JP2002294119A - Ink composition, recording medium, ink jet recording method, and record - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ink composition which gives a record excellent in light resistance, does not cause clogging, and can give the record with a high-quality image hardly yellowing; and to provide a recording medium using the same. SOLUTION: A compound represented by formula (1) (wherein X is H or an oxy radical, hydroxyl, alkyl, alkenyl, alkynyl, aryl, acyl, sulfonyl, sulfinyl, alkoxy, aryloxy or acyloxy group; R<1> , R<2> , R<3> , and R<4> are each H or an alkyl; and Z is a nonmetal atom group necessary for completing a 5- to 7-membered ring) and at least one inorganic salt selected from among compounds represented by MS2 O4 , MSO3 , MS2 O3 , MPH2 O2 , and MPHO3 (wherein M is an alkali or alkaline earth metal) are incorporated into the ink composition and/or the recording medium.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink composition, a recording medium, an ink-jet recording method, and a recorded matter, and more particularly, to an ink composition having excellent light stability (light resistance) without clogging of the ink. , Excellent yellowing resistance of recorded matter,
The present invention relates to an ink composition, a recording medium, a recorded matter, and an inkjet recording method capable of obtaining a high-quality image.

[0002]

2. Description of the Related Art An ink jet recording method is a printing method in which small droplets of an ink composition fly and adhere to a recording medium such as paper for recording. This method has a feature that high-resolution and high-quality images can be printed at a high speed with a relatively inexpensive device. Conventionally, various ink compositions have been proposed for use in recording by this ink jet recording method.

In recent years, weather resistance (especially light resistance) of recorded images has been improved.
There has been an increasing demand for improving the ink composition, and consequently, various measures have been taken to incorporate a light stabilizer such as a hindered amine compound into the ink composition.

For example, dyes and pigments 19 [Dyes and
d Pigments 19] (1992) 235-24
7, a hindered amine light stabilizer, 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl, is added to an aqueous solution containing a dye to prevent photodeterioration of the dye. It states that it can. JP-A-11-170686, which was filed after the publication of the above-mentioned document (dye and pigment 19), discloses that a specific compound (the 2,2,6 , 6-tetramethyl-4-hydroxypiperidine-1-oxyl or a derivative thereof) to stabilize the water-soluble dye. The compound captures radicals such as R. (alkyl radical) generated by photoexcitation of a carbonyl compound or the like and ROO (peroxide radical) generated by the reaction of R. with oxygen in the air to form a color. It functions to stop the progress of the photooxidation reaction of the material and to prevent light deterioration, and the printed matter inkjet-recorded using the recording liquid has excellent light resistance.

However, by recording using the ink composition containing the above-mentioned light stabilizer, the light fastness of the recorded image is improved. When a recorded matter is stored in a file equipped with a film containing an antioxidant composed of a derivative, or when the film is attached to the recorded matter, the recorded matter may turn yellow due to the effect of the light stabilizer. Problems have arisen.

This is considered to be due to the reaction of a specific phenol derivative due to the action of a light stabilizer such as a hindered amine compound contained in the ink composition fixed on the recording medium. Specific phenolic derivatives include BHT (2,6-di-t-butyl-4-).
Methylphenol) and the like.

That is, since the phenol-based derivative contained in the film has sublimability, it migrates from the film to the recorded matter, and the action of the light stabilizer in the recorded matter causes the phenol-based derivative to react with the phenol-based derivative. It is considered that the reactant generated through the dimerization and quinonation causes yellowing of the recorded matter. In particular, when the light stabilizer has an oxy radical, the reaction proceeds particularly remarkably, and it is considered that yellowing is more likely to occur.

[0007] Even when the compound as a light stabilizer does not have an oxy radical, the oxy radical is added to the compound as a light stabilizer by an oxidation reaction in the process of storing the recorded matter in the air. Due to the generation, the yellowing reaction proceeds, albeit slowly, and the yellowing of the recorded matter also occurs.

Accordingly, an object of the present invention is to provide an ink composition and a recording composition which are capable of obtaining a high-quality image which is excellent in light fastness of the recorded matter, does not cause clogging, and has almost no yellowing of the recorded matter. It is to provide a medium, an ink jet recording method, and a recorded matter.

[0009]

Means for Solving the Problems The present inventor has studied diligently.
As a result, the ink composition, a colorant, water, the general formula
Compound represented by (1) and MS₂O₄, MSO₃, M
S₂O₃, MPH₂O ₂, MPHO₃(M is an alkali
Metal or alkaline earth metal)
At least one inorganic salt selected from the group consisting of
Light resistance, clogging resistance, and
It has been found that a recorded matter having excellent yellowing resistance can be obtained.

Further, the present inventor has proposed that a recording medium has a receiving layer, in which the compound represented by the general formula (1), MS ₂ O ₄ , MSO ₃ , MS ₂ O ₃ , MPH
By including at least one or more inorganic salts selected from the group consisting of compounds represented by ₂ O ₂ and MPHO ₃ (M is an alkali metal or an alkaline earth metal), light resistance and yellow resistance are improved. It has been found that a recorded matter excellent in denaturation can be obtained.

The present invention has been made based on the above findings, and provides an ink composition containing a colorant, water, the compound represented by the above general formula (1), and predetermined inorganic salts. And a recording medium having a receiving layer containing the compound represented by the general formula (1) and predetermined inorganic salts. Further, the present invention provides a recorded matter obtained by using the ink composition and / or the recording medium, and a recording method.

In the above, the inorganic salts are MS
₂ O ₄ , MSO ₃ , MS ₂ O ₃ , MPH ₂ O ₂ , MPH
At least one or more inorganic salts selected from the group consisting of compounds represented by O ₃ (M is an alkali metal or an alkaline earth metal).

The inorganic salts are preferably potassium salts or sodium salts.

In the above, the compound represented by the general formula (1) has a water-soluble group W (W is a hydroxyl group, a -SO ₃ H group,
Sulfate group, -P (O) (OH) (OR), -P
(O) (OR) ₂ , a carboxyl group, an amino group, a carbamoyl group or a salt thereof, a salt of a phenolic hydroxyl group, a polyethylene glycol ether group, —C ＝ NH (NH ₂ )
Of representative salts, salts of -NHC = NH (NH ₂₎ a, (R is an alkyl group or an aryl group). ) Is preferable.

In the compound represented by the general formula (1), it is preferable that Z is a group of non-metallic atoms necessary for completing a six-membered ring.

In the compound represented by the general formula (1), X is preferably an oxy radical group.

The compound represented by the general formula (1) is preferably contained in the ink composition in an amount of from 0.05% by weight to 10% by weight.

The above-mentioned inorganic salts are contained in the ink composition in an amount of 0.0
It is preferable that the content is 1% by weight or more and 10% by weight or less.

In the above, the weight ratio of the compound represented by the general formula (1) to the inorganic salts (former / latter) is 1:
It is preferably from 25 to 5: 1.

The ink composition may further contain a penetrant and / or a humectant.

With the above structure, dimerization and quinone formation of the phenol derivative can be prevented, so that a recorded matter having excellent light fastness and excellent yellowing resistance can be obtained.

In the above-mentioned recording medium of the present invention, the compound represented by the general formula (1) is contained in the ink receiving layer in order to ensure sufficient ink absorption to the recording medium and to obtain yellowing resistance. Is preferably 0.01% by weight or more and 10% by weight or less based on the total weight of
More preferably, it is in the range of not less than 5% by weight and not more than 5% by weight.

In the recording medium of the present invention, in order to ensure sufficient absorption of the ink to the recording medium and to obtain yellowing resistance, the contained inorganic salts are contained in an amount of 0.01 wt. % To 10% by weight, more preferably 0.5% to 5% by weight.

In the recording medium of the present invention, in order to ensure sufficient light fastness and to obtain good yellowing resistance, the weight ratio of the compound represented by the general formula (1) to the inorganic salt is contained. Is preferably in the range of 1:25 or more and 5: 1 or less, and more preferably in the range of 1: 5 or more and 3: 1 or less.

With the above structure, dimerization and quinone formation of the phenol derivative can be prevented, so that a recorded matter having excellent light resistance and yellowing resistance can be obtained.

In the ink jet recording method of the present invention, recording is performed by discharging droplets of an ink composition and attaching the droplets to a recording medium. It is characterized by using a composition.

In the ink jet recording method of the present invention, the recording is performed by discharging droplets of the ink composition and attaching the droplets to a recording medium. Is used.

According to the ink jet recording method of the present invention, recording is performed by discharging droplets of an ink composition and attaching the droplets to a recording medium.
The present invention is characterized in that an ink receiving layer is provided on a base material, and a recording medium containing the above-mentioned inorganic salts in the ink receiving layer is used as the recording medium using the above ink composition.

In the ink jet recording method of the present invention, recording is performed by discharging droplets of an ink composition and attaching the droplets to a recording medium.
An ink composition containing a colorant, water and the above-mentioned inorganic salts is used, and the recording medium is used as the recording medium.

Further, the present inventors have conducted intensive studies based on these inventions. As a result, the compound represented by the general formula (1) is contained in the ink composition, and the above-mentioned inorganic salts are recorded. Similarly, it has been found that a recorded matter having excellent light resistance and clogging resistance and excellent yellowing resistance can be obtained even when contained in a medium.

That is, in the ink jet recording method of the present invention, the ink composition comprises a colorant, water, and a compound represented by the general formula (1):
And a recording medium comprising the above-mentioned inorganic salts.

The ink composition used in the recording method of the present invention contains a colorant, water, and a compound represented by the general formula (1).

In the ink jet recording method of the present invention, recording is performed by discharging droplets of an ink composition and attaching the droplets to a recording medium.
An ink composition containing a colorant, water and the compound represented by the general formula (1) is used, and the recording medium is used as the recording medium.

In the above recording method of the present invention, in order to have sufficient light fastness and sufficient clogging resistance, the content of the compound represented by the general formula (1) is determined based on the total amount of the ink. The content is preferably 0.05% by weight or more and 10% by weight or less, and more preferably 0.5% by weight or more and 5% by weight or less. Further, the content of the inorganic salts is preferably 0.01% by weight or more and 10% by weight or less.

The recording medium used in the recording method of the present invention is a recording medium in which an ink receiving layer is provided on a base material, and the ink receiving layer contains the above-mentioned inorganic salts.

In the above recording method of the present invention, in order to ensure sufficient ink absorbency with respect to the recording medium and to obtain yellowing resistance, the contained inorganic salts are added in an amount of 0.1 to the total weight of the ink receiving layer. It is preferable that the content be from 01% by weight to 10% by weight, more preferably from 0.5% by weight to 5% by weight.
More preferably, it is in the following range.

By using these recording methods, it is possible to obtain a recorded matter which is excellent in light resistance and yellowing resistance.

[0038]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the ink composition of the present invention will be described below.

The ink composition according to the present invention comprises a colorant,
It comprises water, a compound represented by the following general formula (1), and inorganic salts, wherein the inorganic salts are MS ₂ O ₄ , MSO
₃ , MS ₂ O ₃ , MPH ₂ O ₂ , and MPHO ₃ (M is an alkali metal or an alkaline earth metal) and is at least one or more inorganic salts selected from the group consisting of compounds.

[0040]

Embedded image (In the formula (1), X is hydrogen, an oxy radical group, a hydroxyl group,
An alkyl group, an alkenyl group, an alkynyl group, an aryl group, an acyl group, a sulfonyl group, a sulfinyl group, an alkoxy group, an aryloxy group or an acyloxy group, wherein R ¹ , R ² , R ³ and R ⁴ are each hydrogen or an alkyl group; And Z is a group of non-metallic atoms necessary to complete the 5- to 7-membered ring. Here, any two groups of R ^{1 to} R ⁴ and Z may be bonded to each other to form a 5- to 7-membered ring. The compound represented by the above (1) is preferably a compound having a water-soluble group W and represented by the following general formula.

[0041]

Embedded image(W is a hydroxyl group, -SO₃H group, sulfate ester
Group, -P (O) (OH) (OR), -P (O) (O
R)₂, Carboxyl, amino, carbamoyl, etc.
Or salts thereof, phenolic hydroxyl group salts, polyethylene
Glycol ether group, -C = NH (NH₂) Salt,-
NHC = NH (NH₂Wherein R is an alkyl group.
Or an aryl group). X is hydrogen, oxyradi
Cal group, hydroxyl group, alkyl group, alkenyl group, alkynyl
Group, aryl group, acyl group, sulfonyl group, sulfy
Nyl, alkoxy, aryloxy, or acyl
Roxy group, R¹, R², R³And R⁴Is it
Each represents hydrogen or an alkyl group, and Z is a 5- to 7-membered ring.
This is a group of non-metallic atoms necessary for the formation. Where R
¹~ R ⁴And any two groups of Z are bonded to each other
To form a 5- to 7-membered ring. In the general formula (1), as the alkyl group represented by X
Is, for example, a methyl group, an ethyl group, an n-propyl group, is
o-propyl, n-butyl, t-butyl, n-o
Butyl group, benzyl group, hexadecyl group and the like,
Examples of the alkenyl group include an allyl group and an oleyl group.
Examples of the alkynyl group include, for example, an ethynyl group
And the aryl group is, for example, phenyl
Group, naphthyl group, etc.
For example, acetyl, benzoyl, pentanoyl, etc.
And a sulfonyl group such as methanesulfonyl
Group, benzenesulfonyl group, toluenesulfonyl group, etc.
Examples of the sulfinyl group include, for example, methanes
Rufinyl group, benzenesulfinyl group and the like,
As the alkoxy group, for example, methyloxy group, ethyl
Oxy group, i-propyloxy group, n-butyloxy
Group, cyclohexyloxy group, n-octyloxy group,
A 1-octyloxy group, a benzyloxy group, and the like;
Examples of the aryloxy group include a phenoxy group and the like.
Examples of the acyloxy group include, for example, acetyl
An oxy group, a benzoyloxy group and the like can be mentioned. these
Any of the groups may have a substituent, the substituent and
A sulfonyl group, a carboxyl group, a hydroxy group
And the like. Particularly, when X is an oxyradical group,
Is preferred.

In the general formula (1), R ¹ , R ² ,
R ³ and R ⁴ represent a hydrogen or an alkyl group as described above. The alkyl group is selected from the same category as the alkyl group represented by X. Particularly, a methyl group is preferable.

In the compound represented by the general formula (1), those in which Z is a group of non-metallic atoms necessary for completing a six-membered ring are preferable.

Hereinafter, specific examples of the compound represented by the formula (1) will be shown.

[0045]

Embedded image In the ink composition, the compound represented by the general formula (1)
The content is preferably 0.05% by weight or more and 10% by weight or less, more preferably 0.1% by weight or more and 5% by weight or less. Inorganic salts are MS ₂ O ₄ , MS
O ₃ , MS ₂ O ₃ , MPH ₂ O ₂ , MPHO ₃ (M is
At least one selected from the group consisting of compounds represented by the following formulas (alkali metals or alkaline earth metals). As the alkali metal, K, Na, and Li are preferable, and as the alkaline earth metal, Mg, Ca, B
a is preferred. In particular, the inorganic salts of the present invention are preferably potassium salts or sodium salts.

Specific examples of inorganic salts include, for example, K₂S
₂O₄, Na₂S₂O₄, Li₂S ₂O₄, MgS₂O
₄, CaS₂O₄, BaS₂O₄, K₂SO₃, Na₂
SO ₃, Li₂SO₃, MgSO₃, CaSO₃, Ba
SO₃, K₂S₂O₃, Na ₂S₂O₃, Li₂S₂O
₃, MgS₂O₃, CaS₂O₃, BaS₂O₃, KP
H₂O₂, NaPH₂O₂, LiPH₂O₂, Mg (P
H₂O₂)₂, Ca (PH₂O₂)₂, Ba (PH₂O
₂), K₂PHO₃, Na₂PHO₃,₂Li ₂PHO
₃, MgPHO₃, CaPHO₃, BaPHO₃Is raised
Can be In particular, if it is a potassium or sodium salt
In this case, the yellowing resistance of the recorded matter is remarkably improved.

These inorganic salts may be used alone or in combination.

The inorganic salt is preferably contained in the ink composition at 0.01% by weight to 10% by weight, more preferably at 0.1% by weight to 5% by weight. With the preferred content, the yellowing resistance of the recorded matter is remarkably improved.

In the present invention, the weight ratio of the compound represented by the general formula (1) to the inorganic salts (former / latter) is preferably 1:25 or more and 5: 1 or less, particularly preferably 1: 5. It is more preferable that the ratio be at least 3: 1. By setting the preferred weight ratio, the yellowing resistance of the recorded matter is remarkably improved.

Dyes and pigments can be used as the coloring agent. As the dye, a water-soluble dye is preferable, and specific examples thereof include those classified into acid dyes, direct dyes, catalytic dyes, reactive dyes, soluble vat dyes, sulfur dyes and food dyes in the color index. . Also,
Even those not described in the color index can be preferably used in many cases. Specific examples of these include CI Direct Black 17, 19, 32, 3
8, 51, 62, 71, 74, 75, 112, 117,
154, 163, 168, CI Acid Black 7, 2
4, 26, 48, 52, 58, 60, 107, 109,
118, 119, 131, 140, 155, 156, 1
87, CI Food Black 1, 2, CI Reactive Black 5, CI Direct Yellow 11, 28, 33,
39, 44, 58, 86, 100, 132, 142, 3
30, CI Acid Yellow 3, 19, 23, 25, 2
9, 38, 49, 59, 62, 72, CI Basic Yellow 11, 51, CI Disperse Yellow 3, 5,
CI Reactive Yellow 2, CI Direct Red 2
3, 79, 80, 83, 99, 220, 224, 22
7, CI Acid Red 1, 8, 17, 18, 32, 3
5, 37, 42, 52, 57, 92, 115, 119,
131, 133, 134, 154, 186, 249, 2
54, 256, CI Basic Red 14, 39, CI
Disperse Red 60, CI Direct Blue 6,
8, 15, 25, 71, 76, 80, 86, 90, 10,
6, 108, 123, 163, 165, 168, 19
9, 226, CI Acid Blue 9, 29, 40, 6
2, 74, 102, 104, 113, 117, 120,
175, 183, CI Basic Blue 41, CI Reactive Blue 15, CI Direct Violet 4
7, 51, 90, 94, CI Acid Violet 1
1, 34, 75 and the like. The pigment is not particularly limited, and any of an inorganic pigment and an organic pigment can be used. As the inorganic pigment, in addition to titanium oxide and iron oxide, carbon black produced by a known method such as a contact method, a furnace method, and a thermal method can be used. Examples of organic pigments include azo dyes (including azo lakes, insoluble azo pigments, condensed azo pigments, chelated azo pigments, etc.) and polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazines) Pigments, thioindigo pigments, isoindolinone pigments,
Quinofuraron pigments, dye chelates (eg, basic dye chelates, acid dye chelates, etc.), nitro pigments, nitroso pigments, aniline black, and the like can be used.

Particularly, carbon black used as black ink includes No. 2300, No. 900, MCF88, N
o.33, No.40, No.45, No.52, MA7, MA8, MA100, No2200B, etc., manufactured by Columbia Raven5750, Raven5250, Raven5000,
Raven3500, Raven1255, Raven700 etc. are manufactured by Cabot
Regal 400R, Regal 330R, Rega l660R, Mogul L, Monarch70
0, Monarch 800, Monarch 880, Monarch 900, Monarch
1000, Monarch 1100, Monarch 1300, Monarch 1400 etc. are Degussa Color Black FW1, Color Black FW
2, Color Black FW2V, Color Black FW18, Color Black
FW200, Color Black S150, Color Black S160, Color
Black S170, Printex 35, Printex U, Printex V, Pri
ntex 140U, Special Black 6, Special Black 5, Speci
al Black 4A, Special Black 4 etc. can be used.

Pigments used in the yellow ink include CI Pigment Yellow 1, CI Pigment Yellow 2,
CIPigment Yellow 3, CIPigment Yellow 12, CIP
igmentYellow 13, CIPigment Yellow 14C, CIPigme
nt Yellow 16, CIPigment Yellow 17, CIPigment Y
ellow 73, CIPigment Yellow 74, CIPigment Yello
w 75, CIPigment Yellow 83, CIPigment Yellow 9
3, CIPigment Yellow95, CIPigment Yellow97, C.
I. Pigment Yellow 98, CIPigment Yellow 119, CIP
igment Yellow 110, CIPigment Yellow114, CIPigm
ent Yellow128, CIPigment Yellow129, CIPigment
Yellow 138, CIPigment Yellow 150, CIPigment Ye
llow 151, CIPigment Yellow154, CIPigment Yellow
155, CIPigment Yellow 180, CIPigment Yellow 18
5, and the like.

Pigments used in magenta ink include CI Pigment Red 5, CI Pigment Red 7, CI
Pigment Red 12, CIPigment Red 48 (Ca), CIPigmen
t Red 48 (Mn), CIPigment Red 57 (Ca), CIPigment
Red 57: 1, CIPigment Red112, CIPigment Red 122,
CIPigment Red 123, CIPigment Red 168, CIPig
ment Red 184, CIPigment Red 202 and the like.

Further, pigments used in cyan ink include CI Pigment Blue 1, CI Pigment Blue 2, C.I.
I. Pigment Blue 3, CIPigment Blue 15: 3, CIPigme
nt Blue 15:34, CIPigment Blue 15: 4, CIPigment
Blue 16, CIPigment Blue22, CIPigment Blue 60,
CIVat Blue 4 and CIVat Blue 60.

The amount of the coloring agent to be added is preferably 0.1% by weight or more and 20% by weight or less in the ink composition.
The content is more preferably from 5% by weight to 10% by weight. Also,
In the case of a pigment, the particle size is preferably 10 μm or less, more preferably 0.1 μm or less. In the ink composition of the present invention, water is used as a solvent. As water, pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, distilled water,
Alternatively, any of ultrapure water can be preferably used.

The ink composition of the present invention may further contain a penetrant and / or a humectant.

As the penetrating agent, compounds capable of reducing the surface tension of the ink, promoting the penetration of the ink into the recording medium, and shortening the ink drying time can be widely used. For example, ethanol, propanol, isopropanol, butanol,
Examples thereof include lower alcohols such as pentanol, cellosolves such as ethylene glycol monoethyl ether and ethylene glycol monobutyl ether, carbitols such as diethylene glycol monobutyl ether and triethylene glycol monobutyl ether glycol ether, and nonionic surfactants.

As the humectant, a compound capable of suppressing evaporation of water and keeping the ink moist and improving the ejection stability can be widely used. For example, polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, glycerin, diglycerin, 1,3-propanediol, 1,5-pentanediol, maltitol, maltose, and sorbitol Saccharides such as trimethylolethane, glycerin derivatives such as trimethylolpropane, carbonates such as ethylene carbonate, imidazole derivatives such as imidazole and 2-methylimidazole, pyridinol derivatives such as 2-pyridinol and 3-pyridinol, and urea. No.

The ink composition of the present invention may further contain, if necessary, auxiliaries generally used in ink jet recording inks. Such auxiliaries include pH adjusters, chelating agents, preservatives, rust inhibitors and the like. With the above configuration, dimerization and quination of the phenolic derivative can be prevented,
It is possible to obtain a recorded matter which is excellent in light resistance and clogging resistance and is also excellent in yellowing resistance. Further, in the present invention, a compound represented by the general formula (1) and MS ₂ O ₄ ,
MSO ₃ , MS ₂ O ₃ , MPH ₂ O ₂ , MPHO ₃ (M
Is an alkali metal or an alkaline earth metal), at least one or more inorganic salts selected from the group consisting of compounds represented by, separately or in addition to the ink composition,
Even when applied on a recording medium as an application liquid,
Works effectively. In this case, it is desirable that the application liquid is prepared in the same range as the above-described composition of the ink composition except for the coloring material. Next, a preferred embodiment of the recording medium according to the present invention will be described. As the ink receiving layer, those which are at least composed of an ink absorbing pigment, an ink fixing agent and a binder are known as those capable of reproducing a color image or a photographic image with high image quality. The ink receiving layer of the medium further contains the compound represented by the general formula (1) and the above-mentioned inorganic salts. As the compound represented by the general formula (1), it is preferable to use the same compound as that used in the above-mentioned ink composition. The compound represented by the general formula (1) accounts for 0.01% by weight based on the total dry weight of the ink receiving layer.
It is preferably contained in an amount of not less than 10% by weight and particularly,
More preferably, the content is 0.1% by weight or more and 5% by weight or less. Inorganic salts, in the total dry weight of the ink receiving layer,
The content is preferably 0.01% by weight or more and 10% by weight or less, more preferably 0.1% by weight or more and 5% by weight or less. When the content is in the preferable range, the yellowing resistance of the recorded matter is remarkably improved. In the present invention, the weight ratio (former / latter) of the compound represented by the general formula (1) and the inorganic salt is preferably from 1:25 to 5: 1, and particularly from 1: 5 to 3: 1. It is more preferred that: When the weight is in the preferable range, the yellowing resistance of the recorded matter is remarkably improved. One or more known white pigments can be used as the ink absorbing pigment, and examples thereof include silica such as synthetic amorphous silica and colloidal silica, and colloidal alumina. In addition, as white pigments, in addition to silica and alumina, light calcium carbonate, heavy calcium carbonate, magnesium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, titanium carbonate White, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, pseudoboehmite, aluminum hydroxide, magnesium hydroxide, lithopone, zeolite,
Examples thereof include white inorganic pigments such as hydrohaloysite, styrene-based plastic pigments, acrylic-based plastic pigments, and organic pigments such as polyethylene, melamine resin, and urea resin. These ink absorbing pigments are preferably contained in an amount of 30% by weight to 90% by weight, more preferably 40% by weight to 80% by weight, based on the total dry weight of the ink receiving layer. As the ink fixing agent, a cationic compound is particularly preferable, and primary to
Examples include low molecular weight compounds having a quaternary amine or quaternary ammonium base, oligomers having these groups, or polymers having these groups. As a specific example,
Diallyldimethylammonium chloride polymer, diallyldimethylammonium chloride-sulfur dioxide copolymer, diallyldimethylammonium salt polymer such as diallyldimethylammonium chloride-acrylamide copolymer, diallylamine hydrochloride-sulfur dioxide copolymer, diallylmethylamine hydrochloride copolymer, polyallylamine, polyethyleneimine Polyethyleneimine quaternary ammonium salt compound, (meth) acrylic acid alkylammonium salt polymer, (meth) acrylamidoalkylammonium salt polymer, ionicene containing quaternary ammonium salt, polyalkyleneamine dicyandiamide ammonium salt condensate and the like. . These ink fixing agents are preferably contained in an amount of 1% by weight to 30% by weight, more preferably 5% by weight to 10% by weight, based on the total dry weight of the ink receiving layer. Examples of the binder include oxidized starch, etherified starch, starch derivatives such as phosphated starch, cellulose derivatives such as carboxymethylcellulose and hydroxyethylcellulose, casein, gelatin, soybean protein, polyvinyl alcohol or derivatives thereof, polyvinylpyrrolidone, and maleic anhydride. Resin, styrene-butadiene copolymer, conjugated diene-based copolymer latex such as methyl methacrylate-butadiene copolymer, acrylic-based such as acrylate- and methacrylate-ester copolymer or copolymer-based acrylic polymer Polymer latex, vinyl-based polymer latex such as ethylene-vinyl acetate copolymer, or functional group-modified polymer latex with functional group-containing monomer such as carboxyl group of these various polymers, melamine resin Aqueous adhesives such as thermosetting resins such as urea resins, acrylates such as polymethyl methacrylate, polymers or copolymers of methacrylates, polyurethane resins, unsaturated polyester resins, vinyl chloride vinyl acetate copolymers, and polyvinyl chloride Synthetic resin-based adhesives such as butyral and alkyd resin can be used. These binders are preferably contained in an amount of from 10% by weight to 60% by weight, more preferably from 20% by weight to 50% by weight, based on the total dry weight of the ink receiving layer. The ink receiving layer may further include a known dye fixing agent (waterproofing agent), a fluorescent whitening agent, a surfactant, an antifoaming agent,
Various additives such as a regulator, a fungicide, an ultraviolet absorber and an antioxidant may be contained. As described above, the configuration of the ink receiving layer has been described.As the ink receiving layer, silica or alumina is used as a main component, and the particle size of the silica or alumina and the content of other components are adjusted. It is particularly preferable that the porosity of the ink receiving layer is 30% or more and 80% or less. By setting the porosity to 30% or more, in particular, it is possible to reliably secure the absorbability of the ink to the recording medium.
Strength can be reliably given to the ink receiving layer. As the substrate, a paper or plastic sheet is used, and any of a light-transmitting material and a light-impermeable material can be used. As these substrates, conventionally known ones can be used. Specifically, examples of the paper include those made of pulp raw materials of wood pulp or non-wood pulp mainly composed of natural cellulose fibers. Materials include polyester resin, diacetate resin, triacetate resin,
An acrylic resin, a polycarbonate resin, a polyvinyl chloride resin, a polyimide resin, cellophane, celluloid and the like can be mentioned. The recording medium of the present invention is a coating liquid in which each of the above components is dissolved or dispersed in a suitable solvent such as water, a roll coating method, a spray coating method,
It can be suitably obtained by coating the above-mentioned base material by a known coating method such as a rod bar coating method or an air knife coating method, and subsequently drying it. Drying after coating can be performed using a general dryer, and is generally performed in a range of 100 ° C to 150 ° C. By adopting the above configuration, it is possible to obtain a recorded matter which is excellent in image storability and light fastness and also excellent in yellowing resistance. Further, the ink jet recording method of the present invention will be described. In the ink jet recording method of the present invention, by performing ink jet recording using the ink composition and / or the recording medium, the general formula (1) and the above-mentioned inorganic salts can suitably coexist in the recorded matter. This makes it possible to obtain a recorded matter having excellent light fastness and excellent yellowing resistance. Furthermore, in the ink jet recording method of the present invention, a case where the ink composition contains a colorant, water, and a compound represented by the general formula (1), and the recording medium contains the above-mentioned inorganic salts. In this case, it is possible to obtain a recorded matter having sufficient light resistance and excellent yellowing resistance.

[0060]

EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

(Preparation of Ink Composition) Each component having the composition shown in Table 1 was stirred at room temperature for 30 minutes, and then 1 μm
Each of the ink compositions was obtained by filtration with a m. membrane filter.

[0062]

[Table 1] (Lightfastness test) Each of the above ink compositions was filled in a special cartridge using an ink jet printer PM800C (manufactured by Seiko Epson Corporation), and a recording medium dedicated for ink jet (manufactured by Seiko Epson Corporation, PM Photo Paper) ). This was left to stand in a room temperature and normal humidity environment without direct light for one day, and the light resistance of the obtained recorded matter was evaluated under the following conditions.

First, light irradiation was performed using a Xenon weatherometer Ci5000 (manufactured by ATLAS), and the printed matter was exposed at a black panel temperature of 35 ° C., a relative humidity of 60% and an ultraviolet light irradiance of 340 nm of 0.18 W / m ² . . The irradiation condition was 180 kJ / m ² (light irradiation for 278 hours under the above conditions) or 360 kJ / m ² (light irradiation for 556 hours under the above conditions).

After the irradiation, the reflection density of each color component of the recorded matter was measured using a spectrophotometer GRETAG SPM (manufactured by GRETAG). The conditions at that time were as follows: the light source D50, no light source filter, the white standard was absolute white, and the viewing angle was 2 °. The residual concentration was evaluated according to the following criteria.

Evaluation A: Exceeds 90% of the initial value.

Evaluation B: 80% or more and less than 90% of the initial value.

Evaluation C: Less than 80% of the initial value.

(Clogging Leaving Test) An ink cartridge filled with the ink composition was loaded into the printer described above,
After confirming that the ink composition is normally ejected at the initial stage, the printer is turned off and the ink cartridge is loaded, and the temperature is 40 ° C. and the humidity is 20% RH for 1 to 12 months. I left it. After leaving the printer for a predetermined period of time, move the printer to a normal temperature environment, wait until the temperature of the main unit has dropped to normal temperature, turn on the power, perform printing again, and perform the number of recovery operations required until print quality equivalent to that before leaving the printer was obtained. Was examined. The evaluation was performed according to the following criteria.

Evaluation A: Print quality equivalent to the initial one was obtained by the return operation of 0 to 2 times.

Evaluation B: The print quality equivalent to the initial one was obtained by the return operation three to five times.

Evaluation C: Print quality equivalent to the initial one could not be obtained after 6 or more return operations.

(Yellowing resistance test) In the same manner as in the light resistance test, a printed matter was obtained on a recording medium exclusively for ink jet (PM photo paper, manufactured by Seiko Epson Corporation, trade name).

Next, the obtained printed matter was placed in a clear file (manufactured by Mitsubishi Pencil Co., Ltd., trade name: CL-A420) and left for 3 days to 1 month in an environment of a temperature of 40 ° C. and a humidity of 20% RH. After standing for a predetermined time, the printed matter was taken out of the clear file, and the color change of the non-printed portion and the discoloration of the printed portion and its surroundings were visually checked according to the following criteria.

Evaluation A: Good without any yellow color change.

Evaluation B: It seems that yellowing is slightly observed, but there is no problem in image quality.

Evaluation C: The printed part and its periphery are yellowed.

(Printing Evaluation Test Results) The above ink composition 1
Table 2 shows the results of the tests performed using Nos. To 9 above.

[0078]

[Table 2] As can be seen from Table 2, in Examples 1 to 5 using the ink composition containing the compound represented by the general formula (1) and a predetermined inorganic salt, Comparative Examples 1 to 4 were light-fast. sex,
Although all of the resistance to clogging and the resistance to file yellowing could not be satisfied, satisfactory results were obtained for all of them.

(Preparation of Recording Medium) A substrate was weighed at 100 g /
m2 ^high- quality paper, and 15 g of a coating liquid (weight of the ink-receiving layer component: weight of water = 20: 80) obtained by mixing the ink-receiving layer components and water shown in Table 3 with the high-quality paper. / M ² . After coating, 130 ° C using a dryer,
Layering was performed for 2 minutes to produce recording media A to O.

[0080]

[Table 3] (Results of printing evaluation test) Each ink composition and each recording medium were combined and printed as shown in Table 4, and a light resistance test and a yellowing resistance test were performed in the same manner as described above. Table 4 shows the results of each test.

[0081]

[Table 4] As can be seen from Table 4, in Examples 6 to 12, Comparative Examples 5 to 9 failed to satisfy all of light resistance, clogging resistance and file yellowing resistance.
All satisfactory results were obtained.

[0082]

The ink composition and recording medium of the present invention,
Further, according to the inkjet recording method of the present invention, it is possible to obtain a high quality image having excellent light fastness of the recorded matter, no clogging, and further excellent yellowing resistance of the recorded matter.

The recorded matter of the present invention is excellent in light resistance of a recorded image and yellowing resistance.

Continuation of the front page (72) Inventor Kazuhiko Kitamura 3-3-5 Yamato, Suwa City, Nagano Prefecture Inside Seiko Epson Corporation (72) Inventor Tetsuya Aoyama 3-5-5 Yamato Suwa City, Nagano Prefecture Seiko Epson Corporation (72) Inventor Kyoichi Oka 3-3-5 Yamato, Suwa City, Nagano Prefecture Seiko Epson Corporation (72) Inventor Nobuo Uotani 1-1-1, Onodai, Midori-ku, Chiba City, Chiba Prefecture Showa Denko KK (72) Inventor Hiroshi Takahashi 1-1-1, Onodai, Midori-ku, Chiba City, Chiba Prefecture Inside the Research Institute of Showa Denko KK (72) Inventor Yuji Ito 1-1-1, Onodai, Midori-ku, Chiba City, Chiba Prefecture F-term in the Company Research Laboratory (reference) 2C056 EA13 FC01 FC02 FC06 2H086 BA01 BA02 BA15 BA21 BA31 BA53 BA59 BA62 4J039 BA04 BA18 BA19 BA29 BA30 BC05 BC07 BC12 BC16 BC19 BC20 BC29 BC33 BC36 BC39 BC44 BC45 BC50 BC54 BC56 BC60 BE01 BE03 BE04 BE06 EA16 EA17 EA19 EA21 EA34 EA35 EA41 EA42 GA24

Claims (24)

[Claims] 1. An ink composition comprising a colorant, water, a compound represented by the following general formula (1), and inorganic salts, wherein the inorganic salts are MS ₂ O ₄ , MSO ₃ , MS ₂ O ₃ ,
An ink composition comprising at least one inorganic salt selected from the group consisting of compounds represented by MPH ₂ O ₂ and MPHO ₃ (M is an alkali metal or an alkaline earth metal). Embedded image (In the formula (1), X is hydrogen, an oxy radical group, a hydroxyl group,
An alkyl group, an alkenyl group, an alkynyl group, an aryl group, an acyl group, a sulfonyl group, a sulfinyl group, an alkoxy group, an aryloxy group or an acyloxy group, wherein R ¹ , R ² , R ³ and R ⁴ are each hydrogen or an alkyl group; And Z is a group of non-metallic atoms necessary to complete the 5- to 7-membered ring. Here, any two groups of R ^{1 to} R ⁴ and Z may be bonded to each other to form a 5- to 7-membered ring. ) 2. A compound represented by the general formula (1):
A compound having a water-soluble group W and represented by the following general formula:
The ink composition according to claim 1, wherein Embedded image(W is a hydroxyl group, -SO₃H group, sulfate ester
Group, -P (O) (OH) (OR), -P (O) (O
R)₂, Carboxyl, amino, carbamoyl, etc.
Or salts thereof, phenolic hydroxyl group salts, polyethylene
Glycol ether group, -C = NH (NH₂) Salt,-
NHC = NH (NH₂Wherein R is an alkyl group.
Or an aryl group). X is hydrogen, oxyradi
Cal group, hydroxyl group, alkyl group, alkenyl group, alkynyl
Group, aryl group, acyl group, sulfonyl group, sulfy
Nyl, alkoxy, aryloxy, or acyl
Roxy group, R¹, R², R³And R⁴Is it
Each represents hydrogen or an alkyl group, and Z is a 5- to 7-membered ring.
This is a group of non-metallic atoms necessary for the formation. Where R
¹~ R ⁴And any two groups of Z are bonded to each other
To form a 5- to 7-membered ring. ) 3. The ink composition according to claim 1, wherein the inorganic salt is a potassium salt or a sodium salt. 4. The compound according to claim 1, wherein in the compound represented by the general formula (1), Z is a group of nonmetal atoms necessary for completing a six-membered ring. Ink composition. 5. The compound represented by the general formula (1), wherein X is an oxy radical group.
The ink composition according to claim 1. 6. A compound represented by the general formula (1):
The ink composition according to any one of claims 1 to 5, wherein the ink composition contains 0.05% by weight or more and 10% by weight or less in the ink composition. 7. The ink according to claim 7, wherein the inorganic salt is contained in an ink composition.
The ink composition according to any one of claims 1 to 6, comprising from 01% by weight to 10% by weight. 8. The weight ratio of the compound represented by the general formula (1) to the inorganic salts (former / latter) is 1:25 or more and 5: 1.
The ink composition according to claim 1, wherein: 9. The ink composition according to claim 1, further comprising a penetrant and / or a humectant. 10. A recording medium having an ink receiving layer provided on a base material, wherein the ink receiving layer contains a compound represented by the following general formula (1) and an inorganic salt: The inorganic salts are MS ₂ O ₄ , MSO ₃ , MS ₂ O ₃ ,
A recording medium which is at least one or more inorganic salts selected from the group consisting of compounds represented by MPH ₂ O ₂ and MPHO ₃ (M is an alkali metal or an alkaline earth metal). Embedded image (In the formula (1), X is hydrogen, an oxy radical group, a hydroxyl group,
An alkyl group, an alkenyl group, an alkynyl group, an aryl group, an acyl group, a sulfonyl group, a sulfinyl group, an alkoxy group, an aryloxy group or an acyloxy group, wherein R ¹ , R ² , R ³ and R ⁴ are each hydrogen or an alkyl group; And Z is a group of non-metallic atoms necessary to complete the 5- to 7-membered ring. Here, any two groups of R ^{1 to} R ⁴ and Z may be bonded to each other to form a 5- to 7-membered ring. ) 11. The compound represented by the general formula (1) is present in an amount of 0.01% by weight or more and 10% by weight based on the total amount of the ink receiving layer.
The recording medium according to claim 10, wherein: 12. The recording medium according to claim 10, wherein the inorganic salt is contained in an amount of 0.01% by weight or more and 10% by weight or less based on the total amount of the ink receiving layer. 13. The method according to claim 10, wherein a weight ratio (former / latter) of the compound represented by the general formula (1) to the inorganic salt is in a range of 1:25 or more and 5: 1 or less. The recording medium according to claim 1. 14. An ink jet recording method for ejecting droplets of an ink composition and attaching the droplets to a recording medium for recording, wherein the ink composition is any one of claims 1 to 9. 13. An ink jet recording method, comprising using the ink composition according to any one of the above items. 15. An ink-jet recording method in which droplets of an ink composition are ejected, and the droplets are attached to a recording medium to perform recording, wherein the recording medium is any one of claims 10 to 13. An ink-jet recording method using the recording medium described in (1). 16. An ink jet recording method in which droplets of an ink composition are ejected and the droplets are attached to a recording medium to perform recording, wherein the ink composition is used as the ink composition.
14. An ink jet recording method using the ink composition according to any one of claims 10 to 13, and using the recording medium according to any one of claims 10 to 13 as the recording medium. 17. An ink jet recording method in which droplets of an ink composition are ejected, and the droplets are attached to a recording medium to perform recording, wherein the ink composition is any one of claims 1 to 9. The recording medium is provided with an ink receiving layer on a substrate, and the ink receiving layer contains MS ₂ O ₄ , MSO ₃ ,
A recording medium containing at least one inorganic salt selected from the group consisting of compounds represented by MS ₂ O ₃ , MPH ₂ O ₂ , and MPHO ₃ (M is an alkali metal or an alkaline earth metal) is used. Characteristic ink jet recording method. 18. A method for ejecting a droplet of an ink composition, comprising:
Ink-jet recording, in which recording is performed by adhering ink to a recording medium
A method, wherein the ink composition comprises a colorant, water, MS
₂O₄, MSO₃, MS₂O ₃, MPH₂O₂, MPH
O₃(M is an alkali metal or alkaline earth metal)
At least one selected from the group consisting of the compounds represented by
An ink composition containing the above-mentioned inorganic salts, and the recording medium according to any one of claims 10 to 13.
Characterized by using the recording medium described in (1).
Jet recording method. 19. An ink jet recording method for ejecting droplets of an ink composition and attaching the droplets to a recording medium for recording, wherein the ink composition comprises a colorant, water, An ink composition containing a compound represented by the formula (1) is used. As the recording medium, an ink receiving layer is provided on a base material, and MS ₂ O ₄ and MS are contained in the ink receiving layer.
O ₃ , MS ₂ O ₃ , MPH ₂ O ₂ , MPHO ₃ (M is
An ink jet recording method comprising using a recording medium containing at least one or more inorganic salts selected from the group consisting of compounds represented by alkali metals or alkaline earth metals). Embedded image (In the formula (1), X is hydrogen, an oxy radical group, a hydroxyl group,
An alkyl group, an alkenyl group, an alkynyl group, an aryl group, an acyl group, a sulfonyl group, a sulfinyl group, an alkoxy group, an aryloxy group or an acyloxy group, wherein R ¹ , R ² , R ³ and R ⁴ are each hydrogen or an alkyl group; And Z is a group of non-metallic atoms necessary to complete the 5- to 7-membered ring. Here, any two groups of R ^{1 to} R ⁴ and Z may be bonded to each other to form a 5- to 7-membered ring. ) 20. An ink jet recording method in which droplets of an ink composition are ejected and the droplets are attached to a recording medium to perform recording, wherein the ink composition comprises a colorant, water, An inkjet recording method, comprising using an ink composition containing a compound represented by the formula (1), and using the recording medium according to any one of claims 10 to 13 as the recording medium. Embedded image (In the formula (1), X is hydrogen, an oxy radical group, a hydroxyl group,
An alkyl group, an alkenyl group, an alkynyl group, an aryl group, an acyl group, a sulfonyl group, a sulfinyl group, an alkoxy group, an aryloxy group or an acyloxy group, wherein R ¹ , R ² , R ³ and R ⁴ are each hydrogen or an alkyl group; And Z is a group of non-metallic atoms necessary to complete the 5- to 7-membered ring. Here, any two groups of R ^{1 to} R ⁴ and Z may be bonded to each other to form a 5- to 7-membered ring. ) 21. The ink composition according to claim 19, wherein the content of the compound represented by the general formula (1) is 0.05% by weight or more and 10% by weight or less.
The ink-jet recording method as described above. 22. The ink jet recording method according to claim 18, wherein the content of the inorganic salt in the ink composition is 0.01% by weight or more and 10% by weight or less. 23. The ink jet recording method according to claim 17, wherein the content of the inorganic salt in the recording medium is 0.01% by weight or more and 10% by weight or less. 24. A recorded matter recorded by the inkjet recording method according to claim 14. Description: