate. In addition, the printing system that can introduce the thermal energy necessary for the formation of the functional group-containing resin fine particles contained in the binder resin composition is remarkably limited and is not practical. The glass transition temperature is a value obtained using a DSC (differential scanning calorimeter).

  The measurement of the glass transition temperature by DSC (differential scanning calorimeter) can be performed as follows. About 2 mg of a sample obtained by drying the binder resin composition is weighed on an aluminum pan, the test container is set on a DSC measurement holder, and the endothermic peak of the chart obtained under a temperature rising condition of 5 ° C./min is read. The peak temperature at this time is defined as the glass transition temperature of the present invention.

  In the present invention, the particle structure of the functional group-containing resin fine particles may be a multilayer structure, so-called core-shell particles. For example, by localizing a resin in which a monomer having a functional group is mainly polymerized in the core part or the shell part, or by providing a difference in Tg or composition between the core part and the shell part, Drying property, film forming property, and mechanical strength can be improved.

  The average particle size of the functional group-containing resin fine particles is preferably from 10 to 500 nm, more preferably from 30 to 250 nm, from the viewpoint of the film formability of the binder resin composition and the stability of the particles. Further, when a large amount of coarse particles exceeding 1 μm are contained, the stability of the particles is impaired, and the ink jetting property is remarkably deteriorated. Therefore, it is preferable that the coarse particles exceeding 1 μm are at most 5% by weight. In addition, the average particle diameter in the present invention represents a volume average particle diameter and can be measured by a dynamic light scattering method.

  The average particle diameter can be measured by the dynamic light scattering method as follows. The functional group-containing resin fine particle dispersion is diluted with water 200 to 1000 times depending on the solid content. About 5 ml of the diluted solution is injected into a cell of a measuring apparatus [Microtrack manufactured by Nikkiso Co., Ltd.], and the measurement is performed after inputting the solvent (water in the present invention) and the refractive index condition of the resin according to the sample. The peak of the volume particle size distribution data (histogram) obtained at this time is defined as the average particle size of the present invention.

  The binder resin composition for water-based inkjet inks of the present invention can contain a film forming aid, an antifoaming agent, a leveling agent, a preservative, a pH adjusting agent, a viscosity adjusting agent, and the like as required.

  The film-forming aid is responsible for the temporary plasticization function that helps the formation of the coating film and evaporates relatively quickly after the coating film is formed, thereby improving the strength of the coating film. Is preferably a solvent having a temperature of 110 to 200 ° C. Specifically, propylene glycol monobutyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, dipropylene glycol monopropyl ether, carbitol, butyl carbitol, dibutyl carbitol, benzyl alcohol, etc. Is mentioned. Among these, ethylene glycol monobutyl ether and propylene glycol monobutyl ether are particularly preferable because they have a high film forming auxiliary effect in a small amount. These film forming assistants are preferably contained in the binder resin composition in an amount of 0.5 to 15% by weight.

  The viscosity modifier may be used in an amount of 1 to 100 parts by weight with respect to 100 parts by weight of the functional group-containing resin fine particles. Examples of the viscosity modifier include carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, polyacrylic acid (and its salt), oxidized starch, phosphorylated starch, and casein.

  The binder resin composition for aqueous inkjet inks of the present invention can be suitably used for aqueous inkjet inks, but can also be used for other printing inks.

  The binder resin composition for an aqueous inkjet ink of the present invention can be suitably used for an aqueous inkjet ink in which a pigment, a pigment dispersion resin, water, and a humectant component are generally blended.

  In the ink-jet ink of the present invention, it is preferable to use 1 to 20% by weight, and more preferably 2 to 15% by weight, of the aqueous ink-jet binder resin composition in terms of solid content. If the binder resin composition is less than 1% by weight, the pigment particles cannot be completely coated on the printing material, and the friction resistance and water resistance may be lowered. On the other hand, when the binder resin composition exceeds 20% by weight, the viscosity of the ink-jet ink is increased, and proper ink physical properties cannot be maintained, and problems such as adversely affecting ejection performance may occur.

  As the pigment, for example, an achromatic pigment such as carbon black, titanium oxide, calcium carbonate, or a chromatic organic pigment can be used. Examples of the organic pigment include insoluble azo pigments such as toluidine red, toluidine maroon, Hansa Yellow, Benzidine Yellow, and pyrazolone red, soluble azo pigments such as Ritolol Red, Helio Bordeaux, Pigment Scarlet, and Permanent Red 2B, alizarin, indanthrone, Derivatives from vat dyes such as thioindigo maroon, phthalocyanine organic pigments such as phthalocyanine blue and phthalocyanine green, quinacridone organic pigments such as quinacridone red and quinacridone magenta, perylene organic pigments such as perylene red and perylene scarlet, isoindo Isoindolinone organic pigments such as Linon Yellow and Isoindolinone Orange, and pyranthrone organic pigments such as Pilanthrone Red and Pilanthrone Orange Thioindigo organic pigments, condensed azo organic pigments, benzimidazolone organic pigments, quinophthalone organic pigments such as quinophthalone yellow, isoindoline organic pigments such as isoindoline yellow, and other pigments such as flavanthrone yellow and acylamide yellow Nickel azo yellow, copper azomethine yellow, perinone orange, anthrone orange, dianthraquinonyl red, dioxazine violet and the like.

  When organic pigments are exemplified by color index (CI) numbers, C.I. I. Pigment Yellow 12, 13, 14, 17, 20, 24, 74, 83, 8893, 109, 110, 117, 120, 125, 128, 129, 137, 138, 139, 147, 148, 150, 151, 153 154, 155, 166, 168, 180, 185, C.I. I. Pigment orange 16, 36, 43, 51, 55, 59, 61, C.I. I. Pigment Red 9, 48, 49, 52, 53, 57, 97, 122, 123, 149, 168, 177, 180, 192, 202, 206, 215, 216, 217, 220, 223, 224, 226, 227, 228, 238, 240, C.I. I. Pigment violet 19, 23, 29, 30, 37, 40, 50, C.I. I. Pigment blue 15, 15: 1, 15: 3, 15: 4, 15: 6, 22, 60, 64, C.I. I. Pigment green 7, 36, C.I. I. Pigment brown 23, 25, 26, and the like.

  Specific examples of carbon black include “Special Black 350, 250, 100, 550, 5, 4, 4A, 6” “Printex U, V, 140 U, 140 V, 95, 90, 85, 80, 75, 55, manufactured by Degussa. 45, 40, P, 60, L6, L, 300, 30, 3, 35, 25, A, G ", Cabot's" REGAL 400R, 660R, 330R, 250R "," MOGUL E, L ", Mitsubishi Chemical “MA7, 8, 11, 77, 100, 100R, 100S, 220, 230” “# 2700, # 2650, # 2600, # 200, # 2350, # 2300, # 2200, # 1000, # 990, # 980, # 970, # 960, # 950, # 900, # 850, # 750, # 650, # 52, # 50, # 47, # 45, # 4 5L, # 44, # 40, # 33, # 332, # 30, # 25, # 20, # 10, # 5, CF9, # 95, # 260 ”and the like.

  Specific examples of titanium oxide include “Taipeku CR-50, 50-2, 57, 80, 90, 93, 95, 953, 97, 60, 60-2, 63, 67, 58, 58- manufactured by Ishihara Sangyo Co., Ltd. 2, 85 "" Tipekes R-820, 830, 930, 550, 630, 680, 670, 580, 780, 780-2, 850, 855 "," Tipekes A-100, 220 "," Tipekes W-10 " PF-740, 744 "" TTO-55 (A), 55 (B), 55 (C), 55 (D), 55 (S), 55 (N), 51 (A), 51 (C) " "TTO-S-1, 2", "TTO-M-1, 2", "Titanics JR-301, 403, 405, 600A, 605, 600E, 603, 805, 806, 701, 800, 808" manufactured by Teika "Titanic EN-1, C, 3, 4, 5 ", and the like manufactured by Du Pont" Taipyua R-900,902,960,706,931 ". Organic pigments such as yellow, magenta, cyan and black are usually used in an amount of 0.2 to 15% by weight, preferably 0.5 to 10% by weight in 100% by weight of the water-based inkjet ink. Moreover, in the case of white titanium oxide, it is preferable to mix | blend in the ratio of 5 to 50 weight% normally, Preferably it is 10 to 45 weight%.

  Examples of the pigment dispersion resin include acrylic, styrene-acrylic, polyester, polyamide, polyurethane, and fluorine resins. The pigment dispersion resin is used in an amount of 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 10 parts by weight of the pigment. If the pigment-dispersed resin is less than 0.5 parts by weight with respect to 10 parts by weight of the pigment, the pigment dispersion stability may be lowered, causing a problem in stability over time. On the other hand, when the pigment dispersion resin exceeds 20 parts by weight with respect to 10 parts by weight of the pigment, the viscosity of the ink may be significantly increased and ejection from the nozzles may be adversely affected.

  Examples of the humectant component include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, polyethylene glycol, glycerin, tetraethylene glycol, dipropylene glycol, ketone alcohol, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, Examples include 1,2-hexanediol, N-methyl-2-pyrrolidone, substituted pyrrolidone, 2,4,6-hexanetriol, tetrafurfuryl alcohol, 4-methoxy-4-methylpentanone, and the like. The humectant component is usually used in an amount of 10 to 60% by weight, preferably 20 to 50% by weight, in 100% by weight of the water-based inkjet ink. If the humectant component is less than 10% by weight, there may be a problem in ejection stability due to drying of the ink at the nozzle. On the other hand, if the humectant component exceeds 60% by weight, the drying property after printing may be lowered.

  Examples of the substrate to which the aqueous inkjet ink of the present invention can be suitably applied include a penetrating base material such as fine paper, and a non-penetrating base material such as art paper and coated paper. The binder resin composition of the present invention exhibits good resistance even for non-permeable base materials that are particularly demanding of friction resistance, alcohol resistance, gasoline resistance, and the like.

  Examples of the ink jet printing method using the water-based ink jet ink of the present invention include an ink jet method having an on-demand type recording head. Examples of the on-demand type include a piezo method, a thermal ink jet method, and an electrostatic method, but the piezo method is most preferable.

  Moreover, the water-based inkjet ink of this invention can introduce | transduce a heat drying process into a printing process as needed in order to reinforce the drying property and tolerance of printed matter. By introducing the heat drying step, the film forming property of the binder resin composition may be improved, and an appropriate heat treatment is preferable. The heat treatment step can be used to such an extent that it does not affect the printing step (inkjet printing speed). For example, the heat treatment step is generally carried out at 40 to 100 ° C. for 1 to 200 seconds.

  EXAMPLES The present invention will be described more specifically with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. In the examples, “part” represents “part by weight” and “%” represents “% by weight”.

[Example 1]
A reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser was charged with 40 parts of ion exchange water and 0.2 part of Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd.) as a surfactant. , 40 parts of 2-ethylhexyl acrylate, 50 parts of methyl methacrylate, 7 parts of styrene, 2 parts of dimethylacrylamide, 1 part of methacrylic acid, 53 parts of ion-exchanged water, and Aqualon KH-10 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) An additional 1% of the pre-emulsion with 1.8 parts premixed was added. After raising the internal temperature to 60 ° C. and sufficiently purging with nitrogen, 10 parts of a 5% aqueous solution of potassium persulfate and 20 parts of a 1% aqueous solution of anhydrous sodium bisulfite were added to initiate polymerization. After maintaining the reaction system at 60 ° C. for 5 minutes, the remaining pre-emulsion, 5% aqueous solution of potassium persulfate, and 1% aqueous solution of anhydrous sodium bisulfite were maintained for 1.5 hours while maintaining the internal temperature at 60 ° C. The mixture was added dropwise and stirring was continued for 2 hours. After confirming that the conversion rate exceeded 98% by solid content measurement, the temperature was cooled to 30 ° C. Diethylaminoethanol was added to adjust the pH to 8.5, and the solid content was adjusted to 40% with ion exchange water to obtain a resin fine particle water dispersion. In addition, solid content was calculated | required by 150 degreeC 20 minute baking residue. The obtained resin fine particle water dispersion was made into the binder resin composition.

[Examples 2 to 10, 12 and Comparative Examples 1, 2, 4 to 7, 10 to 13]
The compounding compositions shown in Tables 1 and 2 were synthesized in the same manner as in Example 1 to obtain resin fine particle water dispersions. The obtained resin fine particle water dispersion was made into the binder resin composition of Examples 2-10, and Comparative Examples 1, 2, 4-7, and 10-13. However, in Comparative Examples 2 and 6, the resin aggregated during the emulsion polymerization, and the desired resin fine particle aqueous dispersion could not be obtained.

[Examples 11, 13, and 14 and Comparative Examples 3, 8, and 9]
The compounding compositions shown in Tables 1 and 2 were synthesized in the same manner as in Example 1 to obtain resin fine particle water dispersions. Binder resin compositions of Examples 11, 13, and 14 and Comparative Examples 3, 8, and 9 were obtained by adding and mixing the compound (f) as a crosslinking agent to the obtained resin fine particle aqueous dispersion.

[Measurement of tensile strength and elongation]
The obtained binder resin composition was poured into a 20 cm × 10 cm rectangular mold and allowed to stand at 40 ° C. overnight to obtain a dried film of the binder resin composition having a thickness of 0.5 mm. This was cut out into 6 cm x 0.5 cm, and it was set as the test piece for measuring tensile breaking strength and tensile breaking elongation. The measurement was performed under a constant temperature and humidity condition of a temperature of 25 ° C. and a humidity of 50% using a tensile tester [Tensilon manufactured by Orientec Co., Ltd.] with a chuck distance of 20 mm and a tensile speed of 50 mm / min. Tables 1 and 2 show the tensile rupture strength and the tensile rupture elongation calculated in consideration of the film thickness from the tensile rupture strength and tensile rupture elongation obtained by the measurement. However, in Comparative Example 4, cracks occurred in the dried film, and no film sample was obtained.

[Measurement of glass transition temperature (Tg)]
The glass transition temperature (Tg) was measured by DSC (differential scanning calorimeter). About 2 mg of a sample obtained by drying the binder resin composition was weighed on an aluminum pan, the aluminum pan was set on a DSC measurement holder, and the endothermic peak of the chart obtained under a temperature rising condition of 5 ° C./min was read. Table 1 and Table 2 show the peak temperature at this time as the glass transition temperature.

[Examples 15 to 28 and Comparative Examples 14 to 24]
[Preparation of inkjet ink]
14 parts of pigment [Lionol Blue 7351, manufactured by Toyo Ink Co., Ltd.], 20 parts of pigment dispersion resin [Johncril 61J, NV30%, manufactured by BASF Corporation] and 66 parts of ion-exchanged water were dispersed in a paint conditioner for 2 hours. A concentrated pigment dispersion was obtained. With respect to 10 parts of the solid content of the binder resin composition obtained in Examples 1 to 14 and Comparative Examples 1, 3 to 5, and 7 to 13, 50 parts of the above pigment concentrate, 20 parts of glycerin as a humectant, 1, 40 parts of 3-propanediol was added, ion-exchanged water was added so that the solid content was 11.5%, and then kneaded to obtain aqueous inkjet inks of Examples 15 to 28 and Comparative Examples 14 to 24. .

[Evaluation of inkjet ink]
The above aqueous inkjet ink was applied onto art paper, and further heated at 100 ° C. for 3 minutes to obtain an ink film for evaluation. Using this coating film, the friction resistance, water resistance, methanol resistance, and ethanol resistance were evaluated.

(Abrasion resistance)
Art paper was further superimposed on the ink coating film prepared above, and a 50 reciprocating friction test was performed at a load of 250 g. About the ink coated material after friction, the state of ink peeling or scratches was determined by visual judgment. Evaluation criteria are shown below in a 10-step evaluation. The evaluation results are shown in Table 3 and Table 4.
10: No peeling, no scratch ← → 1; Completely peeling

(water resistant)
The peeled state of the ink when the cotton swab dipped in ion-exchanged water was rubbed on the ink coating prepared above was evaluated by visual judgment. The evaluation criteria are shown below. The evaluation results are shown in Table 3 and Table 4.
○: No peeling △: Partial peeling ×: Completely peeling

(Solvent resistance)
The peeled state of the ink when the cotton swab dipped in methanol and ethanol was rubbed on the ink coating prepared above was evaluated by visual judgment. The evaluation criteria are shown below. The evaluation results are shown in Table 3 and Table 4.
○: No peeling △: Partial peeling ×: Completely peeling

As shown in Table 3 and Table 4, the water-based inkjet inks of Examples 15 to 28 including the binder resin compositions synthesized in Examples 1 to 14 have excellent friction resistance, water resistance, and solvent resistance, and are excellent. It was found to be resistant. On the other hand, the water-based inkjet ink containing the binder resin composition synthesized in Comparative Examples 1, 3 to 5, and 7 to 13 showed a decrease in friction resistance, water resistance, and solvent resistance, and ink resistance was not sufficient. Further, in Comparative Examples 2 and 6, aggregation occurred at the time of resin fine particle synthesis, and evaluation was not possible.

Claims (4)

At least one selected from the group consisting of an amide group-containing ethylenically unsaturated monomer (a), a hydroxyl group-containing ethylenically unsaturated monomer (b), and a carboxyl group-containing ethylenically unsaturated monomer (c). A binder resin composition for an aqueous inkjet ink comprising functional group-containing resin fine particles obtained by emulsion polymerization of an ethylenically unsaturated monomer (A) containing 0.1 to 15% by weight of a monomer,
The film formed from the binder resin composition has a tensile breaking strength at 25 ° C. of 10 to 30 N / mm ² , a tensile breaking elongation of 100 to 1000%, and
A binder resin composition for water-based inkjet inks having a glass transition temperature of 10 to 100 ° C.   The binder resin composition for water-based inkjet ink according to claim 1, wherein the ethylenically unsaturated monomer (A) contains 0.1 to 10% by weight of the monomer (d) having two or more ethylenically unsaturated groups. object. The ethylenically unsaturated monomer (A) contains 0.5 to 10% by weight of the carbonyl group-containing ethylenically unsaturated monomer (e), and
The binder resin composition for water-based inkjet inks of Claim 1 or 2 in which a binder resin composition contains the compound (f) which has a functional group which can react with a carbonyl group. The inkjet ink containing the binder resin composition for water-based inkjet inks in any one of Claims 1-3.