JP6004065B2 - Ink composition and inkjet recording method - Google Patents

Description

  The present invention relates to an ink composition and an ink jet recording method.

  A so-called ink jet recording method for recording images and characters with minute ink droplets ejected from nozzles of an ink jet recording head has been conventionally used for recording on the surface of an ink-absorbing recording medium such as paper. As an ink composition used in such an ink jet recording method, a solution in which a coloring material such as various dyes and / or pigments is dissolved or dispersed in a mixture having a high boiling point organic solvent and water is widely used.

  On the other hand, not only water-absorbing recording media such as paper but also ink non-absorbing or low-absorbing recording media such as printing paper, synthetic paper, and films, an ink composition that can be recorded by the ink jet recording method is required. Has been. In response to such a demand, an ink composition that can be recorded on a non-ink-absorbing or low-absorbing recording medium has been proposed (see Patent Document 1).

  On the other hand, as an ink using a polysiloxane surfactant, for example, a stencil ink composed of a W / O type emulsion containing a surfactant having two or more different HLB values (see Patent Document 2), an HLB value. Is known, such as an ink composition for waterless lithographic printing (see Patent Document 3) containing one or more nonionic surfactants in the range of 11 to 15.

JP 2007-217671 A JP-A-6-220383 Japanese Unexamined Patent Publication No. 63-178178

  However, since the ink composition proposed in Patent Document 1 contains a high-boiling organic solvent, the ink tends to be insufficiently dried when recording on a non-ink-absorbing or low-absorbing recording medium. In some cases, print quality such as uneven density, blocking, ink adhesion failure, etc. may be impaired. In addition, an ink composition that does not contain a high-boiling organic solvent cannot prevent the nozzles of an inkjet recording head from being dried, and the nozzles are likely to be clogged, and the storage stability of the ink may be reduced. It was.

  On the other hand, the ink compositions proposed in Patent Document 2 and Patent Document 3 exhibit repelling and aggregation unevenness caused by insufficient wettability on the surface of the recording medium when the recording medium is a non-absorbing recording medium such as a film. In some cases, the print quality was insufficient.

  SUMMARY An advantage of some aspects of the invention is that it provides an ink composition and an ink jet recording method that can be printed on various recording media.

  The present invention has been made in view of the above problems, and its object is to reduce repelling and aggregation unevenness on various recording media, particularly non-absorbing or low-absorbing recording media. Another object of the present invention is to provide an ink composition and an ink jet recording method that can obtain printing quality with excellent solid filling, can reduce clogging of nozzles, and are excellent in ink storage stability.

  SUMMARY An advantage of some aspects of the invention is to solve at least a part of the problems described above, and the invention can be implemented as the following forms or application examples.

[Application Example 1]
One aspect of the ink composition according to the present invention is:
Comprising at least a coloring material, two or more polysiloxane surfactants having different water solubility, and an alkyl polyol having a boiling point within the range of 180 to 230 ° C. at 1 atm. It is characterized by being recorded on a non-ink-absorbing or low-absorbing recording medium substantially free of alkyl polyols having a boiling point of 280 ° C. or higher under atmospheric pressure.

  According to the ink composition of Application Example 1, by using the polysiloxane surfactant and the alkyl polyols in combination, various recording media, particularly non-absorbing or low-absorbing recording media, There is little repellency and aggregation unevenness, it is possible to obtain print quality with excellent solid filling, nozzle clogging can be reduced, and ink storage stability is also excellent.

[Application Example 2]
The ink composition of Application Example 1 may include a lipophilic polysiloxane surfactant having the characteristics (a) and a hydrophilic polysiloxane surfactant having the characteristics (b).
(A) A lipophilic polysiloxane surfactant having an HLB value of 4 to 8, or wherein R is a methyl group in the following formula (1).
(B) A hydrophilic polysiloxane surfactant having an HLB value of 9 to 20 or R in the following formula (1) being a hydrogen atom.

（式中、Ｒは水素原子又はメチル基を表し、ａは２〜１３の整数を表し、ｍは０以上の整数を表し、ｎは１〜５の整数を表す。）

(In the formula, R represents a hydrogen atom or a methyl group, a represents an integer of 2 to 13, m represents an integer of 0 or more, and n represents an integer of 1 to 5.)

[Application Example 3]
In the ink composition of Application Example 1 or Application Example 2, the mass ratio of the lipophilic polysiloxane surfactant content / the hydrophilic polysiloxane surfactant content in the ink composition is 1 / It can be 20 or more and 2/1 or less.

[Application Example 4]
In the ink composition of any one of Application Examples 1 to 3, the content of the hydrophilic polysiloxane surfactant in the ink composition is more than the content of the lipophilic polysiloxane surfactant. Can be many.

[Application Example 5]
The ink composition of any one of Application Examples 1 to 4 may include glycol ethers having an HLB value calculated by the Davis method in the range of 4.2 to 8.0.

[Application Example 6]
In the ink composition according to any one of Application Examples 1 to 5, the alkyl polyols are C4-7 1,2-linear alkyldiols, and C4-7 1,2-linear alkyl. The relationship between the mass of the diol / the mass with the glycol ether may be more than 1/1 and 20/1 or less.

[Application Example 7]
One aspect of the recording apparatus according to the present invention can record the ink composition of any one of Application Examples 1 to 6.

[Application Example 8]
One aspect of the recorded matter according to the present invention is a recorded matter recorded by the inkjet recording method of Application Example 7.

  Hereinafter, preferred embodiments of the present invention will be described in detail. The embodiment described below describes an example of the present invention. In addition, the present invention is not limited to the following embodiments, and includes various modifications that are implemented within a range that does not change the gist of the present invention.

(1. Ink composition)
Comprising at least a coloring material, two or more polysiloxane surfactants having different water solubility, and an alkyl polyol having a boiling point within the range of 180 to 230 ° C. at 1 atm. It is characterized in that it is substantially free of alkyl polyols having a boiling point of 280 ° C. or higher under atmospheric pressure and is recorded on an ink or a low-absorbing recording medium.

  Hereinafter, each component used for this Embodiment is demonstrated in detail.

(2. Color material)
The ink composition according to the present embodiment includes a color material. Examples of the color material include dyes and pigments, and pigments are preferable from the viewpoint of water resistance, gas resistance, light resistance, and the like. As such a pigment, an inorganic pigment and an organic pigment can be used as the pigment, and each pigment can be used alone or in combination. As the inorganic pigment, for example, in addition to titanium oxide and iron oxide, carbon black produced by a known method such as a contact method, a furnace method, or a thermal method can be used. Examples of the organic pigment include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments), polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, Dioxazine pigments, thioindigo pigments, isoindolinone pigments, quinofullerone pigments, etc.), dye chelates (for example, basic dye-type chelates, acidic dye-type chelates), nitro pigments, nitroso pigments, aniline black, and the like can be used.

  Examples of yellow organic pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 16, 17, 24, 34, 35, 37, 53, 55, 65, 73, 74, 75, 81, 83, 93, 94, 95, 97, 98, 99, 108, 109, 110, 113, 114, 117, 120, 124, 128, 129, 133, 138, 139, 147, 150, 151, 153, 154, 155, 167, 172, 180, 185, 188, 213 and the like.

  Examples of magenta organic pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48 (Ca), 48 (Mn), 53, 57 (Ca), 57: 1, 88, 112, 114, 122, 123, 144, 146, 149, 150, 166 168, 170, 171, 175, 176, 177, 178, 179, 184, 185, 187, 194, 202, 209, 219, 224, 245, 247, 254, 264 or C.I. I. Pigment violet 19, 23, 32, 33, 36, 38, 43, 50 and the like.

  Examples of cyan organic pigments include C.I. I. Pigment Blue 1, 2, 3, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 15:34, 16, 18, 22, 25, 60, 65, 66, 75, C. I. Bat Blue 4, 60 and the like.

  Examples of black pigments include carbon blacks (CI pigment black 7) such as furnace black, lamp black, acetylene black and channel black, inorganic pigments such as iron oxide pigments; aniline black (CI pigment black 1) ) And other organic pigments.

  Examples of pigments other than those described above include C.I. I. Pigment green 7, 10, 36, 37, C.I. I. Pigment brown 3, 5, 25, 26, C.I. I. Pigment orange 2, 5, 7, 13, 14, 15, 16, 24, 34, 36, 38, 40, 43, 63, 64, C.I. I. Pigment white 4, 6, 6: 1, 7, 18, 26, and the like.

  These pigments are preferably contained in the range of 0.5% by mass or more and 20% by mass or less, more preferably in the range of 1% by mass or more and 10% by mass or less with respect to the total amount of the ink composition. If the content is less than 0.5% by mass, the print density (color developability) may be insufficient. If the content is more than 10% by mass, glossiness on glossy media, nozzle clogging, ejection failure, etc. There may be a problem with reliability such as stability.

  Further, from the viewpoint of color development and glossiness on glossy media, it is preferable that the volume average particle diameter of the pigment in the ink (hereinafter referred to as the average particle diameter as appropriate) is in the range of 50 nm to 400 nm. These average particle diameters can be obtained by particle diameter measurement using a Microtrac UPA150 (manufactured by Microtrac) or a particle size distribution analyzer LPA3100 (manufactured by Otsuka Electronics Co., Ltd.).

(3. Dispersant)
In order to apply the pigment to the ink composition, the pigment needs to be stably dispersed and held in water. As the method, a method of dispersing with a resin dispersant such as a water-soluble resin and / or a water-dispersible resin (hereinafter, a pigment treated by this method is referred to as “resin-dispersed pigment”), a water-soluble surfactant A method of dispersing with a surfactant of an agent and / or a water-dispersible surfactant (hereinafter, a pigment treated by this method is referred to as “surfactant-dispersed pigment”), hydrophilic functional groups on the surface of pigment particles Is chemically and physically introduced so that it can be dispersed and / or dissolved in water without a dispersant such as the above-mentioned resin or surfactant (hereinafter referred to as a “surface-treated pigment”. And the like). The ink composition according to the present embodiment can use any of the above-mentioned resin dispersion pigment, surfactant dispersion pigment, and surface treatment pigment, and can be used in a mixed form as necessary. Resin dispersed pigments are preferred.

  Examples of the resin dispersant used for the resin dispersion pigment include polyvinyl alcohols, polyacrylic acid, acrylic acid-acrylonitrile copolymer, vinyl acetate-acrylic acid ester copolymer, acrylic acid-acrylic acid ester copolymer, and styrene. -Acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid-acrylic acid ester copolymer, styrene-α-methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene-acrylic acid- Acrylate ester copolymer, styrene-maleic acid copolymer, styrene-maleic anhydride copolymer, vinyl naphthalene-acrylic acid copolymer, vinyl naphthalene-maleic acid copolymer, vinyl acetate-maleic acid ester copolymer Polymer, vinyl acetate-crotonic acid copolymer, vinyl acetate-acrylic Examples thereof include acid copolymers and salts thereof. Among these, a copolymer of a monomer having a hydrophobic functional group and a monomer having a hydrophilic functional group, and a polymer composed of a monomer having both a hydrophobic functional group and a hydrophilic functional group are preferable. As the form of the copolymer, any form of a random copolymer, a block copolymer, an alternating copolymer, and a graft copolymer can be used.

  Examples of the salt include basic compounds such as ammonia, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, dipropylamine, butylamine, isobutylamine, diethanolamine, triethanolamine, triisopropanolamine, aminomethylpropanol, and morpholine. Of the salt. The addition amount of these basic compounds is not particularly limited as long as it is equal to or more than the neutralization equivalent of the resin dispersant.

  The molecular weight of the resin dispersant is preferably in the range of 1,000 to 100,000 as the weight average molecular weight, and more preferably in the range of 3,000 to 10,000. When the molecular weight is in the above range, the pigment is stably dispersed in water, and viscosity control when applied to the ink composition is easy.

  Moreover, it is preferable that it is the range of 20-300 as an acid value, and it is more preferable that it is the range of 40-150. When the acid value is within this range, the dispersibility of the pigment particles in water is stable, and the water resistance and color developability of the recorded matter recorded with the ink composition using the pigment particle are improved.

  Commercially available products can be used as the resin dispersant described above. Specifically, Joncryl 67 (weight average molecular weight: 12,500, acid value: 213), Joncryl 678 (weight average molecular weight: 8,500, acid value: 215), Joncryl 586 (weight average molecular weight: 4,600) , Acid value: 108), joncryl 611 (weight average molecular weight: 8,100, acid value: 53), joncryl 680 (weight average molecular weight: 4,900, acid value: 215), joncryl 682 (weight average molecular weight) : 1,700, acid value: 238), joncryl 683 (weight average molecular weight: 8,000, acid value: 160), joncryl 690 (weight average molecular weight: 16,500, acid value: 240) , Manufactured by BASF Japan Ltd.).

  The surfactant used in the surfactant-dispersed pigment includes alkane sulfonate, α-olefin sulfonate, alkyl benzene sulfonate, alkyl naphthalene sulfonate, acylmethyl taurate, and dialkyl sulfo oxalate. Anionic surfactants such as alkyl sulfate ester salts, sulfated olefins, polyoxyethylene alkyl ether sulfate ester salts, alkyl phosphate ester salts, polyoxyethylene alkyl ether phosphate ester salts, monoglycerite phosphate ester salts, Amphoteric surfactants such as alkyl pyridium salts, alkyl amino acid salts, alkyl dimethyl betaines, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, polyoxyethylenes Alkylamide, glycerol alkyl esters, nonionic surfactants such as sorbitan alkyl esters.

The amount of the resin dispersant or the surfactant added to the pigment is preferably 1 part by mass to 100 parts by mass, and more preferably 5 parts by mass to 50 parts by mass with respect to 100 parts by mass of the pigment. By being in this range, the dispersion stability of the pigment in water can be ensured.
As the surface-treated pigment, as the hydrophilic functional group, -OM, -COOM, -CO -, - SO 3 M, -SO 2 NH 2, -RSO 2 M, -PO 3 HM, -PO 3 M 2 , —SO ₂ NHCOR, —NH ₃ , —NR ₃ (wherein M represents a hydrogen atom, an alkali metal, ammonium, or organic ammonium, and R represents an alkyl group having 1 to 12 carbon atoms or a substituent. And a phenyl group which may have or a naphthyl group which may have a substituent). These functional groups are physically and / or chemically introduced by grafting directly to the pigment particle surface and / or via multivalent groups. Examples of the polyvalent group include an alkylene group having 1 to 12 carbon atoms, a phenylene group which may have a substituent, or a naphthylene group which may have a substituent.

In addition, as the surface-treated pigment, -SO ₃ M and / or -RSO ₂ M (M is a counter ion, hydrogen ion, alkali metal ion, ammonium ion is added to the pigment particle surface by a treatment agent containing sulfur. Or an organic ammonium ion) that has been surface-treated so as to be chemically bonded, that is, the pigment has no active protons, no reactivity with sulfonic acid, and the pigment is insoluble or hardly soluble. The pigment is dispersed in a solvent, and then surface-treated so that —SO ₃ M and / or —RSO ₂ M are chemically bonded to the particle surface by amidosulfuric acid or a complex of sulfur trioxide and tertiary amine, It is preferably one that can be dispersed and / or dissolved in water.

  The functional group grafted on one pigment particle may be single or plural kinds. The type and degree of the functional group to be grafted may be appropriately determined in consideration of the dispersion stability in the ink, the color density, the drying property on the front surface of the inkjet recording head, and the like.

  The resin-dispersed pigment, surfactant-dispersed pigment, and surface-treated pigment described above are dispersed in water as follows: for resin-dispersed pigment, pigment, water, and resin dispersant; for surfactant-dispersed pigment, pigment and water. For surfactants and surface-treated pigments, add surface-treated pigment and water, and water-soluble organic solvents / neutralizers, etc., as necessary, ball mill, sand mill, attritor, roll mill, agitator mill, Henschel mixer, It can be performed by a conventionally used disperser such as a colloid mill, an ultrasonic homogenizer, a jet mill, or an ang mill. In this case, the pigment particle size may be dispersed until the average particle size is in the range of 20 nm to 500 nm, more preferably in the range of 20 nm to 200 nm, and particularly preferably in the range of 50 to 180 nm. It is preferable at the point which ensures the dispersion stability in water.

  In the present specification, the “average particle size” means a volume-based average particle size unless otherwise specified. The average particle diameter can be measured by a particle size distribution measuring apparatus using a laser diffraction scattering method as a measurement principle. As the laser diffraction type particle size distribution measuring device, for example, a particle size distribution meter (for example, “Microtrack UPA Series” manufactured by Nikkiso Co., Ltd.) based on the dynamic light scattering method can be used.

(4. Water-insoluble resin)
In the present invention, the resin dispersant may be a water-insoluble resin. Water insoluble refers to a resin having a solubility in 100 g of water at 25 ° C. of less than 1 g, for example. The structure of the water-insoluble resin is not particularly limited, but two preferred examples are given.

  The first example is made of a block copolymer resin of a monomer having a hydrophobic group and a monomer having a hydrophilic group, and contains at least a monomer having a salt-forming group.

  Monomers having hydrophobic groups are methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, dodecyl. Methacrylates such as methacrylate, octadecyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, glycidyl methacrylate, vinyl esters such as vinyl acetate, vinylcyan compounds such as acrylonitrile and methacrylonitrile, styrene, α-methylstyrene, Vinyltoluene, 4-t-butylstyrene, chlorost Emissions, vinyl anisole, include aromatic vinyl monomers such as vinyl naphthalene, may also be used alone, or a combination of two or more kinds.

  Examples of the monomer having a hydrophilic group include polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, and ethylene glycol / propylene glycol monomethacrylate. These can be used alone or in admixture of two or more. In particular, polyethylene glycol (2-30) monomethacrylate, polyethylene glycol (1-15) / propylene glycol (1-15) monomethacrylate, polypropylene glycol (2-30) methacrylate, methoxypolyethylene glycol (2-30) methacrylate, methoxy Glossiness of a printed image is improved by using a monomer component constituting a branched chain such as polytetramethylene glycol (2-30) methacrylate and methoxy (ethylene glycol / propylene glycol copolymer) (1-30) methacrylate. .

  Monomers having a salt-forming group include acrylic acid, methacrylic acid, styrene carboxylic acid, maleic acid and the like, and each can be used alone or in combination of two or more.

  Furthermore, a macromonomer such as a styrene macromonomer or a silicone macromonomer having a polysynthetic functional group at one end, or other monomers can be used in combination.

  The second example is a water-insoluble resin having a hydrophilic structural unit (a) and a hydrophobic structural unit (b). The hydrophilic structural unit (a) is not particularly limited as long as it is derived from a hydrophilic group-containing monomer, and even if it is derived from one kind of hydrophilic group-containing monomer, it contains two or more hydrophilic groups. It may be derived from a monomer. The hydrophilic group is not particularly limited, and may be a dissociable group or a nonionic hydrophilic group.

  The water-insoluble resin in the present invention includes a dissociable group and / or a nonionic hydrophilic group using a monomer having a dissociable group (dissociable group-containing monomer) and / or a monomer having a nonionic hydrophilic group. Can be introduced.

  The dissociable group is preferable from the viewpoint of stability in an emulsified or dispersed state. Examples of the dissociable group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group. Among these, a carboxyl group is preferable from the viewpoint of dispersion stability when an ink composition is formed.

  The hydrophilic group-containing monomer is preferably a dissociable group-containing monomer, and more preferably a dissociable group-containing monomer having a dissociable group and an ethylenically unsaturated bond. Examples of the dissociable group-containing monomer include an unsaturated carboxylic acid monomer, an unsaturated sulfonic acid monomer, and an unsaturated phosphoric acid monomer.

  The hydrophobic structural unit (b) preferably includes a structural unit having an aromatic ring bonded to an atom forming the main chain via a linking group. In such a structural unit having an aromatic ring, the aromatic ring has a structure in which the aromatic ring is bonded to an atom forming the main chain of the water-insoluble resin through a linking group and is not directly bonded to an atom forming the main chain of the water-insoluble resin. Since an appropriate distance is maintained between the hydrophobic aromatic ring and the hydrophilic structural unit, the water-insoluble resin and the pigment are likely to interact with each other and are strongly adsorbed to further improve dispersibility. .

  A more detailed preferred monomer type of the second example is described in JP2011-162692.

  The water-insoluble resin is preferably a styrene- (meth) acrylic acid copolymer as in the case of the water-soluble resin described above.

  The molecular weight of the resin dispersant is preferably in the range of 1,000 to 100,000 as the weight average molecular weight, and more preferably in the range of 3,000 to 10,000. When the molecular weight is in the above range, the pigment is stably dispersed in water, and viscosity control when applied to the ink composition is easy.

  Moreover, it is preferable that it is the range of 50-300 as an acid value, and it is more preferable that it is the range of 70-150. When the acid value is within this range, the dispersibility of the pigment particles in water can be stably secured, and the water resistance of the recorded matter recorded with the ink composition using the pigment particle becomes good.

(5. Alkyl polyols)
The ink composition according to the present embodiment comprises alkyl polyols having a boiling point within the range of 180 to 230 ° C. at 1 atmosphere. The ink composition according to the present embodiment includes alkyl polyols that satisfy the above-described boiling range, thereby controlling the wettability, permeability, and drying properties of the ink composition without being significantly affected by the type of recording medium. Can do. As a result, it is possible to record images with excellent fixability on various recording media, particularly non-ink-absorbing or low-absorbing recording media, and reduce clogging of the nozzles of the inkjet recording head. Can do.

  The alkyl polyols in the ink composition according to the present embodiment are added with glycol ethers having an HLB value calculated by the Davis method in the range of 4.2 to 8.0. In addition, the component has a characteristic of a solubilizing agent in the ink vehicle.

  The alkyl polyols contained in the ink composition according to the present embodiment have a boiling point within a range of 180 to 230 ° C. under 1 atm, and contain at least one kind of polyols within a range of 190 to 220 ° C. It is preferable. As the polyols, C4-7 1,2-linear alkyldiols are preferable. From the viewpoint of compatibility with the glycol ether, the relationship of (mass of C4-7 1,2-linear alkyldiol) / (mass with the glycol ether) is preferably more than 1/1 and 20/1. Or less, more preferably 2/1 or more and 16/1 or less by mass ratio, and still more preferably 4/1 or more and 16/1 or less by mass ratio.

  If the boiling point of the alkyl polyols contained in the ink composition under 1 atm is less than 180 ° C., the ink composition may become more dry, which may cause clogging of the nozzles of the inkjet recording head. When the boiling point at 1 atm is higher than 230 ° C., the drying property of the ink composition is lowered, so that the density unevenness of the printed image recorded on the non-ink-absorbing recording medium is particularly noticeable and the fixing property of the image is reduced. May decrease.

  Specific examples of alkyl polyols having a boiling point within the range of 180 to 230 ° C. under 1 atm include propylene glycol [188 ° C.], 1,3-propanediol [210 ° C.], 1,2-butanediol [ 194 ° C], 1,3-butanediol [208 ° C], 1,4-butanediol [230 ° C], 1,2-pentanediol [210 ° C], 3-methyl-1,3-butanediol [203 ° C] ], 2-ethyl-2-methyl-1,3-propanediol [226 ° C.], 2-methyl-1,3-propanediol [214 ° C.], 2-methyl-2-propyl-1,3-propanediol [230 ° C], 2,2-dimethyl-1,3-propanediol [210 ° C], 2-methylpentane-2,4-diol [197 ° C], dipropylene glycol [230 ° C] , 1,2-heptane-diol [227 ° C.] and the like. In addition, the numerical value in a parenthesis represents the boiling point under 1 atmosphere.

  The content of the alkyl polyols is based on the total amount of the ink composition from the viewpoint of improving the wettability and penetrability to the recording medium to reduce unevenness in density, and ensuring ink storage stability and ejection reliability. It is preferably included in the range of 5% by mass to 30% by mass. When the content is less than 5% by mass, the storage stability of the ink composition is lowered, and the drying property of the ink composition is increased, which may cause clogging of the nozzles of the inkjet recording head. On the other hand, when it exceeds 30% by mass, the drying property of the ink composition decreases, so that the density unevenness of the printed image recorded on the non-ink-absorbing recording medium is noticeable, and the fixing property of the image may be decreased. is there. Moreover, it becomes difficult to adjust the viscosity of the ink composition to a range suitable for the ink jet recording method.

  Among the above-mentioned alkyl polyols, 1,2-linear alkyl diols having a carbon number in the range of 4 to 7 (hereinafter sometimes abbreviated as “C4-7”) have the above functions. In addition, in synergy with the glycol ethers that are essential components of the ink composition of the present invention, the ink composition has the effect of further increasing the wettability of the ink composition with respect to the recording medium to uniformly wet it, and the effect of further increasing the permeability. Therefore, the ink composition can be further reduced by adding C4-7 1,2-linear alkyldiols to the ink composition. Also, C4-7 1,2-linear alkyldiols are excellent in compatibility with the glycol ethers described above. Here, “compatible” means that among the components constituting the ink composition, in the ink composition using water as a main solvent, the glycol ethers and C4-7 1,2-linear alkyldiols The combination of each material and the ratio of each material is such that the mixture of the materials is completely dissolved. By including a C4-7 1,2-linear alkyldiol having excellent compatibility with the glycol ethers in the ink composition, the solubility of the glycol ether in the ink composition can be increased, and the ink Improvement of storage stability and discharge stability can be realized. Moreover, since it becomes easy to increase the content of the glycol ethers in the ink composition, it is possible to contribute to further improving the quality of the recorded image.

  Specific examples of C4-7 1,2-linear alkyldiols having such properties include 1,2-butanediol [194 ° C.], 1,2-pentanediol [210 ° C.], 1,2- Examples thereof include hexanediol [224 ° C.], 1,2-heptanediol [227 ° C.] and the like. Among these, in particular, C2-C6 (carbon number is 4-6) 1,2-linear alkyldiol such as 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol is water. From the viewpoint of solubility in water and compatibility with the glycol ethers, moisture retention against nozzle clogging, and drying of printed images, 50% by mass or more of alkyl polyols in the ink is preferably C4. It is preferably a 1,2-linear alkyl diol having ˜6 (having 4 to 6 carbon atoms).

  The addition amount of C4-7 1,2-linear alkyl diols is selected from the viewpoints of compatibility with the glycol ethers, storage stability of the ink composition, and ejection stability, particularly from the viewpoint of preventing clogging. Preferably it is the range of 0.5 mass%-25 mass% with respect to the composition whole quantity, Most preferably, it is the range of 1 mass%-20 mass%. In particular, in the second step (drying step) of the ink jet recording method to be described later using the ink composition, the evaporation and scattering rate of C4-7 1,2-linear alkyldiols is sufficiently high. There is an extraordinary effect that the recorded matter is dried quickly and the recording speed is improved. There is no problem in terms of odor in each process.

  Furthermore, the ink composition of the present invention is substantially free of alkyl polyols having a boiling point of 280 ° C. or higher at 1 atm. By including an alkyl polyol having a boiling point of 280 ° C. or higher at 1 atm, the drying property of the ink composition is greatly reduced. As a result, in various recording media, particularly in non-ink-absorbing or low-absorbing recording media, not only unevenness of image density is noticeable, but also image fixing properties cannot be obtained. Examples of alkyl polyols having a boiling point of 280 ° C. or higher at 1 atm include glycerin having a boiling point of 290 ° C. at 1 atm.

  “Substantially not contained” means that it is not contained in an amount that sufficiently exhibits the significance of addition. Specific examples of “substantially free” of the above alkyl polyol include, for example, 1.0% by mass or more, preferably 0.5% by mass or less, more preferably 0.1% by mass or less, More preferably 0.05% by mass or less, particularly preferably 0.01% by mass or less, and most preferably 0.001% by mass or less.

(6. Polysiloxane surfactant)
The water-based pigment ink composition according to the present invention contains two or more polysiloxane surfactants having different HLB values.

  In a preferred embodiment, one or more lipophilic polysiloxane surfactants having an HLB value of 2 to 8 and one or more hydrophilic polysiloxane surfactants having an HLB value of 9 to 20 are used. Containing. A surfactant having an HLB value of less than 4 is not preferable because it is difficult to dissolve in a water-based ink solvent. On the other hand, the HLB value of the surfactant used as the hydrophilic polysiloxane surfactant is preferably 9 to 20, and more preferably 9 to 16.

  The “HLB value (hydrophilic lipophilic balance)” is a value determined from the balance between the hydrophilic group and the lipophilic group of the surfactant molecule. When the HLB value is high, the hydrophilicity is high. It indicates that the surfactant is a surfactant, and a low HLB value indicates that the surfactant is highly lipophilic. In this specification, “hydrophilic” and “lipophilic” mean that when two types of polysiloxane surfactants having different HLB values are simply compared, one of them is “hydrophilic” with respect to the other. ”And“ lipophilic ”, only“ hydrophilic ”polysiloxane surfactants and“ lipophilic ”polysiloxane surfactants are generally hydrophilic surfactants, respectively. It is not meant to be an agent or a lipophilic surfactant. The polysiloxane surfactant is preferably a polyether siloxane surfactant.

  Commercially available polysiloxane surfactants can be used. For example, as the hydrophilic polysiloxane surfactant, KF-6011 (HLB value = 14.5), KF-6013 ( HLB value = 10), KF-6004 (HLB value = 9), KF-6043 (HLB value = 14.5), KF-643 (HLB value = 14), KF-640 (HLB value = 14), KF- 351A (HLB value = 12), KF-354L (HLB value = 16) [all manufactured by Shin-Etsu Silicone Co., Ltd.], FZ-2105 (HLB value = 11), L-7604 (HLB value = 13), FZ- 2104 (HLB value = 14) [both manufactured by Toray Dow Corning Co., Ltd.] and the like, and as the lipophilic polysiloxane surfactant, KF-945 (HLB) = 4), KF-6020 (HLB value = 4), X-22-6191 (HLB value = 2), X-22-4515 (HLB value = 5), KF-6015 (HLB value = 5), KF- 6017 (HLB value = 5), KF-6038 (HLB value = 3) [all manufactured by Shin-Etsu Silicone Co., Ltd.], FZ-2116 (HLB value = 5), FZ-2120 (HLB value = 6), L- 720 (HLB value = 7), L-7002 (HLB value = 7), FZ-2123 (HLB value = 8) [all manufactured by Toray Dow Corning Co., Ltd.] and the like can be used.

  The content of the polysiloxane surfactant in the water-based pigment ink composition according to the present invention is not particularly limited, but the hydrophilic polysiloxane surfactant and the lipophilic property with respect to the total mass of the water-based pigment ink composition. The total amount with the polysiloxane-based surfactant is preferably 0.01 to 10% by mass, more preferably 0.05 to 2% by mass. If the content is less than 0.01% by mass, the effect of lowering the surface tension may be insufficient. If the content exceeds 10% by mass, the wettability on the nozzle surface may be deteriorated without dissolving.

  The ratio of the hydrophilic polysiloxane surfactant to the lipophilic polysiloxane surfactant contained in the aqueous pigment ink composition according to the present invention is not particularly limited, but the content of the lipophilic polysiloxane surfactant is not limited. / Mass ratio of hydrophilic polysiloxane surfactant content is preferably 1/20 to 2/1, more preferably 1/15 to 1/3. When the mass ratio is less than 1/20 or exceeds 2/1, the effect of the present invention, that is, the effect of improving good glossiness and sharpness may be reduced. Further, as described above, it is preferable that the amount of hydrophilic polysiloxane surfactant is larger than that of the new oily polysiloxane surfactant, and more preferably twice or more times the amount of hydrophilic polysiloxane surfactant is preferable. .

  Moreover, what is shown to following formula (1) can be used preferably as a polysiloxane type surfactant. The polysiloxane surfactant is not particularly limited, but 20% by mass of propylene glycol, 10% by mass of 1,2-hexanediol, 0.1% by mass of the polyether siloxane surfactant, and water. When an aqueous solution containing 69.9% by mass is used, it is preferable to use an aqueous solution having a 1 Hz dynamic surface tension of 26 mN / m or less. For example, it can be measured using a bubble pressure dynamic surface tension meter BP2 (manufactured by KRUS).

  Moreover, as polysiloxane type surfactant, following formula (1)

（式中、Ｒは水素原子又はメチル基を表し、ａは２〜１３の整数を表し、ｍは０以上の整数を表し、ｎは１〜５の整数を表す。）
で表される一種又は二種以上の化合物を含んでなることが好ましい。さらに、上記式（１）の化合物において、Ｒは水素原子又はメチル基を表し、ａは２〜１１の整数を表し、ｍは２０〜７０の整数を表し、ｎは２〜５の整数である一種又は二種以上の化合物を含んでなることである。がより好ましい。さらにまた、上記式（１）の化合物において、Ｒは水素原子又はメチル基を表し、ａは９〜１３の整数を表し、ｍは２〜４の整数を表し、ｎは１〜２の整数である一種又は二種以上の化合物を含んでなることがより好ましい。

(In the formula, R represents a hydrogen atom or a methyl group, a represents an integer of 2 to 13, m represents an integer of 0 or more, and n represents an integer of 1 to 5.)
It is preferable to comprise 1 type, or 2 or more types of compounds represented by these. Furthermore, in the compound of the above formula (1), R represents a hydrogen atom or a methyl group, a represents an integer of 2 to 11, m represents an integer of 20 to 70, and n is an integer of 2 to 5. One or two or more compounds are included. Is more preferable. Furthermore, in the compound of the above formula (1), R represents a hydrogen atom or a methyl group, a represents an integer of 9 to 13, m represents an integer of 2 to 4, and n represents an integer of 1 to 2. More preferably, it comprises one or more compounds.

  By using such a specific polysiloxane-based surfactant, ink beading and bleeding are further improved even when the recording medium is non-absorbent or printed on printing paper.

  In the compound of the above formula (1), ink beading can be further improved by using a lipophilic polysiloxane surfactant in which R is a methyl group. In the compound of the above formula (1), ink bleeding can be further improved by using a hydrophilic polysiloxane surfactant in which R is a hydrogen atom. R is a methyl group surfactant, preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.70% by mass.

  In the compound of the above formula (1), by appropriately adjusting the blending ratio of the compound in which R is a methyl group and the compound in which R is a hydrogen atom, a high-quality image without further bleeding or beading can be realized, Further, it is effective as a regulator when the fluidity varies depending on the pigment type and the amount of resin.

  Commercially available surfactants such as those described above may be used. For example, Olfine PD-501, Olfine PD-570 (manufactured by Nissin Chemical Industry Co., Ltd.), KF-954A, KF-353A, KF6017, X-22-6551, AW-3 (all manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-347, 348 (all manufactured by Big Chemie Japan Co., Ltd.) and the like can be used.

  The ink composition according to the present invention further includes other surfactants, specifically, a fluorine-based surfactant, an acetylene glycol-based surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, and the like. It may be added.

  Of these, acetylene glycol surfactants are preferably used in combination. As a result, the ink has less air bubbles and has the effect of reducing the surface tension of the ink.

  Examples of acetylene glycol surfactants include Surfinol 104, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 104S, 420, 440, 465, 485, SE, SE-F, 504, 61. DF37, CT111, CT121, CT131, CT136, GA, DF110D (all trade names, manufactured by Air Products and Chemicals, Inc.), Olfin B, Y, P, A, STG, SPC, E1004, E1010, PD-001 , PD-002W, PD-003, PD-004, EXP. 4001, EXP. 4036, EXP. 4051, AF-103, AF-104, AK-02, SK-14, AE-3 (all trade names, manufactured by Nissin Chemical Industry Co., Ltd.), acetylenol E00, E00P, E40, E100 (all trade names, Kawaken Fine Chemical Co., Ltd.).

(7. Glycol ethers)
The ink composition according to the present embodiment preferably includes glycol ethers having an HLB value calculated by the Davis method in the range of 4.2 to 8.0. The ink composition according to the present embodiment includes the glycol ethers satisfying the above HLB value range, so that the wettability / penetration speed can be controlled without being significantly affected by the type of the recording medium. As a result, a clear image with little density unevenness can be recorded on various recording media, in particular, non-ink-absorbing or low-absorbing recording media.

Here, the HLB value of the glycol ethers used in the present embodiment is a value for evaluating the hydrophilicity of the compound proposed by Davis et al., For example, the document “JT Davies and EK Rideal,“ It is a numerical value obtained by the Davis method defined in Interface Phenomena “2nd ed. Academic Press, New York 1963”, which is a value calculated by the following equation (2).
HLB value = 7 + Σ [1] + Σ [2] (2)
(However, [1] represents the number of hydrophilic groups and [2] represents the number of hydrophobic groups.)
Table 1 below exemplifies the number of representative hydrophilic groups and hydrophobic groups.

  The glycol ethers contained in the ink composition according to the present embodiment have an HLB value calculated by the Davis method in the range of 4.2 to 8.0, and in the range of 5.8 to 8.0. More preferably. When the HLB value is less than 4.2, the hydrophobicity of glycol ethers increases, and the affinity with water as the main solvent may decrease, and the storage stability of the ink may decrease. When the HLB value is greater than 8.0, the effect of wettability / penetration to the recording medium is reduced, and the density unevenness of the image may be noticeable. In particular, the wettability effect on a non-ink-absorbing or low-absorbing recording medium that is a hydrophobic surface tends to be significantly reduced.

  Specific examples of such glycol ethers include ethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monoisohexyl ether, diethylene glycol monohexyl ether, triethylene glycol monohexyl ether, diethylene glycol monoisohexyl ether, triethylene glycol Ethylene glycol monoisohexyl ether, ethylene glycol monoisoheptyl ether, diethylene glycol monoisoheptyl ether, triethylene glycol monoisoheptyl ether, ethylene glycol monooctyl ether, ethylene glycol monoisooctyl ether, diethylene glycol monoisooctyl ether, triethylene glycol Monoisooctylate , Ethylene glycol mono-2-ethylhexyl ether, diethylene glycol mono-2-ethylhexyl ether, triethylene glycol mono-2-ethylhexyl ether, diethylene glycol mono-2-ethylpentyl ether, ethylene glycol mono-2-ethylpentyl ether, ethylene glycol mono -2-methylpentyl ether, diethylene glycol mono-2-methylpentyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, tripropylene glycol monomethyl Examples include ether. These can be used individually by 1 type or in mixture of 2 or more types.

  Among the glycol ethers exemplified above, the alkyl group contained in the glycol ethers preferably has a branched structure. By containing a glycol ether having an alkyl group having a branched structure, a clear image with little shading unevenness can be recorded particularly on a non-ink-absorbing or low-absorbing recording medium. Specifically, ethylene glycol monoisobutyl ether, ethylene glycol monoisohexyl ether, diethylene glycol monoisohexyl ether, triethylene glycol monoisohexyl ether, ethylene glycol monoisoheptyl ether, diethylene glycol monoisoheptyl ether, triethylene glycol monoiso Heptyl ether, ethylene glycol monoisooctyl ether, diethylene glycol monoisooctyl ether, triethylene glycol monoisooctyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol mono-2-ethylhexyl ether, triethylene glycol mono-2-ethylhexyl ether , Diethylene glycol mono-2-ethyl Inch ether, ethylene glycol mono-2-ethyl pentyl ether, ethylene glycol mono-2-methylpentyl ether, diethylene glycol mono-2-methylpentyl ether, and the like.

  Among the branched structures of the alkyl group contained in the glycol ethers, a 2-methylpentyl group, a 2-ethylpentyl group, and a 2-ethylhexyl group are more preferable, and a 2-ethylhexyl group is particularly preferable from the viewpoint of further improving color developability. preferable. Specifically, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol mono-2-ethylhexyl ether, triethylene glycol mono-2-ethylhexyl ether, diethylene glycol mono-2-ethylpentyl ether, ethylene glycol mono-2-ethylpentyl ether , Ethylene glycol mono-2-methylpentyl ether, diethylene glycol mono-2-methylpentyl ether, etc., ethylene glycol mono-2-ethylhexyl ether, diethylene glycol mono-2-ethylhexyl ether, triethylene glycol mono-2-ethylhexyl ether Etc. are particularly preferred.

  The content of the glycol ethers is improved with respect to the total amount of the ink composition from the viewpoint of improving the wettability and penetrability to the recording medium to reduce unevenness in density, and ensuring ink storage stability and ejection reliability. It is preferably included in the range of 0.05% by mass or more and 6% by mass or less. If it is less than 0.05% by mass, the wettability, penetrability, and drying properties of the ink composition will be poor, and it may be difficult to obtain a clear image, and the printing density (coloring property) may be insufficient. is there. On the other hand, if it exceeds 6% by mass, the viscosity of the ink becomes high and the clogging of the head may occur, or the storage stability may not be obtained because it is not completely dissolved in the ink composition. The content of the glycol ether is more preferably in the range of 0.1% by mass to 2% by mass with respect to the total amount of the ink composition.

(8. Resin particles)
The ink composition according to the present embodiment contains polymer particles as resin particles. By including resin particles in the ink composition, an image having excellent abrasion resistance can be formed on the recording medium. In particular, when recording using an ink composition comprising the resin particles on a non-ink-absorbing or low-ink-absorbing recording medium such as vinyl chloride, polypropylene, or polyethylene, the second step in the inkjet recording method described later ( By passing through the drying step, an image having excellent abrasion resistance can be obtained. The reason is that in the second step (drying step) in the ink jet recording method to be described later, the resin particles have a function of solidifying the ink and further firmly fixing the solidified ink on the recording medium. This is because this effect can be further enhanced.

  The first polymer particles used in the ink composition are selected from the group consisting of polyolefin resins, acrylic resins, methacrylic resins, styrene resins, urethane resins, acrylamide resins, epoxy resins, and mixtures thereof. Preferably, those to be prepared are mentioned. Among them, those selected from the group consisting of polyolefin resins, acrylic resins and urethane resins are more preferable. Particularly, as the polyolefin resins, any resins selected from ethylene-polar monomer copolymers and olefin elastomers are used. It is preferable that These resins may be used as homopolymers or copolymers, and may be used as either a single phase structure or a multiphase structure (core-shell type). More specifically, ethylene- (meth) ethyl acrylate Copolymer, Ethylene-methyl (meth) acrylate copolymer, Ethylene- (meth) propyl acrylate copolymer, Ethylene- (meth) butyl acrylate copolymer, Ethylene- (meth) acrylic acid hexyl copolymer Ethylene- (meth) acrylic acid-2-hydroxyethyl copolymer, ethylene- (meth) acrylic acid-2-hydroxypropyl copolymer, ethylene- (meth) acrylic acid glycidyl copolymer, etc. (Meth) acrylic acid ester copolymer, ethylene- (meth) acrylic acid copolymer, ethylene-maleic acid copolymer, ethylene- Malic acid copolymer, ethylene-ethylenically unsaturated acid copolymer such as ethylene-crotonic acid copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl propionate copolymer, ethylene-vinyl stearate, etc. Ethylene-vinyl ester copolymer, further polyacrylic acid ester or its copolymer, polymethacrylic acid ester or its copolymer, polyacrylonitrile or its copolymer, polycyanoacrylate, polyacrylamide, polyacrylic acid, poly Methacrylic acid, polyethylene, polypropylene, polybutene, polyisobutylene, polystyrene or copolymers thereof, petroleum resin, chroman indene resin, terpene resin, polyvinyl acetate or copolymer thereof, polyvinyl alcohol, polyvinyl acetal, Examples include vinyl ether, polyvinyl chloride or a copolymer thereof, polyvinylidene chloride, fluororesin, fluororubber, polyvinyl carbazole, polyvinyl pyridine, polyvinyl imidazole, polybutadiene or a copolymer thereof, polychloroprene, polyisoprene, and natural resin. . In particular, it has good compatibility with non-ink-absorbing films such as vinyl chloride, polypropylene, and polyethylene (has a hydrophobic portion in the molecular structure), and also has a hydrophilic portion that has strong adhesiveness. For example, an ethylene-vinyl ester copolymer, an ethylene- (meth) acrylic acid ester copolymer, and the like are preferable, and an ethylene-vinyl acetate copolymer is more preferable.

  In particular, an ethylene-vinyl acetate polymer particle obtained by mixing about 8 to 35% by mass of an ethylene monomer with a vinyl acetate monomer and emulsion-polymerizing it under high pressure to give an emulsion is excellent in water resistance, weather resistance, and alkali resistance. Adhesion to polyolefin films such as polypropylene and polyethylene and abrasion resistance are also improved. The ethylene-vinyl acetate copolymer preferably has a vinyl acetate content of 8 to 35% by mass, particularly 12 to 30% by mass in terms of adhesion, abrasion resistance, water resistance and the like.

  The average particle diameter of the first polymer particles is preferably 200 nm or more, more preferably in the range of 200 nm to 550 nm, and preferably in the range of 200 to 350 nm. If the average particle size of the polymer particles is less than 200 nm, sufficient abrasion resistance on fine paper, which is an ink-absorbing recording medium, cannot be obtained.

  The heat distortion temperature (in the present invention, Tg or MFT) is preferably less than 100 ° C., more preferably in the range of 0 ° C. to 90 ° C., more preferably 0 ° C. to 50 ° C., Most preferably, it is the range of 20 to 40 degreeC. It is preferable that at least one kind of such polymer particles is contained. If the thermal deformation temperature of the polymer particles is 100 ° C. or higher, the heating temperature in the second step (drying step) described later may be required to be 100 ° C. or higher, and the non-recording medium shrinks or expands due to heat to form a printed image. Since wrinkles occur, it may not be preferable. Moreover, by including the component whose heat distortion temperature is 0 degreeC or more, the effect in which a stronger resin film is formed in the 2nd process (drying process) mentioned later is high. Therefore, the rub resistance of the recorded image is further improved. Also, ink clogging at the nozzle tip of the ink jet recording head is unlikely to occur. On the other hand, when polymer particles composed only of components having a heat distortion temperature of less than 0 ° C. are used, when a second step (drying step) described later is performed, a solid resin film is hardly formed and the recorded image Rubbing resistance may be poor. Furthermore, ink solidified material is generated at the nozzle tip, and clogging is likely to occur.

  The ink composition contains the second polymer particles, and the constituents of the second polymer particles include, for example, carnauba wax, candeli wax, beeswax, rice wax, lanolin and other plant / animal waxes; paraffin wax, microcrystalline Petroleum waxes such as wax, polyethylene wax, polyethylene oxide wax, petrolatum; mineral waxes such as montan wax and ozokerite; synthetic waxes such as carbon wax, Hoechst wax, polyolefin wax, stearamide, α-olefin / anhydrous malein Natural / synthetic wax emulsions such as acid copolymers, blended waxes, and the like can be used singly or in combination. Among these, preferred wax types are polyolefin waxes, particularly polyethylene wax and polypropylene wax, with polyethylene wax being most preferred. As the wax particles, commercially available products can be used as they are. For example, Nopcoat PEM17 (trade name, manufactured by San Nopco), Chemipearl W4005 (trade name, manufactured by Mitsui Chemicals), AQUACER 507, AQUACER 515, AQUACER 526, AQUACER 531, AQUACER 537, AQUACER 552, AQUACER 593, AQUACER 840, AQUACER 1547 (trade name, manufactured by Big Chemie Japan Co., Ltd.) and the like.

  The average particle diameter is preferably less than 200 nm, more preferably in the range of 20 nm to 100 nm. When the average particle size is 200 nm or more, the abrasion resistance of the recorded image becomes worse when printing on an ink non-absorbing recording medium having a smooth surface such as a film.

  The heat distortion temperature is preferably 100 ° C. or higher, but is preferably in the range of 100 ° C. to 200 ° C. from the viewpoint of abrasion resistance. When the heat distortion temperature is less than 100 ° C., the polymer particles are softened by frictional heat when rubbed, so that sufficient abrasion resistance cannot be obtained.

  In particular, in the ink composition according to the present embodiment, an ethylene-vinyl acetate copolymer polymer particle is used as the first polymer particle having an average particle diameter of 200 nm or more and a thermal deformation temperature of less than 100 ° C., and the average particle diameter is When polyethylene wax particles were used as the second polymer particles having a heat deformation temperature of 100 ° C. or higher and less than 200 nm, recording was performed on any recording medium having ink absorptivity, low ink absorptivity, and non-ink absorptivity. Good abrasion resistance can be obtained even in a printed image. The reason why the recorded image has good abrasion resistance by using the above-described polymer particles in combination is not yet clear, but is presumed as follows.

  Since the components constituting the ethylene-vinyl acetate copolymer particles have a good affinity for non-ink-absorbing or low-absorbing recording media and water-insoluble colorants, the second step (drying step) ) Is firmly fixed on the recording medium while wrapping the coloring material when the resin film is formed. On the other hand, the component of the polyethylene wax particles is also present on the surface of the resin film, and has a characteristic of reducing the frictional resistance on the surface of the resin film. Because of the synergistic effect of the ethylene skeleton that is common to these resins, it is possible to form a resin film that is difficult to be scraped off from the outside and difficult to peel off from the recording medium. It is assumed that it will improve.

  The total amount of the first polymer particles having an average particle diameter of less than 200 nm and a heat distortion temperature of 100 ° C. or more and the second polymer particles having an average particle diameter of 200 nm or more and a heat deformation temperature of less than 100 ° C. It is preferably in the range of 0.5% by mass to 10% by mass in terms of solid content with respect to the total amount of the ink composition. By being within this range, the ink composition according to the present embodiment and a second step which will be described later as a preferred ink jet recording method can be used on various recording media, particularly non-ink-absorbing or low-absorbing recording media. By combining (drying step), the ink composition can be solidified and fixed.

  The content ratio of the first polymer particles and the second polymer particles in the resin particles is preferably in the range of first polymer particles: second polymer particles = 1: 5 to 10: 1 on a mass basis in terms of solid content. Within this range, the above-described mechanism works well, and the recorded image has good abrasion resistance.

  In the ink composition according to the present embodiment, it is preferable that both the first polymer particles and the second polymer particles are contained in a fine particle state (that is, an emulsion state or a suspension state). By containing the resin particles in a fine particle state, it is easy to adjust the viscosity of the ink composition to an appropriate range in the ink jet recording method, and it is easy to ensure storage stability and ejection stability.

(9. Water)
The ink composition according to the present embodiment includes water. Water is a main medium of the ink composition, and is a component that is evaporated and scattered in a second step (drying step) described later. The water is preferably water from which ionic impurities such as pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, distilled water or ultrapure water are removed as much as possible. Further, when water sterilized by ultraviolet irradiation or addition of hydrogen peroxide is used, it is preferable because generation of mold and bacteria can be prevented when the pigment dispersion and the ink composition using the pigment dispersion are stored for a long period of time. .

(10. Other additives)
From the viewpoint of further improving the characteristics of the ink composition according to the present embodiment, in addition to the components described above, a penetrating solvent, a humectant, an antiseptic / antifungal agent, and an antioxidant as necessary , PH adjusting agents, chelating agents and the like can be added.

  Examples of preservatives and fungicides include sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, 1,2-dibenzthiazoline-3-one ( ICI's Proxel CRL, Proxel BND, Proxel GXL, Proxel XL-2, Proxel TN) and the like.

  Furthermore, examples of pH adjusters, solubilizers or antioxidants include amines such as diethanolamine, triethanolamine, propanolamine, morpholine and their modified products, potassium hydroxide, sodium hydroxide, lithium hydroxide, etc. Inorganic salts, ammonium hydroxide, quaternary ammonium hydroxide (tetramethylammonium, etc.), carbonates such as potassium carbonate, sodium carbonate, lithium carbonate and other phosphates, or N-methyl-2-pyrrolidone, allophanate, methyl aloha Examples include L-ascorbic acid and salts thereof, such as allophanates such as benzoate, biurets such as biuret, dimethyl biuret, and tetramethyl biuret.

  In addition, the ink composition according to the present invention may contain an antioxidant and a UV absorber, and examples thereof include Tinuvin 328, 900, 1130, 384, 292, 123, 144, manufactured by Ciba Specialty Chemicals. 622, 770, 292, Irgacor 252153, Irganox 1010, 1076, 1035, MD1024, lanthanide oxide, and the like.

(11. Dissolution aid)
The ink composition according to the present invention preferably contains a dissolution aid in addition to the above components.
The ink composition containing the ink composition, particularly when using a film-based non-ink-absorbing recording medium made of polyvinyl chloride, polyethylene terephthalate, polyethylene, polypropylene, or the like, is used when droplets of the ink composition are attached. Wetting and spreading are uniform, and a solid image has a characteristic that a clear and clear image with little shading unevenness and bleeding can be obtained.

  Examples of solubilizers include pyrrolidones such as N-methyl-2-pyrrolidone and 2-pyrrolidone, lactones such as γ-butyrolactone, sulfoxides such as dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, and the like. The imidazolidinones, ureas such as urea, thiourea and tetramethylurea can be preferably used. Of these, pyrrolidones and lactones are more preferable. The amount of the recording medium solubilizer may be appropriately determined, but is preferably about 0.1 to 30% by mass, more preferably about 0.1 to 10% by mass, and more preferably about 0.5 to 5% by mass. It is. Most preferably, it is the range of 1 mass%-3 mass%. For example, 2-pyrrolidone has a relatively high boiling point (245 ° C.), and if it is added in a large amount, it becomes difficult to dry the ink, so that the rub resistance when printing on a non-ink-absorbing recording medium may be reduced. .

(12. Physical properties of ink composition)
The pH of the ink composition is preferably neutral or alkaline, and more preferably in the range of 7.0 to 10.0. If the pH is acidic, the storage stability and dispersion stability of the ink composition may be impaired. In addition, problems such as corrosion of metal parts used in the ink flow path in the ink jet recording apparatus are likely to occur. The pH can be adjusted to neutral or alkaline using the pH adjusting agent described above.

  The viscosity of the ink composition is preferably in the range of 1.5 mPa · s to 15 mPa · s at 20 ° C. Within this range, ink ejection stability can be ensured in the first step described later.

  The surface tension of the ink composition is preferably 15 mN / m to 40 mN / m, and more preferably 20 mN / m to 30 mN / m at 25 ° C. Within this range, ink ejection stability can be ensured in the first step described later, and appropriate wettability with respect to a non-ink-absorbing or low-absorbing recording medium can be secured.

(13. Method for producing ink composition)
The ink composition according to the present embodiment can be obtained by mixing the materials described above in an arbitrary order and removing impurities by filtering or the like as necessary. Here, the colorant is preferably prepared in advance in a state of being uniformly dispersed in an aqueous medium and then mixed in view of ease of handling and the like.

  As a method for mixing the respective materials, a method in which the materials are sequentially added to a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer and stirred and mixed is preferably used. As a filtration method, centrifugal filtration, filter filtration, or the like can be performed as necessary.

(14. Inkjet recording method)
The ink jet recording method according to the present embodiment includes a first step of forming an image by discharging droplets of the ink composition described above onto a recording medium, and the recording at the time of the first step or after the first step. And a second step of drying the ink composition on the recording medium by heating the medium. Hereinafter, each step will be described in detail.

14-1. First Step The first step in the ink jet recording method according to the present embodiment is a step of forming an image by ejecting droplets of the ink composition described above onto a recording medium by an ink jet recording method.

  As the ink jet recording method, any method can be used as long as it is a method in which the above-described ink composition is ejected as droplets from a fine nozzle and the droplets are attached to a recording medium. As the ink jet recording method, for example, the following four methods can be mentioned.

  The first method is called an electrostatic attraction method. A strong electric field is applied between a nozzle and an acceleration electrode placed in front of the nozzle, and ink is continuously ejected from the nozzle in the form of droplets. Is a method in which a print information signal is applied to the deflection electrode while it is flying between the deflection electrodes and recorded, or an ink droplet is ejected corresponding to the print information signal without being deflected.

  The second method is a method in which ink droplets are forcibly ejected by applying pressure to the ink liquid with a small pump and mechanically vibrating the nozzle with a crystal resonator or the like. The ejected ink droplet is charged simultaneously with the ejection, and a printing information signal is given to the deflection electrode and recorded while the ink droplet flies between the deflection electrodes.

  The third method is a method using a piezoelectric element, in which a pressure and a print information signal are simultaneously applied to an ink liquid using a piezoelectric element, and ink droplets are ejected and recorded.

  The fourth method is a method in which the ink liquid is rapidly expanded in volume by the action of thermal energy, and the ink liquid is heated and foamed with a microelectrode in accordance with a print information signal, and ink droplets are ejected and recorded.

14-2. Second Step The second step in the ink jet recording method according to the present embodiment is a step of drying the ink composition on the recording medium at least during the first step and after the first step. By incorporating the second step, part or all of the liquid medium contained in the ink composition deposited on the recording medium is quickly evaporated and scattered, and the average particle size contained in the ink composition A film of first polymer particles having a heat distortion temperature of less than 100 ° C. is formed. Thereby, even on a non-ink-absorbing recording medium such as a plastic film having no ink absorbing layer, a high-quality image with little unevenness in density can be obtained in a short time, and a film made of resin is formed. As a result, the dried ink adheres to the recording medium and the image is fixed.

  The second step is not particularly limited as long as it is a method of promoting evaporation and scattering of the liquid medium present in the ink composition. As a method used in the second step, a method of applying heat to the recording medium at least during the first step and after the first step, a method of blowing air on the ink composition on the recording medium after the first step, and The method etc. which combine them are mentioned. Specifically, forced air heating, radiation heating, conduction heating, high frequency drying, microwave drying, and the like are preferably used.

  The temperature range for applying heat in the second step is not particularly limited as long as it can promote evaporation and scattering of the liquid medium present in the ink composition. Is 40 ° C to 90 ° C, more preferably in the range of 40 ° C to 80 ° C. When the temperature exceeds 100 ° C., defects such as deformation may occur depending on the type of the recording medium, which may hinder the conveyance of the recording medium after the second step, or may contract when the recording medium cools to room temperature. May fail.

  The heating time in the second step is not particularly limited as long as the liquid medium present in the ink composition can be evaporated and scattered, and a film of polymer particles can be formed. It can be set as appropriate in consideration of the printing speed.

(15. Non-absorbing or low-absorbing recording medium)
Any recording medium may be used as desired. Among these, in the ink jet recording method according to the present embodiment, a non-absorbing or low-absorbing recording medium other than plain paper can be suitably used. In the present specification, “non-ink-absorbing and low-absorbing recording medium” means “recording in which the water absorption from the start of contact to 30 msec ^1/2 in the Bristow method is 10 mL / m ² or less. Medium ". This Bristow method is the most popular method for measuring the amount of liquid absorbed in a short time, and is also adopted by the Japan Paper Pulp Technology Association (JAPAN TAPPI). For details of the test method, refer to Standard No. of “JAPAN TAPPI Paper Pulp Test Method 2000”. 51 "Paper and paperboard-Liquid absorbency test method-Bristow method".

  As a non-ink-absorbing recording medium, for example, a plastic film coated on a base material such as a plastic film or paper that is not surface-treated for ink jet printing (that is, not formed with an ink absorbing layer) is used. And those having a plastic film adhered thereto. Examples of the plastic here include polyvinyl chloride, polyethylene terephthalate, polycarbonate, polystyrene, polyurethane, polyethylene, and polypropylene. Examples of the ink-absorbing recording medium include main printing paper such as art paper, coated paper, and matte paper, and examples of the ink-absorbing recording medium include high-quality paper, plain paper, and recycled paper.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited at all by these Examples.

(16. Preparation of ink composition)
16-1. Preparation of pigment dispersion

  The pigment dispersion used in this example was prepared as follows. As a carbon black (CI Pigment Black 7 (PBk7)), 65 parts by mass of Color Black S170 (trade name: manufactured by Degussa Huls Co., Ltd.) is used as a styrene-acrylic acid-based dispersion resin, John Kuryl 611 (trade name: BASF Japan Co., Ltd.) 35 parts by mass, potassium hydroxide 1.70 parts by mass, 250 parts by mass of ultrapure water purified by the ion exchange method and reverse osmosis method were mixed and dispersed for 10 hours in a ball mill with zirconia beads. . The obtained dispersion undiluted solution was filtered through glass fiber filter paper GA-100 (trade name: manufactured by Advantech Toyo Co., Ltd.) to remove coarse particles, and the pigment concentration was adjusted to 15% by mass.

  When the particle size distribution of the obtained pigment dispersion was measured with Microtrac UPA150 (Nikkiso Co., Ltd.), the average particle size of the pigment was 117 nm.

16-2. Preparation of Ink Composition Using the pigment dispersion prepared as described above, ink compositions having different black material compositions were prepared using the material compositions shown in Tables 3 to 5. For each ink composition, the materials shown in Tables 3 to 5 are placed in a container, mixed and stirred for 2 hours with a magnetic stirrer, and then filtered through a membrane filter with a pore size of 10 μm to remove impurities such as dust and coarse particles. It was prepared by doing. The numerical values in Tables 3 to 5 all indicate mass%, and ion exchange water was added so that the total amount of ink was 100 mass%. The surfactant species are shown in Table 2.

Further, yellow ink (Pigment Yellow 74), cyan ink (Pigment Blue 15: 3), and magenta ink (Pigment Red 122) were prepared in the same manner.
In the table, StAc-EM is a styrene acrylic copolymer resin emulsion, PG is propylene glycol, 12BD is 1,2-butanediol, 12PD is 1,2-pentanediol, 12HD is 1,2-hexanediol, 3Me13BD Is 3-methyl-1,3-butanediol, Gly is glycerin, EHDG is diethylene glycol mono-2-ethylhexyl ether, EHG is ethylene glycol mono-2-ethylhexyl ether, BTG is triethylene glycol monobutyl ether, TEA is triethanolamine , PVC represents polyvinyl chloride, and PP represents polypropylene.

  In addition, KF-945 is a polysiloxane surfactant made from Shin-Etsu silicone, FZ-2123 is a polysiloxane surfactant made from Toray Dow Corning, and KF-6013 is a polysiloxane surfactant made from Shin-Etsu silicone. KF-354L is a polysiloxane surfactant made of Shin-Etsu Silicone, Surfynol 420 is an acetylene glycol surfactant made by Air Products and Chemicals, Inc., Surfynol 485 is Air Products and Chemicals, Inc. This is an acetylene glycol surfactant, and BYK348 is a polysiloxane surfactant manufactured by Big Chemie Japan.

  In Tables 4 and 5, Surfactant A is a polysiloxane surfactant. In the above formula (1), R is a methyl group, a is an integer of 9 to 13, and m is 2. A compound wherein n is an integer of 1 to 2, R is a hydrogen atom, a is an integer of 7 to 11, m is an integer of 30 to 50, and n is 3 to 3. The compound which is an integer of 5 was prepared by mixing at 3: 7.

  Surfactant B is a polysiloxane surfactant, and in the above formula (1), R is a methyl group, a is an integer of 9 to 13, m is an integer of 2 to 4, a compound in which n is an integer of 1 to 2, a compound in which R is a hydrogen atom, a is an integer of 7 to 11, m is an integer of 30 to 50, and n is an integer of 3 to 5. , Were prepared by mixing 1: 9.

  Surfactant C is a polysiloxane surfactant AW-3 (manufactured by Shin-Etsu Chemical Co., Ltd.) and polysiloxane surfactant X-22-6551 (manufactured by Shin-Etsu Chemical Co., Ltd.) in a mass ratio of 9 : 1 mixed.

  Surfactant D is a polysiloxane surfactant, and in the above formula (1), R is a methyl group, a is an integer of 9 to 13, m is an integer of 2 to 4, It is a compound in which n is an integer of 1 to 2.

(17. Evaluation of ink composition)
[Evaluation 1. Evaluation of uneven density of recorded material]
Ink-absorbing high-quality paper (trade name “55PW8R”, manufactured by Lintec Co., Ltd.), low-absorptive printing paper (trade name “POD gloss coat”, manufactured by Oji Paper Co., Ltd.), non-ink-absorbing polypropylene A film (trade name “SY51M 2.6 mil. PPWhite TC RP37 2.2 mil. HIGH DENITY WHITE”, manufactured by UPM RAFLATA, hereinafter abbreviated as “SY51M”) was used. In addition, as an ink jet recording type printer, an ink jet printer (product name “PX-G930”, manufactured by Seiko Epson Corporation, nozzle resolution: 180 dpi) in which a heater capable of changing the temperature is attached to the paper guide unit was used.

An ink jet printer was filled with one of the ink compositions, and an image was recorded on one of the recording media. As the image pattern, a filled pattern that can be recorded in 10% increments with a duty ratio in the range of 50 to 100% at a resolution of 720 dpi and 720 dpi was used. As the recording condition, the heater setting of the printer was set to “setting at which the temperature of the recording surface is 40 ° C.”. Furthermore, a drying process was performed by blowing air at a temperature of 80 ° C. on the recorded matter during and immediately after recording. The intensity of the air blowing was such that the wind speed on the surface of the recording medium was about 2 to 5 m / sec. The blowing time immediately after recording was 1 minute. The density unevenness of the recorded material when recorded under such conditions was visually confirmed. The evaluation criteria are shown below.
A: Uneven density was not observed even at a duty of 80% or more.
B: No uneven density was observed up to a duty of 70%.
C: Density unevenness was not observed up to a duty of 60%.
D: Density unevenness was observed even at a duty of 60% or less.

[Evaluation 2. Storage stability of ink composition]
Each ink composition shown in Tables 3 to 5 was sealed in a sample bottle and allowed to stand in a 60 ° C. environment for 2 weeks. The storage stability of the ink composition was evaluated based on the change in the viscosity of the ink after standing. The evaluation criteria are shown below, and the evaluation results are shown in Tables 3 to 5.

<Viscosity change>
A: Change rate is less than ± 5% compared to the viscosity immediately after preparation.
B: Change rate is ± 5% or more and less than ± 10% compared to the viscosity immediately after preparation.
C: Change rate is ± 10% or more and less than ± 20% compared to the viscosity immediately after preparation.
D: The rate of change is ± 20% or more compared to the viscosity immediately after preparation.

[Evaluation 3. Head clogging]
Each ink composition shown in Tables 3 to 5 was filled in a head of an ink jet printer (product name “PX-G930”, manufactured by Seiko Epson Corporation, nozzle resolution: 180 dpi) which is an ink jet recording type printer. After filling, print a nozzle check pattern to confirm that there is no filling failure or nozzle clogging, and then remove the printer head cap (that is, the head nozzle surface is easy to dry) to 25 ° C / It was left for one week in an environment of 40-60% RH. After leaving, a cleaning operation was performed as necessary, a nozzle check pattern was printed, and the discharge state of the nozzle was observed to evaluate the clogging of the ink jet head of the ink composition. The evaluation criteria are shown below, and the evaluation results are shown in Tables 3 to 5.

A: The ink composition was normally discharged from all nozzles within 3 cleaning operations.
B: The ink composition was normally ejected from all nozzles within the range of 4 to 6 cleaning operations.
C: The ink composition was normally ejected from all nozzles within the range of 7 to 10 cleaning operations.
D: It was necessary to perform the cleaning operation 11 times or more before the ink composition was normally ejected from all the nozzles, or there was a nozzle that was not ejected normally even if the cleaning operation was performed 11 times or more.

[Evaluation 4. Fixability]
In the same manner as in Evaluation 1, after the recorded matter was printed, it was left in a laboratory at room temperature (25 ° C.) for 5 hours, and then the recording surface was subjected to a Gakushin type friction fastness tester (product name “AB-301”). ”, Manufactured by Tester Sangyo Co., Ltd.), the fixing property was evaluated by confirming the peeled state of the recording surface and the state of ink transfer to the cotton cloth when rubbed 10 times with a cotton cloth under a load of 200 g. The evaluation criteria are shown below, and the evaluation results are shown in Tables 3 to 5.

A: Even after rubbing 10 times, no ink peeling or ink transfer to the cotton cloth was observed.
B: After rubbing 10 times, ink peeling or ink transfer to a cotton cloth was observed.
C: Ink peeling or ink transfer to cotton cloth was observed before rubbing 10 times.

Claims (5)

An ink composition recorded on a non-ink-absorbing or low-absorbing recording medium,
At least a coloring material, a lipophilic polysiloxane surfactant having an HLB value of 2 to 8, a hydrophilic polysiloxane surfactant having an HLB value of 9 to 20, and a boiling point of 180 to 1 atmosphere. alkyl polyols is in the range of 230 ° C., HLB value calculated by the Davis method comprises a glycol ether in the range of 4.2 to 8.0, and water, (but, at one atmosphere An ink composition characterized by not containing 1.0% by mass or more of an alkyl polyol having a boiling point of 280 ° C. or higher .   The mass ratio of the lipophilic polysiloxane surfactant content / the hydrophilic polysiloxane surfactant content in the ink composition is 1/20 or more and 2/1 or less. The ink composition according to claim 1.   The ink composition according to claim 1 or 2, wherein the content of the hydrophilic polysiloxane surfactant in the ink composition is larger than the content of the lipophilic polysiloxane surfactant. object.   The alkyl polyols are C4-7 1,2-linear alkyldiols, and the relationship between the mass of C4-7 1,2-linear alkyldiols / mass with the glycol ether is 1 / The ink composition according to any one of claims 1 to 3, wherein the ratio is more than 1 and 20/1 or less. An inkjet recording method for recording an image on a non-ink-absorbing or low-absorbing recording medium using the ink composition according to any one of claims 1 to 4,
A droplet of the ink composition is ejected from a nozzle onto the recording medium to form the image, and the recording medium is heated to dry the ink composition on the recording medium and is contained in the ink composition. An ink jet recording method comprising: evaporating and scattering a liquid medium to be formed, forming a resin film on the recording medium, and fixing the image.