JP2010221669A - Inkjet treatment liquid, inkjet recording method, and recorded matter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inkjet treatment liquid which enables inkjet discharge, and has tight contact and adhesiveness with an ink-nonabsorbable recording medium, transparency, drying property after discharge, bleeding suppressing property on a recorded image and preservation stability. <P>SOLUTION: The inkjet treatment liquid including at least a cationic polyurethane and a modified polyallylamine is characterized in that the modified polyallylamine is a copolymer of a N,N-dimethylarylamine and a carbamoylated allylamine represented by formula (1). In formula (1), R<SB>1</SB>, R<SB>2</SB>independently show alkyl groups having 1 to 4 carbon atoms respectively, p, q show independently show integers of one or more respectively, and r shows an integer of 0 or more. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a coating suitable for a non-ink-absorptive film material, and more particularly to an ink jet processing liquid, an ink jet recording method using the processing liquid, and a recorded matter.

The ink jet recording method is a method for recording images, characters, etc. by ejecting fine droplets from nozzles and adhering them to various recording media, and it is easy to increase the speed, reduce noise, and make colors. In addition, there is a feature that non-contact printing is possible with respect to a recording medium, and it is used for various applications as a recording apparatus for various images.
Especially for industrial use, it is possible to obtain images that are close to multicolor printing by the plate-making method and silver salt photography method for images formed by the full-color ink jet recording method. It is cheaper than multi-color printing, and its use is expanding recently.
Among these industrial applications, the ability to print a wide variety of small numbers of copies makes it possible to expand the use of labels, stickers, tags, etc. for product descriptions, designs, names, and manufacturer names. is doing.

However, recording media generally used for such labels, seals, tags, etc. are non- (hard) absorbing film media, specifically polyethylene terephthalate from the viewpoint of glossiness and texture, required durability, etc. (PET), polyvinyl chloride (PVC), polypropylene (PP), polyethylene (PE), etc., or ink such as printing paper is not absorbed (is difficult), and is not usually suitable for an ink jet recording system.
Therefore, usually, a dedicated medium having ink jet recording characteristics is prepared by providing an ink receiving layer in advance on the surface of such a non- (hard) absorbing system medium, and used for the label, seal, tag and the like as described above. Inkjet recording is used.

  The present invention incorporates, for example, a process of applying the treatment liquid onto a recording medium by inkjet discharge as a pre-process of inkjet recording, and as a series of systems, a film system (PET, (PVC, PP, PE) Media and the like can be printed by an ink jet printer.

  The present inventor has found that polyurethane is optimal as a resin having adhesiveness and adhesiveness to various film media, and by adding polyurethane to the treatment liquid, a receiving layer having adhesiveness to the film media is obtained. Succeeded. When printing is performed on the receiving layer formed of the treatment liquid to which this polyurethane is added by an ink jet recording method, the discharged ink is permeated and diffused in each direction after landing on the polyurethane receiving layer, and bleeding occurs (fixing). Insufficient printability) and sufficient print image quality could not be obtained.

  Next, the present inventor examined the use of a cationic polyurethane imparted with reactivity with ink by cationically treating the polyurethane. Such a cationic polyurethane receptor layer was effective to prevent bleeding to some extent, but was not sufficiently fixable. That is, there is a technical limit to the amount of cationic treatment of polyurethane, and the reactivity with the ink is not sufficient. For example, if the coating amount of the treatment liquid is increased in order to improve the reactivity with the ink (the coating amount per unit area is 10 g / m 2 or more), the bleeding can be suppressed. However, in this case, the drying property of the treatment liquid after coating on the film becomes insufficient, making it difficult to use as a series of systems.

  In order to ensure the reactivity to fix the ink, it is effective to use highly cationic polyvalent metal ions or cationic polyallylamine. When left in a state where it is mixed with polyurethane, it gelled, and a treatment liquid satisfying sufficient storage stability and ejection stability could not be obtained.

Therefore, the characteristics required for the “treatment liquid” that is the object of the present invention include the following points.
1) It can be applied on film media and has adhesion and adhesion to film media.
2) It has a function as a receiving layer that absorbs printed ink after coating and drying on a film medium and a function as a fixing layer that reacts with ink.
3) After application on a film medium, it has a drying property at a practical level, while ensuring a stable ejection property in normal printing and a clogging recovery property after being left standing.
4) The processing solution should have practically no deterioration in properties such as physical properties, that is, storage stability.

However, in the conventional technique, a treatment liquid that satisfies all of the above characteristics has not been obtained.
In Patent Document 1, for the purpose of improving ozone resistance while suppressing the occurrence of image bleeding, at least a water-soluble metal salt comprising a cationic polyurethane and a divalent water-soluble magnesium salt and / or a water-soluble calcium salt is used. In addition, an ink jet recording medium is disclosed which further contains boric acid as a water-soluble binder and polyvinyl alcohol as a crosslinking agent.
This technique is intended to improve the characteristics of an image by improving the recording medium itself, and is not a treatment liquid for pre-processing a recording medium by inkjet ejection as described above, but is suitable for inkjet ejection in the first place. It was not.

JP 2007-196395 A

  INDUSTRIAL APPLICABILITY The present invention is an inkjet that can be ejected by inkjet, has adhesion and adhesion to non-ink-absorbing recording media, transparency, drying after ejection, and bleeding suppression of recorded images, and has storage stability. It aims at providing a processing liquid.

As a result of diligent research, the present inventors have found that an inkjet treatment liquid containing cationic polyurethane and modified polyallylamine, wherein the modified polyallylamine is represented by the following general formula (1): ), Or (a), (b), and (c), the ink-jet processing liquid obtained the knowledge that the above-mentioned object can be achieved, and has reached the present invention.
That is, the present invention has the following configuration.

  1. An inkjet processing liquid containing at least a cationic polyurethane and a modified polyallylamine, wherein the modified polyallylamine is represented by the following general formula (1): N, N-dimethylallylamine and carbamoylated allylamine Inkjet treatment liquid characterized by being a co-reactant with

However, R ₁ and R ₂ each independently represent an alkyl group having 1 to 4 carbon atoms, p and q each independently represent an integer of 1 or more, and r represents an integer of 0 or more.

2. Furthermore, the weight average molecular weight of the said modified polyallylamine is 5000 or less, The inkjet processing liquid of Claim 1 characterized by the above-mentioned.
3. Furthermore, the inkjet processing liquid of the said 1 or 2 containing the diacetylene tetraol represented by General formula (2) shown by following Chemical formula 2, and long-chain alkyl glycol ethers.

In the general formula (2), R ₁ and R ₂ each independently represents an alkyl group having 1 to 8 carbon atoms, R ₃ each independently represents a hydrogen atom or a methyl group, and —O—R ₄ — represents Independently represents any one of oxyethyl, oxypropyl, and oxybutyl, R ₅ represents a divalent linking group, and k, l, m, and n each represents an integer of 1 to 100.

4). Furthermore, the inkjet processing liquid in any one of said 1-3 containing 1, 2- hexanediol.
5). Furthermore, the inkjet processing liquid in any one of said 1-4 containing a silicone type surfactant.
6). An inkjet recording method for forming a print image by ejecting droplets of inkjet recording ink onto a recording medium treated with the inkjet processing liquid according to any one of 1 to 5 above.
7). 7. A recorded matter printed by the inkjet recording method described in 6 above.

(Embodiment)
Next, the present invention will be described in more detail based on preferred embodiments thereof.
As described above, the ink jet processing liquid of the present embodiment is characterized by containing a cationic polyurethane and a modified polyamine.
Since the present embodiment is configured as described above, inkjet discharge is possible, and adhesion and adhesion to non-ink-absorbing recording media, transparency, dryness after discharge, and bleeding suppression of recorded images. And storage stability can be provided.
There is no limitation in particular as a cationic polyurethane used for the processing liquid of this embodiment, A well-known thing can be selected suitably and can be used.
Examples thereof include cationic polyurethanes obtained by the following preparations (1) to (2) and the like, and in particular, a composition in which cationic polyurethane is dispersed in water, that is, an aqueous dispersion is preferable.

  The preparation of the cationic polyurethane comprises (1) using a polyester polyol (B1) as a polyol for urethane reaction with the polyisocyanate (A) and a urethane prepolymer using a chain extender (C) having a tertiary amino group. A cationic polyurethane composition is prepared by neutralizing part of this tertiary amino group with an acid or quaternizing with a quaternizing agent to make the amine value in the range of 1 to 40 (KOHmg / g). Can be obtained. (2) Polycarbonate polyol (B2), chain extender (C) having a tertiary amino group, and polyalkylene oxide (D) containing 50% by mass or more of an ethylene oxide chain, the polyisocyanate (A) A cationic polyurethane can be obtained by preparing a urethane prepolymer using, and neutralizing a tertiary amino group introduced by the chain extender (C) with an acid or quaternizing with a quaternizing agent. . By obtaining this cationic polyurethane in a form dispersed in water, it can be obtained as an aqueous dispersion.

Hereinafter, the preparation (1) will be described.
As the polyisocyanate (A), conventionally used polyisocyanates such as aliphatic, alicyclic, aromatic, and araliphatic can be used.

  Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, dodecamethylene diisocyanate, 1,4-butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, Examples include lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, and 3-methylpentane-1,5-diisocyanate.

  Specific examples of the alicyclic polyisocyanate include isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3-bis (isocyanate methyl). A cyclohexane etc. can be mentioned.

  Specific examples of the aromatic polyisocyanate include tolylene diisocyanate, 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4, Examples include 4′-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, and the like.

Specific examples of the araliphatic polyisocyanate include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, α, α, α, α-tetramethylxylylene diisocyanate and the like.
These polyisocyanates may be used alone or in a combination of two or more.

As the polyester polyol (B1), those composed of various polycarboxylic acids and polyols can be used, but depending on the dicarboxylic acid composed of an aliphatic dibasic acid and an aromatic dibasic acid, and an aliphatic glycol. What is comprised is more preferable at the point that adhesiveness becomes high.
Examples of aliphatic dibasic acids include malonic acid, succinic acid, tartaric acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, alkyl succinic acid, linolenic acid, maleic acid, fumaric acid, Examples thereof include mesaconic acid, citraconic acid, itaconic acid, and glutaconic acid, and reactive derivatives such as acid anhydrides, alkyl esters, and acid halides. These aliphatic dicarboxylic acids can be used alone or in combination of two or more. Examples of the aromatic dibasic acid include phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, tetrahydro Examples thereof include phthalic acid and the like, or reactive derivatives thereof such as acid anhydrides, alkyl esters, and acid halides. These aromatic dicarboxylic acids can be used alone or in combination of two or more.

  Examples of the aliphatic glycol include ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 1,6-hexanediol, A propylene glycol etc. can be illustrated and these can be used individually or in combination of 2 or more types.

The chain extender (C) having a tertiary amino group in the molecule is used for introducing the tertiary amino group into the urethane prepolymer. Examples of such chain extenders (C) include N-alkyldialkanolamines such as N-methyldiethanolamine and N-ethyldiethanolamine, N-alkyldiaminoalkylamines such as N-methyldiaminoethylamine and N-ethyldiaminoethylamine, A triethanolamine etc. can be mentioned. These chain extenders (C) having a tertiary amino group can be used alone or in combination of two or more.
The addition amount of the chain extender (C) in the preparation (1) is 5% by mass to 20% by mass with respect to the total of the polyisocyanate (A), the polyester polyol (B1), and the chain extender (C). It is more preferable. If the amount of the chain extender (C) added is less than 5% by mass, the number of tertiary amino groups to be introduced decreases, and the tendency for the adhesion and water resistance of the ink to decrease appears. Moreover, when there is more addition amount of chain extender (C) than 20 mass%, it will become difficult to acquire the effect which improves adhesiveness and durability corresponding to addition amount, and chain extender (C) like this. There is a tendency that a urethane prepolymer having an increased amount of added is difficult to prepare.

  In this embodiment, the free NCO at the end of the urethane prepolymer generated by the reaction of the polyisocyanate (A), the polyester polyol (B1), and the chain extender (C) having a tertiary amino group in the molecule. The content is more preferably in the range of 1% by mass to 5% by mass. When the content of this terminal free NCO is less than 1% by mass, it is not preferable because preparation of the urethane prepolymer becomes difficult. Moreover, when there is more content of terminal free NCO than 5 mass%, since the cohesion force of the water-based polyurethane resin obtained becomes high too much, it is unpreferable at the point of adhesiveness.

In the present embodiment, a cationic urethane prepolymer in which a tertiary amino group introduced by the chain extender (C) and a part thereof are neutralized with an acid or quaternized with a quaternizing agent is prepared. When the tertiary amino group and a part thereof are neutralized with an acid, the acids include formic acid, acetic acid, propionic acid, butyric acid, lactic acid, malic acid, malonic acid, adipic acid and other organic acids, and hydrochloric acid, phosphoric acid, Mention may be made of inorganic acids such as nitric acid. These acids can be used alone or in combination of two or more.
In addition, when quaternizing a tertiary amino group and a part thereof with a quaternizing agent, quaternizing agents include alkyl halides such as benzyl chloride and methyl chloride, sulfate esters such as dimethyl sulfate and diethyl sulfate. Etc. These quaternizing agents can be used in combination of two or more in addition to being used alone.

  As described above, the tertiary amino group and a part thereof are not completely neutralized or quaternized, and only a part of the tertiary amino group is neutralized or quaternized. The amount of the tertiary amino group remaining without being neutralized or quaternized is an amount such that the amine value of the cationic polyurethane is 1 to 40 (KOHmg / g). It can be adjusted by quaternization.

Next, the preparation (2) will be described.
The polyisocyanate (A) used in the preparation (2) is the same as the polyisocyanate (A) used in the preparation (1) and is as described above.

  As said polycarbonate polyol (B2) used for preparation (2), it is obtained by reaction of glycols, such as 1, 4- butanediol, 1, 6- hexanediol, diethylene glycol, and diphenyl carbonate and phosgene, for example. Compounds and the like. These polycarbonate polyols can be used alone or in combination of two or more.

  The addition amount of the polycarbonate polyol (B2) is in the range of 40% by mass to 80% by mass with respect to the total of the polyisocyanate (A), the polycarbonate polyol (B2), the chain extender (C), and the polyalkylene oxide (D). It is preferable that When the addition amount of the polycarbonate polyol (B2) is less than 40% by mass, the durability of the resulting urethane resin is lowered, and the tendency to be inferior in adhesion to film media is not preferable. On the other hand, if it is more than 80% by mass, the cohesive force of the resulting cationic polyurethane becomes insufficient and the durability is also lowered, which is not preferable.

  In this embodiment, the polyalkylene oxide (D) containing an ethylene oxide chain can be used as a constituent component of polyurethane. This polyalkylene oxide (D) is used to increase the affinity with the ink to be printed. Examples of such polyalkylene oxide (D) include ethylene oxide, a copolymer of ethylene oxide and propylene oxide, and the like. These polyalkylene oxides (D) can be used alone or in combination of two or more. When the content of the ethylene oxide chain in the polyalkylene oxide (D) is less than 50% by mass, the affinity with the ink may be lowered.

  The addition amount of the polyalkylene oxide (D) is 3% by mass to 10% by mass with respect to the total of the polyisocyanate (A), the polycarbonate polyol (B2), the chain extender (C), and the polyalkylene oxide (D). Preferably there is. If the addition amount of the polyalkylene oxide (D) is lower than 3% by mass, the affinity with the ink becomes insufficient, such being undesirable. On the other hand, when the amount of polyalkylene oxide (D) added is more than 10% by mass, the water resistance decreases, which is not preferable.

In the preparation (2), the chain extender (C) used is the same as in the preparation (1).
The addition amount of the chain extender (C) used in the preparation (2) is based on the total of the polyisocyanate (A), the polycarbonate polyol (B2), the chain extender (C), and the polyalkylene oxide (D). It is preferable that it is 5 mass%-15 mass%. When the amount of the chain extender (C) added is less than 5% by mass, the tertiary amino groups to be introduced are decreased, and the adhesion tends to be lowered. Moreover, when there is more addition amount of chain extender (C) than 15 mass%, since the effect which improves the adhesiveness corresponding to addition amount will not be acquired, it is unpreferable.
Acid and quaternizing agent when the tertiary amino group introduced by the chain extender (C) used in the preparation (2) and a part thereof are neutralized with an acid or quaternized with a quaternizing agent Is the same as in the case of the preparation (1).

In the preparation of the above (1) and (2), the cationic urethane prepolymer obtained by neutralizing or quaternizing the tertiary amino group and a part thereof is a polyamine compound (D1) as needed when dispersed in water. ) May be used. Examples of polyamine compounds that can be used include, for example, amino groups such as hydrazides such as ethylenediamine, propylenediamine, diethylenetriamine, hexylenediamine, triethylenetetramine, tetraethylenepentamine, isophoronediamine, piperazine, diphenylmethanediamine, hydrazine, and adipic acid dihydrazide. And a compound having two or more.
In the preparation of (1) and (2), a polyol having 3 or more hydroxyl groups may be further added. When a polyol having 3 or more hydroxyl groups is added, adhesion to film media can be improved. However, it is necessary to use the obtained cationic polyurethane as long as the water dispersibility is not impaired. Examples of such polyols include sorbitol, 1,2,3,6-hexanetetraol, 1,4-sorbitan, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, trimethylol. Ethane, trimethylolpropane, pentaerythritol and the like can be mentioned, and these can be used alone or in combination of two or more.
In the preparation of the above (1) and (2), the cationic urethane prepolymer obtained by neutralizing or quaternizing the tertiary amino group or part thereof as described above is then dispersed in water, The cationic polyurethane used in the embodiment and the dispersion thereof are obtained.

For the cationic polyurethane, the resins described in paragraph numbers [0006] to [0048] of JP-A No. 2002-30781 and paragraph numbers [0006] to [0053] of JP-A No. 2002-307812 are used in detail. Can do.
As the cationic polyurethane, commercially available products can be used, and as the commercially available products of the cationic polyurethane, “Hydran CP-7010”, “Hydran CP-7020”, “Hydran CP-7030”, “Hydran CP-7040” can be used. "," Hydran CP-7050 "," Hydran CP-7060 "," Hydran CP-7610 "(trade name, manufactured by Dainippon Ink & Chemicals, Inc.)," Superflex 600 "," Superflex 610 "," Super "Flex 620", "Superflex 630", "Superflex 640", "Superflex 650" (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), "Urethane emulsion WBR-2120C", "Urethane emulsion WBR-2122C" ( Product name, Taisei It can be used § in-Chemical Co., Ltd.), and the like.
The content of the cationic polyurethane is preferably 0.5 wt% to 15 wt%, more preferably 1 wt% to 10 wt%, and even more preferably 2 wt% to 6 wt% in the treatment liquid. .

  The modified polyallylamine contained in the liquid composition according to the present embodiment comprises a repeating unit represented by the following general formula (1) represented by the following chemical formula 3, that is, a co-polymer of N, N-dialkylallylamine and carbamoylated allylamine. Is the basic structure.

However, R ₁ and R ₂ each independently represent an alkyl group having 1 to 4 carbon atoms, p and q each independently represent an integer of 1 or more, and r represents an integer of 0 or more.
R ₁ and R ₂ are preferably the same type of alkyl group, and examples include a methyl group, an ethyl group, a propyl group, and a butyl group, but a methyl group is preferred. R ₃ represents an alkyl group having 1 to 12 carbon atoms or an aryl group. When R ₃ is an alkyl group having 1 to 12 carbon atoms, a linear alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group is preferable. Examples of the aryl group having 1 to 12 carbon atoms include a phenyl group, an o-tolyl group, and an m-tolyl group. A p-tolyl group can be exemplified.
Further, p / (q + r) is preferably 5/95 to 95/5, more preferably 10/90 to 90/10, and particularly preferably 20/80 to 80/20. At this time, the degree of alkoxycarbonylation (or allyloxycarbonylation) q / (q + r) is preferably 0.6 to 1 from the viewpoint of the solubility and stability of the modified polyallylamine according to this embodiment in an organic solvent. .9 to 1 is more preferable, and 0.95 to 1 is particularly preferable. The proportion of the repeating unit (a) is preferably 5% to 95%, more preferably 10% to 90%, and particularly preferably 20% to 80% with respect to the total number of monomers constituting the modified polyallylamine. At this time, the degree of carbamoylation, that is, the ratio of (c1) to the total number of repeating units (b) and (c1) is preferably 60% to 100% from the viewpoint of the solubility and stability of the modified polyallylamine, and 90% ~ 100% is more preferable, and 95% to 100% is particularly preferable.

  The above copolymer of N, N-dialkylallylamine and allylamine can be synthesized, for example, by the method described in WO00 / 21901. Examples of the N, N-dialkylallylamine monomer unit contained in the copolymer include N, N-dimethylallylamine, N, N-diethylallylamine, N, N-dipropylallylamine, and N, N-dibutylallylamine. . Also, N, N-dimethylallylamine is preferably used because of the high solubility of the modified product.

  The weight average molecular weight of such a copolymer is 5,000 or less, more preferably 200 to 3,000, and particularly preferably 500 to 2,000. When the molecular weight is in the above range, the resulting modified polyallylamine dissolves well in the solvent constituting the ink, and the attacking property to the parts used in the ink jet recording apparatus is suppressed, so that the ink flow path component can be It does not attack and is preferable.

  In the present embodiment, the content of the modified polyallylamine may be appropriately determined from the viewpoints of reactivity with ink, storage stability of the processing liquid, and ejection stability, but according to a preferred aspect of the present embodiment. In the liquid composition, it is preferably 0.1 wt% to 30 wt%, more preferably 0.1 wt% to 10 wt%, still more preferably 0.5 wt% to 5 wt%.

  In addition, the treatment liquid of this embodiment can use long-chain alkyl glycol ethers for the purpose of improving the wettability to the film media. Examples of the long-chain alkyl glycol ethers include alkyl glycol ethers having 5 to 8, preferably 6 alkyl chains.

  Specific examples of such long-chain alkyl glycol ethers include, for example, ethylene glycol mono n-pentyl ether, ethylene glycol mono iso-pentyl ether, ethylene glycol mono neopentyl ether, ethylene glycol mono n-hexyl ether, ethylene glycol Monoiso-hexyl ether, diethylene glycol mono n-pentyl ether, diethylene glycol mono iso-pentyl ether, diethylene glycol mono neopentyl ether, diethylene glycol mono n-hexyl ether, diethylene glycol mono iso-hexyl ether, triethylene glycol mono n-pentyl ether, tri Ethylene glycol monoiso-pentyl ether, triethylene glycol mononeope Tyl ether, triethylene glycol mono n-hexyl ether, triethylene glycol mono iso-hexyl ether, propylene glycol mono n-pentyl ether, propylene glycol mono iso-pentyl ether, propylene glycol mono neopentyl ether, propylene glycol mono n-hexyl ether , Propylene glycol mono iso-hexyl ether, dipropylene glycol mono n-pentyl ether, dipropylene glycol mono iso-pentyl ether, dipropylene glycol mono neopentyl ether, dipropylene glycol mono n-hexyl ether, dipropylene glycol mono iso- Hexyl ether, tripropylene glycol mono n-pentyl ether, tripropylene Recall mono iso-pentyl ether, tripropylene glycol mono neopentyl ether, tripropylene glycol mono n-hexyl ether, tripropylene glycol mono iso-hexyl ether, diethylene glycol mono-2-ethylhexyl ether, triethylene glycol mono-2-ethylhexyl ether And tetraethylene glycol mono-2-ethylhexyl ether. These glycol ethers may be added alone or in combination of two or more.

  In particular, ethylene glycol mono n-hexyl ether, diethylene glycol mono n-hexyl ether, triethylene glycol mono n-hexyl ether, propylene glycol mono, in terms of good wettability to the film and good drying properties after application to film media. n-Butyl ether, dipropylene glycol mono n-butyl ether, and tripropylene glycol mono n-butyl ether are preferable, and among them, diethylene glycol has the best balance in terms of wettability to a film, drying property after coating, and water solubility Mono n-hexyl ether.

  The content of the long-chain alkyl glycol ether is preferably 8% by weight or less, more preferably 4% by weight or less in the treatment liquid. If it exceeds 10% by weight, the long-chain alkyl glycol ether is difficult to evaporate, the drying characteristics after applying the treatment liquid to the film media are deteriorated, and the water solubility is lowered, so that it is difficult to dissolve in the treatment liquid. .

In the treatment liquid of this embodiment, diacetylene tetraol represented by the general formula (2) can be used in order to greatly improve the wettability to the film media.
As the diacetylene tetraol represented by the general formula (2), for example, a commercially available product of “Surfinol MD-20” (trade name, manufactured by Air Products and Chemicals Inc.) can also be used.

  The diacetylene tetraol has a great effect on improving the wettability of the treatment liquid with respect to the film media. On the other hand, it is difficult to dissolve in water, and a dissolution aid is required when added to the treatment liquid. The long-chain alkyl glycol ethers described above are effective as the solubilizing agent for diacetylene tetraol. Particularly, ethylene glycol mono n-hexyl ether, diethylene glycol mono n-hexyl ether, triethylene glycol mono n -Hexyl ether, propylene glycol mono n-butyl ether, dipropylene glycol mono n-butyl ether, tripropylene glycol mono n-butyl ether are balanced in terms of the effect as a solubilizer, wettability to the film, and drying properties after coating Is good.

  The content of the diacetylene tetraol is preferably 0.01% to 0.6% by weight, more preferably 0.05% to 0.3% by weight in the treatment liquid.

  In the treatment liquid of the present embodiment, the long-chain alkyl glycol ether as a solubilizing agent in water, or in terms of improving the wettability of the treatment liquid to the film media, or improving the clogging durability of the treatment liquid. From the point of view, alkanediol can be used. Examples of alkanediols include alkanediols such as water-soluble 1,2-alkanediols and water-soluble both-end alkanediols.

  As the water-soluble 1,2-alkanediol, an optionally branched 1,2-alkanediol having 5 or 6 carbon atoms is preferable. 4-methyl-1,2-pentanediol, 1,2-pentane Examples thereof include diol, 3,3-dimethyl-1,2-butanediol, and 1,2-hexanediol. Among these, 1,2-hexanediol is particularly preferably used as a solubilizing agent for long-chain alkyl glycol ethers in water from the viewpoint of further improving the clogging durability of the treatment liquid.

  The water-soluble 1,2-alkanediol is preferably 1% by weight to 10% by weight and more preferably 2% by weight to 8% by weight with respect to the entire treatment liquid. If it exceeds 15% by weight, it is difficult to evaporate, and the treatment liquid applied to the film media is difficult to dry.

As the water-soluble both-end alkanediol, it is preferable to use those having both-end alkanediols having 3 to 10 carbon atoms which may have a branch. 1,3-propanediol, 1,4-butanediol 1,5-pentanediol, 1,6-hexanediol and the like.
The water-soluble both-end alkanediol is preferably contained in an amount of 1% by weight to 10% by weight, more preferably 2% by weight to 8% by weight, based on the entire treatment liquid. By setting it as this range, it becomes easy to achieve both clogging properties and drying properties of the treatment liquid applied to the film media.

  Further, in the present embodiment, a 1.2-alkanediol having 5 to 10 carbon atoms and / or 1 having 3 to 10 carbon atoms, to which a polyoxyethylene chain and / or a polypropylene chain is added as a penetrating solvent. .2-Alkanediol and / or lactams and / or lactones may be included.

Moreover, the processing liquid of this embodiment can contain a silicone type surfactant further as needed.
Specific examples of silicone surfactants include SH3746, SH3748, SH3749, SH3771, SH8400, SH8410, SH8427, SH8700 (trade name, manufactured by Toray Dow Corning Co., Ltd.), TSF4440, TSF4441, TSF4452 (tradename, momentary).・ Performance Materials Japan LLC), BYK-300, BYK-302, BYK-307, BYK-325, BYK-331, BYK-333, BYK-341, BYK-345, BYK-346, BYK- 347, BYK-348, BYK-375, BYK-378, BYK-UV3500 (trade name, Big Chemie Japan Co., Ltd.) and the like.

Among such silicone surfactants, polyorganopolysiloxane surfactants are particularly effective in improving wettability to film media and the like due to a reduction in surface tension of the treatment liquid.
Moreover, it is more preferable that the organopolysiloxane-based surfactant comprises one or more compounds represented by the general formula (3) represented by the following chemical formula 4.

In Chemical Formula 4, R represents a hydrogen atom or a methyl group, a represents an integer of 7 to 11, m represents an integer of 20 to 70, and n represents an integer of 2 to 5.
By using such a specific organopolysiloxane surfactant, it is effective for smoothing the unevenness of the coated surface, particularly when the treatment liquid is applied to film media or the like.

Such a silicone-based surfactant is preferably contained in the treatment liquid according to the present embodiment in an amount of 0.05 to 3% by weight, more preferably 0.1 to 2% by weight. In particular, when the above-described surfactant in which R is a methyl group is used, it is preferable to increase the content as compared with the case in which the above-described surfactant in which R is H is used.
The treatment liquid according to the present embodiment further includes other surfactants, specifically, a fluorosurfactant, an acetylene glycol surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, and the like. It may be added.

  Among these, acetylene glycol surfactants include, for example, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6- Diol, or 3,5-dimethyl-1-hexyn-3ol, 2,4-dimethyl-5-hexyn-3-ol and the like can be mentioned. Commercially available acetylene glycol surfactants can also be used. For example, Olphine E1010, STG, Y (trade name, manufactured by Nissin Chemical Co., Ltd.), Surfynol 61, 104, 82, 465, 485 or TG (Trade name, manufactured by Air Products and Chemicals Inc.).

The treatment liquid according to the present embodiment contains water as a solvent. It is preferable to use pure water or ultrapure water such as ion exchange water, ultrafiltration water, reverse osmosis water, or distilled water. In particular, water obtained by sterilizing these waters by ultraviolet irradiation or addition of hydrogen peroxide is preferable because generation of mold and bacteria is prevented over a long period of time.
The treatment liquid according to the present embodiment can further contain an organic amine, and the pH of the treatment liquid can be easily adjusted to a suitable range. As the organic amine, a tertiary amine can be preferably used.

Examples of the tertiary amine include alkanolamines such as triethanolamine and tripropanolamine. The ink composition according to the present embodiment preferably has a pH of 7 to 10, particularly 7.5 to 9. In particular, when the pH is in a range exceeding 12, the storage stability of the treatment liquid is significantly lowered.
The content of the organic amine with respect to the total weight of the ink composition is 0.01% by weight or more. However, when forming a recorded image, the wettability of the recording medium or the like to the recording surface is improved to increase the ink permeability. And from the viewpoint of ink ejection stability, storage stability, and high-speed printing, it is preferably 0.05% by weight to 5.0% by weight, more preferably 0.1% by weight to 2.0% by weight. %.

The treatment liquid according to the present embodiment preferably contains a recording medium solubilizer in addition to the above components.
As the recording medium solubilizer, pyrrolidones such as N-methyl-2-pyrrolidone and / or lactones such as γ-butyrolactone can be preferably used. The addition amount of the recording medium solubilizer may be appropriately determined, but is preferably about 0.1% by weight to 30% by weight, more preferably about 1% by weight to 20% by weight.

In addition, the treatment liquid according to the present embodiment can contain a wetting agent that does not decrease the drying property after application to the film media for the purpose of improving clogging. Polyhydric alcohols and / or saccharides can be used as the wetting agent. Specific examples of the polyhydric alcohols include glycerin, ethylene glycol, diethylene glycol, triethylene glycol, trimethylolpropane and the like. Specific examples of saccharides include monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides), and polysaccharides. More specifically, glucose, mannose, fructose, ribose, xylose, arabinose, galactose, Examples thereof include aldonic acid, glucitol, (sorbit), maltose, cellobiose, lactose, sucrose, trehalose, maltotriose, and the like. Here, the polysaccharide means a saccharide in a broad sense, and is used to include a substance that exists widely in nature, such as alginic acid, α-cyclodextrin, and cellulose. The derivatives of these saccharides are represented by the reducing sugars of the saccharides described above (for example, sugar alcohol (general formula HOCH ₂ (CHOH) nCH ₂ OH (where n represents an integer of 2 to 5)). ), Oxidized sugars (eg, aldonic acid, uronic acid, etc.), amino acids, thio sugars, etc. Specific examples include maltitol, sorbitol, xylitol and the like. Further, trimethylolpropane, 1,2,6-hexatriol or the like may be used.

  The addition amount of the wetting agent is preferably 0.1% by weight to 10% by weight, more preferably about 0.5% by weight to 5% by weight.

  The treatment liquid according to the present embodiment may further contain a nozzle clogging preventing agent, preservative, antioxidant, conductivity adjusting agent, viscosity adjusting agent, surface tension adjusting agent, oxygen absorber and the like.

  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 BDN, Proxel GXL, Proxel XL-2, Proxel TN) and the like.

  Furthermore, as examples of dissolution aids or antioxidants, alcohols such as ethanol, propanol and butanol, amines such as diethanolamine and morpholine, and their modified products, inorganic substances such as potassium hydroxide, sodium hydroxide and lithium hydroxide Salts, ammonium hydroxide, quaternary ammonium hydroxides (such as tetramethylammonium), carbonates such as potassium carbonate, sodium carbonate, lithium carbonate, and other phosphates, or N-methyl-2-pyrrolidone, 2-pyrrolidone, urea And L-ascorbic acid and salts thereof, such as ureas such as thiourea and tetramethylurea, allophanates such as allophanate and methylallohanate, and biurets such as biuret, dimethylbiuret and tetramethylbiuret.

  In addition, the treatment liquid according to the present embodiment may contain an antioxidant and an ultraviolet absorber. Examples thereof include Tinuvin 328, 900, 1130, 384, 292, 123, and 144 manufactured by Ciba Specialty Chemicals. 622, 770, 292, Irgacor 252 153, Irganox 1010, 1076, 1035, MD1024, lanthanide oxide, and the like.

  According to the present embodiment, there is provided an ink jet recording method for forming a print image by ejecting ink jet ink droplets onto a recording medium treated with the above-described ink jet processing liquid. According to such a recording method, an effect such as suppression of bleeding of a recorded image can be obtained even on a non-ink-absorbing recording medium.

  According to this embodiment, a recorded matter printed by the above-described inkjet recording method is provided. According to such a recorded matter, an effect such as suppression of blurring of a recorded image can be obtained even when a non-ink-absorbing recording medium is used.

(Example)
Hereinafter, the present embodiment will be described in more detail by way of examples. However, the present embodiment is not limited to these examples. Unless otherwise specified, parts are parts by weight. Hereinafter, polyallylamine is referred to as “PAA”.

<Production Example 1>
Production of modified PAA-1 (a copolymer of N, N-dimethylallylamine and allylamine (5/5)).
In a 2-liter four-necked separable flask equipped with a stirrer, a Dimroth reflux condenser, and a thermometer, 431.24 g of a 63,45 wt% N, N-dimethylallylamine hydrochloride aqueous solution and a 58.11 wt% monoallylamine An aqueous hydrochloride solution of 362.25 g was charged. The monomer aqueous solution was heated to 60 ° C., and 146.45 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added as a radical initiator, and polymerization was performed for 120 hours.
After completion of the polymerization, 332.78 g of a 50 wt% sodium hydroxide aqueous solution was added dropwise under ice cooling to neutralize hydrochloric acid. After completion of neutralization, unreacted monomers were distilled off at 50 ° C. under reduced pressure (80 mmHg).
The solution obtained here was desalted by electrodialysis, and an aqueous solution of free type N, N-dimethylallylamine and allylamine having a concentration of 14.35 wt% (copolymerization ratio 5: 5) 1914. 97 g was obtained.
A part of the aqueous copolymer solution was converted to hydrochloride and reprecipitated with an acetone solvent to obtain copolymer hydrochloride. The results of elemental analysis were C = 44.72, H = 9.26, and N = 12.88. These values agreed with the calculated values C = 44.66, H = 9.37, and N = 13.02.

<Production Example 2>
Production of modified PAA-2 (copolymer of N, N-dimethylallylamine and allylamine (3/7)).
In Production Example 1, the amount of N, N-dimethylallylamine hydrochloride aqueous solution (concentration 63.45 wt%) was 258.75 g, and the amount of monoallylamine hydrochloride aqueous solution (concentration 58.11 wt%) was 507.15 g. Were operated in the same manner as in Production Example 1 to obtain 1978.93 g of a copolymer (copolymerization ratio 3: 7) aqueous solution of free type N, N-dimethylallylamine and allylamine having a concentration of 14.27 wt%.

<Production Example 3>
Production of modified PAA-3 (a copolymer of N, N-dimethylallylamine and allylamine (7/3)).
In Production Example 1, except that the amount of N, N-dimethylallylamine hydrochloride aqueous solution (concentration 63.45 wt%) was 603.74 g, and the amount of monoallylamine hydrochloride aqueous solution (concentration 58.11 wt%) was 217.35 g. Were processed in the same manner as in Production Example 1 to obtain 20455.55 g of a copolymer (copolymerization ratio 7: 3) aqueous solution of a free type N, N-dimethylallylamine and allylamine having a concentration of 14.20 wt%.

<Production Example 4>
Production of modified PAA-4 (copolymer of N, N-dimethylallylamine and carbamoylated allylamine (5/5)).
Copolymerization of free type N, N-dimethylallylamine of 14.35 wt% concentration prepared in Preparation Example 1 and allylamine into a 1 l four-necked separable flask equipped with a stirrer, a Dimroth reflux condenser and a thermometer 421.29 g of the combined aqueous solution was charged, and 88.65 g of hydrochloric acid having a concentration of 35 wt% was added dropwise under ice cooling. Subsequently, the mixture was heated to 50 ° C., and 368.37 g of a 7.5% strength sodium cyanate aqueous solution was added dropwise to carry out the reaction for 24 hours.
After completion of the reaction, 34.00 g of sodium hydroxide having a concentration of 50 wt% was added dropwise under ice cooling to neutralize unreacted hydrochloric acid.
The solution obtained here is subjected to electrodialysis, desalted, and an aqueous solution of a copolymer of free type N, N-dimethylallylamine and carbamoylated allylamine having a concentration of 10 wt% (copolymerization ratio 5: 5). 729.61 g (95% yield) was obtained. The weight average molecular weight of this copolymer was 1200.

This copolymer was concentrated to form a solid, and its solubility in various solvents at 10% by weight was examined. As a result, this polymer was insoluble in acetone and acetonitrile, but dissolved in methanol, ethanol, isopropanol, DMSO, and DMF. This result shows that the copolymer of this embodiment is dissolved in an organic solvent as compared with the allylamine polymer.
A part of the aqueous copolymer solution was converted to hydrochloride and reprecipitated with an acetone solvent to obtain copolymer hydrochloride. This result shows that the modified polyallylamine of this embodiment can be a cationic polymer.

  The results of elemental analysis were C = 48.96, H = 8.58, and N = 18.64. These values agreed with the calculated values C = 48.75, H = 9.09, and N = 18.95. Further, the molar fraction of carbamoylation calculated from neutralization titration of copolymer hydrochloride was 47.89%, which almost coincided with the result of elemental analysis.

<Production Example 5>
Production of modified PAA-5 (copolymer (3/7) of N, N-dimethylallylamine and carbamoylated allylamine).
In Production Example 4, instead of the aqueous solution of the free type N, N-dimethylallylamine and allylamine copolymer produced in Production Example 1, the free type N, N having a concentration of 14.27% produced in Production Example 2 was used. -Concentration of 10.02 wt% in the same manner as in Production Example 4 except that 390.23 g of a copolymer aqueous solution of dimethylallylamine and allylamine, 515.72 g of sodium cyanate aqueous solution, and 20.40 g of sodium hydroxide aqueous solution were used. % Of a free type N, N-dimethylallylamine and carbamoylated allylamine copolymer (copolymerization ratio 3: 7) aqueous solution 767.83 g (yield 95%) was obtained. The weight average molecular weight of this copolymer was 1300.

<Production Example 6>
Production of modified PAA-6 (copolymer of N, N-dimethylallylamine and carbamoylated allylamine (7/3)).
In Production Example 4, in place of the aqueous solution of the free type N, N-dimethylallylamine and allylamine copolymer produced in Production Example 1, a free type N, N— concentration of 14.20% produced in Production Example 3 was used. The same operation as in Production Example 4 was conducted except that 459.32 g of an aqueous solution of dimethylallylamine and allylamine (copolymerization ratio 7: 3), 459.32 g of sodium cyanate aqueous solution and 61.98 g of sodium hydroxide aqueous solution were used. As a result, 702.26 g (yield 93%) of a copolymer aqueous solution of free type N, N-dimethylallylamine and carbamoylated allylamine having a concentration of 10.11 wt% was obtained. The weight average molecular weight of this copolymer was 1500.

<Measurement of weight average molecular weight of polymer>
The weight average molecular weight (Mw) of the polymer was measured by gel permeation chromatography (GPC method) using a Hitachi L-6000 type high performance liquid chromatograph. The eluent flow path pump is Hitachi L-6000, the detector is Shodex RI SE-61 differential refractive index detector, the column is Asahi Pack's water-based gel filtration type GS-220HQ (exclusion limit molecular weight 3,000) and GS- 620HQ (exclusion limit molecular weight 2 million) and a double connection were used. The sample was adjusted to a concentration of 0.5 g / 100 ml with an eluent, and 20 μl was used. A 0.4 mol / l sodium chloride aqueous solution was used as an eluent. The column temperature was 30 ° C. and the flow rate was 1.0 ml / min. A calibration curve was determined using polyethylene glycol having a molecular weight of 106, 194, 440, 600, 1470, 4100, 7100, 10300, 12600, 23000 or the like as a standard sample, and the Mw of the polymer was determined based on the calibration curve.

<Adjustment of inkjet processing liquid>
Inkjet processing liquids having the following compositions were prepared.

<Example 1>
In Example 1, “Hydran CP-7020” (manufactured by Dainippon Ink & Chemicals, Inc.) was used as the cationic polyurethane, and “modified PAA-4” prepared in the above (Production Example 4) was used as the modified polyamine.

(Composition of treatment liquid 1)
Hydran CP-7020 (solid content 30%) 15 parts Modified PAA-04 (solid content 10%) 20 parts 1,2-hexanediol 5 parts BYK-347 0.5 part 2-pyrrolidone 5 parts Propylene glycol 5 parts Triethanol Amine 0.1 part Water remaining The treatment liquid having the above composition was sufficiently mixed and stirred, and filtered through a membrane filter having a pore size of 10 μm to prepare a treatment liquid 1.

<Example 2>
A treatment liquid 2 of Example 2 was obtained in the same manner as in Example 1 except that the modified PAA-4 was replaced with the modified PAA-5 in Example 1.

<Example 3>
A treatment liquid 3 of Example 3 was obtained in the same manner as in Example 1 except that the modified PAA-4 was replaced with the modified PAA-6 in Example 1.

<Example 4>
In Example 1, Surfynol MD-20 was used as the diacetylene tetraol, and diethylene glycol mono n-hexyl ether was used as the long-chain alkyl glycol ether.

(Composition of treatment liquid 4)
Hydran CP-7020 (solid content 30%) 15 parts Modified PAA-04 (solid content 10%) 20 parts Diethylene glycol mono n-hexyl ether 0.9 part Surfynol MD-20 0.1 part 1,2-hexanediol 5 Part BYK-347 0.5 part 2-Pyrrolidone 5 part Propylene glycol 4 part Triethanolamine 0.1 part Water Residue Mix and stir the treatment liquid of the above composition sufficiently, and filter the treatment liquid 4 with a pore size 10 μm membrane filter. Produced.

<Comparative Example 1>
A treatment liquid 4 of Comparative Example 1 was obtained in the same manner as in Example 1, except that the modified PAA-4 was replaced with unmodified PAA (PAA-01 manufactured by Nitto Boseki Co., Ltd.).

<Comparative example 2>
A treatment liquid 5 of Comparative Example 2 was obtained in the same manner as in Example 1 except that the modified PAA-4 was replaced with the modified PAA-1 in Example 1.

<Comparative Example 3>
The liquid of Comparative Example 5 was obtained in the same manner as in Example 1, except that the modified PAA4 was replaced with dimethyl-modified PAA (p / r was 95/5 to 100/0 and q = 0). A composition was obtained.

<Comparative example 4>
A treatment liquid of Comparative Example 4 was obtained in the same manner as in Example 1 except that the modified PAA-4 was replaced with water (no addition of the modified PAA-4 was added) in Example 1.

  When the surface tension of the liquid composition was measured by CBVP-Z manufactured by Kyowa Interface Science Co., Ltd., both the liquid compositions of Examples 1 to 4 and the liquid compositions of 1 to 4 of Comparative Examples were 25 to 35 dyn. / Cm.

[Applicability evaluation]
The treatment liquid is filled in an ink jet printer PX-G930 (manufactured by Seiko Epson Corporation), and the discharge amount of the treatment liquid per unit area is (1) 2.5 g / m 2 and (2) 5 g / m 2 with respect to the PET film. As described above, solid printing was performed with each coating amount, and the PET film after printing was dried in a thermostatic bath at 60 ° C. for about 1 minute.
The coated surface of the dried PET film was observed with a microscope (50 times magnification) to evaluate the coating state of the treatment liquid.
A: The treatment liquid on the PET film is uniformly applied without unevenness.
B: Slight streaky coating unevenness is observed in the treatment liquid on the PET film.
C: Coating unevenness is conspicuous in the treatment liquid on the PET film.

(Rubbing resistance evaluation)
The PET film after the coating property evaluation was rubbed 10 times with a cotton cloth with an excess weight of about 500 g using a Sutherland ink laboratory tester. The state of the coated surface after rubbing was evaluated according to the following evaluation criteria.
A: The trace of the part rubbed with cotton cloth is hardly noticed visually.
B: Slight streak can be confirmed on the trace of the part rubbed with cotton cloth.
C: It can confirm visually that the process liquid of the part rubbed with the cotton cloth has peeled.

(Reactivity evaluation)
The treatment liquid is applied and dried on the PET sheet in the same manner as in the above-mentioned rubbing resistance evaluation, and pure ink of an ink jet printer PX-G930 (manufactured by Seiko Epson Corporation) is used on the coated surface of the dried PET sheet. The printing evaluation was carried out. The evaluation was made by comparing and evaluating the bleeding and bleeding of printed images based on the following criteria.
A: There is no blur or bleed in the printed image.
B: Slight bleeding or bleeding is observed in the printed image.
C: Bleeding or bleeding is noticeable in the printed image.

[Evaluation of storage stability]
The processing solution was placed in a glass bottle and sealed, and then left to stand at 70 ° C. for 1 week. Observe the presence or absence of foreign matter (floating matter or sediment) after standing, and for those that do not generate foreign matter, investigate further changes in physical properties (viscosity, surface tension, pH, particle size) and based on the following criteria: Storage stability was evaluated.
A: No foreign matter is generated, and there is no change in physical properties.
B: No foreign matter is generated, but the physical properties slightly change.
C: Foreign matter is generated or the physical properties are remarkably changed.

[Evaluation of clogging]
After filling the processing liquid into an ink jet printer PX-G930 (manufactured by Seiko Epson Corporation) and confirming that all nozzles ejected normally, the power switch of the ink jet printer was turned off and stopped in a normal state. The mixture was left for 2 weeks in an environment of ° C. After being allowed to stand, the number of cleanings required until the treatment liquid was discharged again from all nozzles was examined, and clogging recovery was evaluated based on the following criteria. The discharge status was confirmed by printing a nozzle check pattern on an OHP film for an inkjet printer.
A: All nozzles were recovered by cleaning within 5 times.
B: All nozzles recovered after 5 to 10 cleanings.
C: All nozzles could not be recovered by cleaning 10 times.
Table 1 shows the results of the above evaluations.

The present embodiment is capable of inkjet ejection, has adhesion and adhesion to non-ink-absorbing recording media, transparency, drying after ejection, and bleeding suppression of recorded images, and also has storage stability. The present invention has industrial applicability as an ink jet processing liquid, ink jet recording method and recorded matter.
According to the present embodiment, an inkjet processing liquid having adhesion and adhesion to a non-ink-absorbing recording medium, transparency, drying after ejection, and bleeding suppression of a recorded image, and storage stability, An ink jet recording method and recorded matter can be provided.
That is, by incorporating a process of applying a treatment liquid using a combination of cationic polyurethane and the modified polyallylamine of the above general formula (1) onto a recording medium by inkjet discharge, a series of systems can be used with non- (hard) absorbing media. It enables printing by an inkjet printer on a certain film system (PET, PVC, PP, PE) media, etc. In addition, while having a drying property at a practical level, a stable ejection property in normal printing, The clogging recovery property after leaving can be secured, and further, storage stability can be secured without gelation even when the cationic polyurethane and the modified polyamine of the general formula (1) are allowed to coexist.

Claims (7)

An inkjet processing liquid comprising at least a cationic polyurethane and a modified polyallylamine,
An inkjet processing liquid, wherein the modified polyallylamine is a copolymer of N, N-dimethylallylamine and carbamoylated allylamine represented by the following general formula (1).

In the general formula (1), R ₁ and R ₂ each independently represents an alkyl group having 1 to 4 carbon atoms, p and q each independently represent an integer of 1 or more, and r represents an integer of 0 or more. .   The inkjet processing liquid according to claim 1, wherein the modified polyallylamine has a weight average molecular weight of 5000 or less. Furthermore, the inkjet processing liquid of Claim 1 or 2 containing the diacetylene tetraol represented by following General formula (2), and long-chain alkyl glycol ethers.

(In the general formula (2), R ₁ and R ₂ each independently represents an alkyl group having 1 to 8 carbon atoms, R ₃ independently represents a hydrogen atom or a methyl group, and —O—R ₄ — represents Each independently represents oxyethyl, oxypropyl, or oxybutyl, R ₅ represents a divalent linking group, and k, l, m, and n each represents an integer of 1 to 100.)   Furthermore, the inkjet process liquid in any one of Claims 1-3 containing a 1, 2- alkanediol.   Furthermore, the inkjet processing liquid in any one of Claims 1-4 containing a silicone type surfactant.   An ink jet recording method for forming a printed image by ejecting droplets of ink jet recording ink onto a recording medium treated with the ink jet processing liquid according to claim 1.   A recorded matter printed by the ink jet recording method according to claim 6.