JP5279283B2 - Liquid composition, image forming method, cartridge, recording unit, and ink jet recording apparatus - Google Patents

Abstract

The present invention provides a liquid composition, an image forming method, an ink box, a recording unit and an ink jet recorder, in particular, to a liquid composition which can achieve superior scratch resistance of images at such a level that coloring materials are hardly scraped off even when images are scratched with finger nails under application of such strong pressure as to scratch a recording medium at its non-recorded areas. The liquid composition contains at least a modified siloxane compound having specific structure and a polymer whose acid value and hydrogen bond parameter (deltah) are specified.

Description

  The present invention relates to a liquid composition used together with a pigment ink using a pigment as a coloring material, and an image forming method, a cartridge, a recording unit, and an ink jet recording apparatus applicable to an ink jet recording method using the liquid composition.

  In inkjet recording inks, images formed with pigment inks containing pigments as colorants are more robust, such as light resistance and ozone resistance, compared to images formed with dye inks containing dyes as colorants. Excellent. On the other hand, an image formed with pigment ink has a problem that the color material is scraped off when the image is rubbed with a finger or the like, that is, the scratch resistance is inferior, compared with an image formed with dye ink.

  In response to the above problems, many proposals have been made regarding a method for protecting a recorded matter by applying a surface coat to an image. For example, there is a proposal related to protecting an image by thermally transferring a protective layer transfer sheet to the image (see Patent Document 1). There is also a proposal for protecting an image by simultaneously heating and pressing the image (see Patent Document 2). Furthermore, there is a proposal relating to protecting an image by applying a liquid containing a compound that forms a film to an image formed with pigment ink (see Patent Documents 3 and 4).

Japanese Patent Laid-Open No. 2000-153677 JP 2003-170650 A JP 2004-99766 A JP 2005-81754 A

  However, the degree of scratch resistance required for images to be displayed outdoors such as posters, panels, signs, pop advertisements, etc. is high, and color materials do not scrape off when rubbed with fingers, etc., as in the conventional technology. Such a level is insufficient.

  For example, when printing posters and advertisements, a fairly large recording medium such as A0 size or A1 size is often used, and when carrying a recording medium on which an image is formed, it is generally rolled up into a cylindrical shape. Therefore, the following problems may occur. When the recording medium is rolled, the image may be rubbed with a sharp portion such as a corner of the recording medium. At this time, even when the conventional pigment ink, which is said to satisfy the scratch resistance of the image at a high level, is used, there is a problem that the formed image is scratched and the color material is scraped off. Occurs. Similar problems also occur in other situations. For example, when an image formed with pigment ink is pasted outdoors as a poster, the image is strongly scratched by a sharp object such as a nail. Also at this time, as described above, the problem that the color material is scraped off occurs frequently.

  In the case of using the method described in Patent Document 1 for the above problems, the object of the present invention can be achieved by devising measures such as increasing the strength of the protective layer or increasing the film thickness. I may be able to do it. However, the methods described in Patent Documents 1 and 2 are not so preferable because the apparatus becomes complicated, such as an apparatus for performing thermal transfer and a heat roller. Therefore, in recent years, even when a sharp object such as a nail touches an image, a water-based ink capable of obtaining an image having a higher scratch resistance than before, in which the color material of the image is not scraped off. Development is required.

  In addition to the above four patent documents, there are a number of proposals related to improving the scratch resistance of the image when an image is formed using an ink-jet pigment ink. However, according to the study by the present inventors, no matter which technique is used, it is best to obtain scratch resistance that does not cause scratches when touching the recording medium with a finger.

  For example, in Patent Documents 3 and 4, a water-soluble resin is contained in a topcoat liquid or colorless ink. However, as a result of the study by the present inventors, the binding force between the recording medium, the resin, and the pigment is determined only by the characteristics of the resin, no matter how much the content of the resin effective for improving the scratch resistance of the image is increased. Therefore, it was found that the scratch resistance of the image is improved only to a certain extent. That is, even in the inventions described in Patent Documents 3 and 4 that improve the scratch resistance of an image only by the characteristics of the resin, the invention does not exceed the category of conventional scratch resistance, and the scratch resistance intended by the present invention is not exceeded. The level of sex has not been reached. In other words, these techniques are intended for the present invention, “the coloring material is almost scraped off even when scratched by a sharp object such as a nail by applying a pressure strong enough to scratch the non-recording portion of the recording medium. It has not reached the high level of scratch resistance of “No”. In particular, when the content of the pigment solid content in the ink is 1.2% by mass or less based on the total mass of the ink, the content of the solid content that functions as a filler agent is small. It is difficult to obtain an image having high scratch resistance.

  The above is apparent from the evaluation methods of Examples in Patent Documents 3 and 4. That is, in Patent Document 3, plain paper is placed on an image, and a specific weight is placed and rubbed. In Patent Document 4, an image is rubbed with an eraser. In other words, these evaluation methods are for evaluating the degree of deterioration when the recorded material is rubbed, and can be said to be a fairly gradual evaluation standard as compared with the intended level of scratch resistance of the present invention. .

  Furthermore, in the invention described in Patent Document 3, the application amount of the top coat liquid for protecting the image is more than twice the application amount of the ink, and a considerable time is required until fixing. This is also clear from the fact that the scratch resistance evaluation test of the example of Patent Document 3 is performed after 24 hours. Further, when an image is formed on a recording medium having an ink receiving layer, if the liquid is applied in an application amount that exceeds the ability of the ink receiving layer to hold the liquid, there arises a problem that the recording medium cannot absorb the liquid. That is, as in the invention described in Patent Document 3, it can be said that it is not realistic to set the topcoat liquid application amount far exceeding the ink application amount necessary to form an image.

  Therefore, the object of the present invention is applicable to ink jet recording, and thus satisfies the reliability such as ejection characteristics such as sticking resistance and storage stability, and at the same time, the scratch resistance of an image formed with pigment ink. It is an object of the present invention to provide a liquid composition that can be improved to a higher level. Specifically, it is possible to obtain an image having a high level of scratch resistance in which the coloring material is hardly scraped off even when a pressure is applied to the non-recording portion of the recording medium so as to damage the non-recording portion. It is to provide a liquid composition that can be used. Another object of the present invention is to provide an image forming method, a cartridge, a recording unit, and an ink jet recording apparatus applicable to the ink jet recording method, in which an image having such a high level of scratch resistance can be obtained. It is in.

（式（１）で表される変性シロキサン化合物の重量平均分子量は８，０００以上３０，０００以下であり、式（１）中、Ｒ₁は炭素数１以上２０以下のアルキレン基であり、Ｒ₂は水素原子又は炭素数１以上２０以下のアルキル基であり、ｍは１以上２５０以下、ｎは１以上１００以下、ａは１以上１００以下、ｂは０以上１００以下である。）

（式（２）で表される変性シロキサン化合物の重量平均分子量は８，０００以上５０，０００未満であり、式（２）中、Ｒ₃はそれぞれ独立に、水素原子又は炭素数１以上２０以下のアルキル基であり、Ｒ₄は炭素数１以上２０以下のアルキレン基であり、ｐは１以上４５０以下、ｃは１以上２５０以下、ｄは０以上１００以下である。）

（式（３）で表される変性シロキサン化合物は、重量平均分子量が８，０００以上５０，０００未満、かつＨＬＢが１以上７未満であり、式（３）中、Ｒ₅はそれぞれ独立に、水素原子又は炭素数１以上２０以下のアルキル基であり、Ｒ₆は炭素数１以上２０以下のアルキレン基であり、ｑは１以上１００以下、ｒは１以上１００以下、ｅは１以上１００以下、ｆは０以上１００以下である。） The above object is achieved by the present invention described below. That is, the liquid composition according to the present invention is a liquid composition containing at least a modified siloxane compound and a resin,
The modified siloxane compound is selected from the group consisting of a modified siloxane compound represented by the following formula (1), a modified siloxane compound represented by the following formula (2), and a modified siloxane compound represented by the following formula (3). The resin has an acid value of 90 mgKOH / g or more and 150 mgKOH / g or less, and the hydrogen bond term (δh) of the resin calculated from the solubility parameter of the monomer constituting the resin is 1. Calculated from the solubility parameter of the resin A having 0 cal ^0.5 / cm ^{1.5 to} 3.7 cal ^0.5 / cm ^1.5 and an acid value of more than 150 mg KOH / g and 200 mg KOH / g and constituting the resin A resin B having a hydrogen bond term (δh) of 1.0 cal ^0.5 / cm ^{1.5 to 1.5} cal ^0.5 / cm ^1.5 At least one resin , the resin comprising at least one monomer of acrylic acid and methacrylic acid, styrene, α-methylstyrene, benzyl methacrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, and n-hexyl. It is a resin copolymerized using at least one monomer selected from the group consisting of acrylates .

(The weight average molecular weight of the modified siloxane compound represented by the formula (1) is 8,000 or more and 30,000 or less, and in the formula (1), R ₁ is an alkylene group having 1 to 20 carbon atoms; ₂ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, m is 1 to 250, n is 1 to 100, a is 1 to 100, and b is 0 to 100.

(The weight average molecular weight of the modified siloxane compound represented by the formula (2) is 8,000 or more and less than 50,000, and in the formula (2), each R ₃ is independently a hydrogen atom or a carbon number of 1 or more and 20 or less. R ₄ is an alkylene group having 1 to 20 carbon atoms, p is 1 to 450, c is 1 to 250, and d is 0 to 100.)

(The modified siloxane compound represented by the formula (3) has a weight average molecular weight of 8,000 or more and less than 50,000 and an HLB of 1 or more and less than 7, and in the formula (3), each R ₅ is independently A hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R ₆ is an alkylene group having 1 to 20 carbon atoms, q is 1 to 100, r is 1 to 100, and e is 1 to 100. , F is 0 or more and 100 or less.)

  An image forming method according to another embodiment of the present invention is an image forming method including a step of applying a pigment ink to a recording medium, and a step of applying a liquid composition to the recording medium. As the composition, the liquid composition described above is used. A particularly preferred form is an image forming method in which the pigment ink and the liquid composition are applied to a recording medium by an inkjet method.

  Further, a cartridge according to another embodiment of the present invention is a cartridge comprising a liquid composition container that contains a liquid composition, and the liquid composition contained in the liquid composition container is It is said liquid composition.

  Further, a recording unit according to another embodiment of the present invention is a recording unit comprising a liquid composition container that stores a liquid composition and a recording head that discharges the liquid composition, wherein the liquid composition The liquid composition housed in the object housing section is the liquid composition described above.

  In addition, an ink jet recording apparatus according to another embodiment of the present invention is an ink jet recording apparatus including a liquid composition container that stores a liquid composition and a recording head that discharges the liquid composition, The liquid composition housed in the liquid composition housing section is the liquid composition described above.

  According to the present invention, the scratch resistance of an image formed using a pigment ink can be made far superior to the scratch resistance aimed at by the conventional technique. In other words, according to the present invention, an image having excellent scratch resistance at a level where the coloring material is hardly scraped off even when the nail is scratched by applying a pressure strong enough to scratch the non-recording portion of the recording medium. A liquid composition that can be provided is provided. In addition, according to the present invention, an image forming method applicable to an ink jet recording method, a cartridge, a recording unit, which can stably obtain an image having a remarkably high level of scratch resistance as described above, In addition, an ink jet recording apparatus can be provided.

  Hereinafter, preferred embodiments of the present invention will be described in detail. The greatest point of the present invention is that an ink is formed by using a liquid composition containing a specific modified siloxane compound in addition to a specific resin described later and a pigment ink, and using the ink. The purpose is to make the surface of the formed image slippery. As a result of the surface of the image becoming slippery, it is possible to dramatically improve the scratch resistance of the image as compared with an image formed using a conventional ink and liquid composition. That is, the present invention differs from the idea of improving the scratch resistance by using only the film-forming property of the resin as in the prior art, and an image and a substance (for example, a nail) that contacts the image. This is based on the new idea of paying attention to the frictional force. As a result, according to the present invention, even when the non-recording portion of the recording medium is applied with such a strong pressure as to be scratched and scratched with a nail, not only the coloring material is not scraped off, but also an image in which scars are hardly left. It can also be provided.

  As a result of the study by the present inventors, the frictional force between the image for achieving the object of the present invention and a substance (for example, a nail) in contact with the image, that is, the slipperiness of the image surface is an index of the dynamic friction coefficient. It can be expressed as The dynamic friction coefficient can be measured as follows using a scratch resistance test apparatus. FIG. 1 is a schematic diagram for explaining the scratch resistance test.

  In this test, a polymethyl methacrylate (PMMA) ball is used as the friction material 2-3 that generates a scratch close to a scratch by a nail. Then, scratches are generated as follows using a surface property tester (trade name: Haydon Tribogear TYPE 14DR; manufactured by Shinto Kagaku). Specifically, as shown in FIG. 1, a PMMA ball to which a load is applied from above is brought into contact with the image plane vertically, and the sample 2-2 on the operation stage 2-1 is moved at a predetermined speed. Causes scratches.

  The mass of the metal fitting for fixing the friction material is removed by the balance mechanism 2-5. The scratch resistance of the image surface is evaluated by a vertical load (weight 2-4) applied to the image surface. Further, the horizontal force acting on the friction object when the stage is moved can be measured through the load cell 2-6 connected to the fixture. From the ratio of the horizontal force and the vertical load force during movement, the dynamic friction coefficient of the image surface with respect to the friction object can be measured.

  The present inventors conducted a detailed examination by conducting a scratch resistance test on various images by the method described above. As a result, when an image is formed on a recording medium having a coat layer, if the dynamic friction coefficient of the image is 0.40 or less, further less than 0.35, particularly 0.30 or less, the present invention has a high target. It was found that the image can satisfy the level of scratch resistance. The lower limit of the dynamic friction coefficient is 0.00 or more.

  Here, a liquid containing a specific modified siloxane compound together with a specific resin, which will be described later, in order to set the dynamic friction coefficient of an image formed with pigment ink (hereinafter sometimes simply referred to as “ink”) to 0.40 or less. The background to the construction of the present invention using the composition will be described. First, in order to achieve the object of the present invention, the present inventors have studied a liquid composition containing several types of modified siloxane compounds that have been reported to have an effect of improving the slip property of the coating film surface. Went. However, when the dynamic friction coefficient of an image formed using the liquid composition containing the specific modified siloxane compound is compared with the dynamic friction coefficient of an image formed using the liquid composition not containing the specific modified siloxane compound. It was found that there was no difference in the value of the dynamic friction coefficient. That is, simply using the liquid composition containing any modified siloxane compound investigated by the present inventors, the dynamic friction coefficient intended by the present invention is not reached, and the scratch resistance is sufficient. I found out I couldn't get it. As described above, the reason why the dynamic friction coefficient of the formed image does not change despite the use of the liquid composition containing the modified siloxane compound, which is said to have the effect of improving the slip property of the coating film surface, is clear. Not sure. However, the inventors have found that the modified siloxane compound in the liquid composition penetrates into the inside of the recording medium together with the aqueous medium in the liquid composition, so that the modified siloxane compound exists on the recording medium. I'm guessing that it's because it's not going to happen.

  Accordingly, the present inventors have studied a configuration for leaving most of the modified siloxane compound in the liquid composition on the recording medium. First, the present inventors considered using a modified siloxane compound and a resin in combination, and utilizing a synergistic effect between the properties of the modified siloxane compound and the properties of the resin used in combination therewith. Further, the present invention has a configuration in which the modified siloxane compound is adsorbed to a pigment or a resin in a liquid composition constituting an image and is present on the recording medium together with the resin by utilizing the characteristics of the modified siloxane compound having high hydrophobicity. We thought that it was the best for achieving the purpose of, and proceeded with the examination.

First, the present inventors examined a resin to be contained in a liquid composition. As a result, it was concluded that it is optimal to contain at least one of resin A and resin B having the following characteristics as a resin that can be fixed on a recording medium and form a film having a certain degree of strength. It was. That is, the resin A has an acid value of 90 mgKOH / g or more and 150 mgKOH / g or less, and a hydrogen bond term (δh) of the resin calculated from the solubility parameter of the monomer constituting the resin is at least 3.7 cal. Resin of ^0.5 / cm ^1.5 or less. The resin B has an acid value of more than 150 mgKOH / g and 200 mgKOH / g or less, and a hydrogen bond term of the resin calculated from the solubility parameter of the monomer constituting the resin is at least 1.5 cal ^0.5 / It is a resin of cm ^1.5 or less. Here, the hydrogen bond term (δh) of the resin is a value calculated from a solubility parameter specific to the monomer constituting the resin, and details thereof will be described later.

  In addition, resin which can be used as a structural component of the liquid composition of this invention is not restricted to resin A or resin B mentioned above. That is, when the liquid composition is constituted with a specific modified siloxane compound used in the present invention and the liquid composition is used for image formation, the present invention aims at scratch resistance of an image formed with ink. Any resin can be used as long as it can be made to a high level. Specifically, any resin that has the property of causing solid-liquid separation immediately after applying the liquid composition to the recording medium and fixing it onto the recording medium may be used. Furthermore, the dynamic friction coefficient of the reference evaluation image formed using the ink and the liquid composition containing both the resin and the specific modified siloxane compound described later can be configured to be 0.40 or less. I just need it. That is, any resin can be used as a constituent of the liquid composition of the present invention as long as it is a resin capable of forming a film having a certain degree of strength after remaining on the recording medium after the liquid composition is applied to the recording medium. It is. Furthermore, if it is a resin having such characteristics and adsorbing with a specific modified siloxane compound, which is essential for achieving the object of the present invention, and which improves the slipperiness of the image described later, Is particularly optimal. The “reference evaluation image” in the present invention is an image recorded under the following conditions using a liquid composition containing both a resin and a specific modified siloxane compound and a pigment ink. That is, in an area including at least an image formed with pigment ink, the discharge amount per droplet of liquid composition: 3 ng to 5 ng, resolution: 1,200 dpi × 1,200 dpi, 8-pass bidirectional recording, recording duty: 50% It is an image formed by applying a liquid composition under conditions.

  In the course of the study, the present inventors used at least one kind of resin A and resin B having the above-mentioned characteristics, and a liquid composition and an ink containing the modified siloxane compound studied above. Images were formed and the resulting images were examined for scratch resistance. As a result, by using a specific modified siloxane compound, it is possible to obtain an image that achieves scratch resistance far exceeding the scratch resistance of an image formed using a liquid composition containing only a resin having the above characteristics. I understood.

  Therefore, the present inventors formed an image using a resin having the above-mentioned characteristics, a liquid composition containing a specific modified siloxane compound that was effective in reducing the dynamic friction coefficient, and ink, The dynamic friction coefficient and scratch resistance of the obtained image were examined. As a result, the dynamic friction coefficient of the image is 0.40 or less, and when used in combination with a specific modified siloxane compound, the image formed using a liquid composition containing only a resin having the above characteristics and ink is scratch resistant. It was found that an image having a scratch resistance much higher than that can be obtained.

As a result of the above examination, an optimal configuration of the present invention, which is a liquid composition containing at least one kind of resin A and resin B having the above-described characteristics and a specific modified siloxane compound, is included. It came to. More specifically, at least one kind of resin A and resin B having the following characteristics is used. The resin A has an acid value of 90 mgKOH / g or more and 150 mgKOH / g or less, and the hydrogen bond term of the resin calculated from the solubility parameter of the monomer constituting the resin is 1.0 cal ^0.5 / cm ^1.5 or more and 3.7 cal ^0.5 / Cm ^1.5 or less resin. Resin B has an acid value of more than 150 mgKOH / g and 200 mgKOH / g or less, and a hydrogen bond term of the resin calculated from the solubility parameter of the monomer constituting the resin is 1.0 cal ^0.5 / cm ^1.5 or more. It is a resin of ⁵ cal ^0.5 / cm ^1.5 or less. By using the liquid composition having such a configuration, the modified siloxane compound can be present on the recording medium, and as a result, the modified siloxane compound has a sufficient effect of improving the slip property of the coating film surface, Excellent image scratch resistance can be achieved. Regarding resin A and resin B, the reason why the lower limit of the hydrogen bond term of the resin calculated from the solubility parameter of the monomer constituting the resin is 1.0 cal ^0.5 / cm ^1.5 or more will be described later.

  Further, as a result of studying various modified siloxane compounds, the present inventors have found that it is necessary to use the following modified siloxane compounds in order to realize the intended scratch resistance of the present invention. It was. Specifically, it is selected from the group consisting of a modified siloxane compound represented by the following formula (1), a modified siloxane compound represented by the following formula (2), and a modified siloxane compound represented by the following formula (3). We have found that at least one is optimal. These modified siloxane compounds are used as components of a liquid composition together with a resin, and when the liquid composition and a pigment ink are used in combination, for example, when used for image formation on a recording medium having a coating layer, the standard thereof is used. The dynamic friction coefficient of the evaluation image can be 0.40 or less. The dynamic friction coefficient of the reference evaluation image is a value obtained by the test method described above.

（式（１）で表される変性シロキサン化合物の重量平均分子量は８，０００以上３０，０００以下である。式（１）中、Ｒ₁は炭素数１以上２０以下のアルキレン基であり、Ｒ₂は水素原子又は炭素数１以上２０以下のアルキル基であり、ｍは１以上２５０以下、ｎは１以上１００以下、ａは１以上１００以下、ｂは０以上１００以下である。）

(The weight average molecular weight of the modified siloxane compound represented by the formula (1) is 8,000 or more and 30,000 or less. In the formula (1), R ₁ is an alkylene group having 1 to 20 carbon atoms, and R ₂ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, m is 1 to 250, n is 1 to 100, a is 1 to 100, and b is 0 to 100.

（式（２）で表される変性シロキサン化合物の重量平均分子量は８，０００以上５０，０００未満である。式（２）中、Ｒ₃はそれぞれ独立に、水素原子又は炭素数１以上２０以下のアルキル基であり、Ｒ₄は炭素数１以上２０以下のアルキレン基であり、ｐは１以上４５０以下、ｃは１以上２５０以下、ｄは０以上１００以下である。）

(The weight average molecular weight of the modified siloxane compound represented by the formula (2) is 8,000 or more and less than 50,000. In the formula (2), each R ₃ is independently a hydrogen atom or a carbon number of 1 or more and 20 or less. R ₄ is an alkylene group having 1 to 20 carbon atoms, p is 1 to 450, c is 1 to 250, and d is 0 to 100.)

（式（３）で表される変性シロキサン化合物は、重量平均分子量が８，０００以上５０，０００未満、かつＨＬＢが１以上７未満である。式（３）中、Ｒ₅はそれぞれ独立に、水素原子又は炭素数１以上２０以下のアルキル基であり、Ｒ₆は炭素数１以上２０以下のアルキレン基であり、ｑは１以上１００以下、ｒは１以上１００以下、ｅは１以上１００以下、ｆは０以上１００以下である。）

(The modified siloxane compound represented by the formula (3) has a weight average molecular weight of 8,000 or more and less than 50,000 and an HLB of 1 or more and less than 7. In the formula (3), each R ₅ is independently A hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R ₆ is an alkylene group having 1 to 20 carbon atoms, q is 1 to 100, r is 1 to 100, and e is 1 to 100. , F is 0 or more and 100 or less.)

  The above means that even if it is a modified siloxane compound having the effect of improving the slip property (slip property) of the coating film surface, the optimum effect of the present invention may not always be obtained. ing. That is, for example, when an image is formed using a liquid composition containing a modified siloxane compound having a weight average molecular weight outside the above range in combination with ink, the properties inherent to the modified siloxane compound cannot be sufficiently obtained. In some cases. The reason for this is not clear, but the present inventors speculate as follows. As described above, it is considered that the resin and the modified siloxane compound are adsorbed as a mechanism for achieving the object of the present invention. However, for example, when the weight average molecular weight of the modified siloxane compound represented by the above formula (1) exceeds 30,000, the adsorption between the resin and the modified siloxane compound may be difficult to occur due to the influence of steric hindrance and the like. it is conceivable that. Further, when the weight average molecular weight of the modified siloxane compound represented by the above formula (2) or the above formula (3) is 50,000 or more, adsorption between the resin and the modified siloxane compound occurs due to steric hindrance. It may be difficult. As a result, it is assumed that such a modified siloxane compound penetrates into the inside of the recording medium and cannot reduce the dynamic friction coefficient of the image. On the other hand, when the weight average molecular weight of the modified siloxane compound represented by the above formula (1), formula (2), and formula (3) is less than 8,000, the modified siloxane compound oriented on the surface of the image is It is presumed that the dynamic friction coefficient of the image may not be lowered because it decreases. Alternatively, when the weight average molecular weight is less than 8,000, the modified siloxane compound itself permeates into the inside of the recording medium, so that the dynamic friction coefficient of the image may not be lowered.

The “hydrogen bond term (δh) of the resin calculated from the solubility parameter of the monomer constituting the resin” that defines the resin used in the present invention will be described. First, the solubility parameter will be described. The solubility parameter is affected by the type of functional group in the compound. The solubility parameter is one of the factors for determining the solubility of a plurality of compounds, that is, the strength of affinity between the compounds. When the solubility parameters of each of the plurality of compounds are close, these compounds There is a tendency that the mutual solubility becomes high. The solubility parameter includes the dispersion force term (δd) due to the primary bias of the electron distribution, the polar term (δp) due to the attractive force generated by the dipole moment, and the hydrogen bonds generated by active hydrogen and lone electron pairs. It is divided into the resulting hydrogen bond term (δh). In the present invention, the solubility parameter is applied to the resin, but the greater the value of the hydrogen bond term (δh) of the resin, the greater the affinity between the resin and water. The hydrogen bond term (δh) of the resin can be calculated from the solubility parameter of the monomer constituting the resin. In that case, it can be obtained by using the atomic group summation method proposed by Krebelen, in which organic molecules are handled as atomic groups. (See Krevelen, Properties of Polymer 2nd Edition, New York, 154 (1976).) This method is as follows. First, from the dispersion force parameter Fdi per mole, the polar force parameter Fpi per mole, and the hydrogen bond strength parameter Fhi per mole of each atomic group of the organic molecule, the solubility parameter dispersion force term (δd), polarity term (δp) ), A hydrogen bond term (δh) is obtained. Then, by using these values, the solubility parameter (δ) can be obtained as in the following formula. In the present invention, as described later, the hydrogen bond term (δh) of the resin was calculated using the above-described concept and using the solubility parameter unique to each monomer constituting the resin.

  The present inventors consider whether the resin penetrates into the inside of the recording medium together with the aqueous medium by considering the hydrogen bond term (δh) contributing to the solubility parameter (δ) for the resin contained in the liquid composition. In other words, the inventors have found that it is possible to determine whether the toner remains on the recording medium and is fixed. Although the relationship between the hydrogen bond term (δh) that contributes to the solubility parameter (δ) and the degree of penetration into the recording medium is not clear, the present inventors presume as follows. That is, the hydrogen bond term (δh) is derived from a hydrogen bond, and as the hydrogen bond term of the resin increases, the affinity between the resin and water tends to increase. As in the liquid composition of the present invention, a liquid composition mainly containing an aqueous medium tends to lower the cohesiveness between resins as the resin hydrates as the hydrogen bond term of the resin increases. . Accordingly, it is assumed that the resin tends to penetrate into the recording medium without aggregating on the recording medium, and the ratio of the resin remaining on the recording medium tends to decrease.

According to the study by the present inventors, the preferred range varies depending on the acid value of the resin, but the resin A having the value of the hydrogen bond term of the resin calculated from the solubility parameter of the monomer constituting the resin, which will be described later, and It is preferable to use resin B as a constituent of the liquid composition. That is, a resin (resin A) having an acid value of 90 mgKOH / g or more and 150 mgKOH / g or less, and a resin (resin B) having an acid value of more than 150 mgKOH / g and 200 mgKOH / g or less, The preferred range differs as follows. In the case of the resin A having an acid value in the above range, the value of the hydrogen bond term (δh) of the resin calculated from the solubility parameter of the monomer constituting the resin is 1.0 cal ^0.5 / cm ^1.5 or more and 3.7 cal ^0.5 / cm. It is preferably ^1.5 or less. In the case of the resin B having an acid value in the above range, the value of the hydrogen bond term (δh) of the resin calculated from the solubility parameter of the monomer constituting the resin is 1.0 cal ^0.5 / cm ^1.5 or more and ^1.5 cal ^0.5 / Cm ^1.5 or less is preferable. As a result, it is possible to accurately select a resin that can achieve the effects of the present invention.

[Liquid composition]
Hereafter, each component which comprises the liquid composition of this invention is demonstrated. In addition, it is preferable that the liquid composition of this invention is substantially colorless or light-colored. Here, “substantially colorless or light color” means that the image density is not substantially lowered when a liquid composition is applied to a region containing an image formed with ink. More specifically, it is preferable that the liquid composition does not have a maximum absorption wavelength in the visible region of 400 nm to 700 nm, and the liquid composition satisfying such a condition may be somewhat cloudy. Moreover, it is preferable that the difference between the image density of the image to which the liquid composition is applied and the image density of the image to which the liquid composition is not applied is 0.3 or less, more preferably 0.1 or less. The fact that the liquid composition of the present invention has such characteristics can be achieved, for example, when the liquid composition does not contain a coloring material.

<Modified siloxane compound>
The modified siloxane compound used in the liquid composition of the present invention is a modified siloxane compound represented by the following formula (1), a modified siloxane compound represented by the following formula (2), and a modified siloxane compound represented by the following formula (3). It is at least one selected from the group consisting of siloxane compounds.

In the modified siloxane compounds represented by the following formulas (1), (2), and (3), (C ₂ H ₄ O) is an ethylene oxide unit, and (C ₃ H ₆ O) is Each propylene oxide unit is shown. In each modified siloxane compound, the state in which the ethylene oxide unit and the propylene oxide unit exist in the structure may exist in any state such as a random form or a block form. However, in the present invention, these are preferably present in a random form or a block form. Here, that each unit exists in a random state means that ethylene oxide units and propylene oxide units are irregularly arranged. In addition, the presence of each unit in a block state means that each block is composed of several units as described above, and the blocks configured in this way are regularly arranged. Yes.

（式（１）で表される変性シロキサン化合物の重量平均分子量は８，０００以上３０，０００以下である。式（１）中、Ｒ₁は炭素数１以上２０以下のアルキレン基であり、Ｒ₂は水素原子又は炭素数１以上２０以下のアルキル基であり、ｍは１以上２５０以下、ｎは１以上１００以下、ａは１以上１００以下、ｂは０以上１００以下である。） [Compound of Formula (1)]

(The weight average molecular weight of the modified siloxane compound represented by the formula (1) is 8,000 or more and 30,000 or less. In the formula (1), R ₁ is an alkylene group having 1 to 20 carbon atoms, and R ₂ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, m is 1 to 250, n is 1 to 100, a is 1 to 100, and b is 0 to 100.

R ₁ is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an ethylene group, a propylene group, or a butylene group. R ₂ is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an ethyl group or a propyl group. m is preferably 1 or more and 250 or less, more preferably 1 or more and 100 or less, and particularly preferably 1 or more and 50 or less. n is preferably 1 or more and 100 or less, more preferably 1 or more and 50 or less. a is preferably 1 or more and 100 or less, and more preferably 1 or more and 50 or less. b is preferably 0 or more and 100 or less, and more preferably 1 or more and 50 or less.
The compound represented by the above formula (1) used in the present invention is obtained by an addition reaction of two kinds of compounds represented by the following formula. That is, it can be obtained by addition reaction of a polysiloxane having n hydrogen atoms bonded to n Si, a compound having a structure having one alkene group at the terminal and an ethylene oxide unit and / or a propylene oxide unit. . Specifically, it can be obtained by adding an alkene group to a hydrogen atom of polysiloxane. In these formulas, m is 1 to 250, n is 1 to 100, a is 1 to 100, and b is 0 to 100. R is an alkene group having 1 to 20 carbon atoms.

（式（２）で表される変性シロキサン化合物の重量平均分子量は８，０００以上５０，０００未満である。式（２）中、Ｒ₃はそれぞれ独立に、水素原子又は炭素数１以上２０以下のアルキル基であり、Ｒ₄は炭素数１以上２０以下のアルキレン基であり、ｐは１以上４５０以下、ｃは１以上２５０以下、ｄは０以上１００以下である。） [Compound of Formula (2)]

(The weight average molecular weight of the modified siloxane compound represented by the formula (2) is 8,000 or more and less than 50,000. In the formula (2), each R ₃ is independently a hydrogen atom or a carbon number of 1 or more and 20 or less. R ₄ is an alkylene group having 1 to 20 carbon atoms, p is 1 to 450, c is 1 to 250, and d is 0 to 100.)

R ₃ is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom, an ethyl group, or a propyl group. R ₄ is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an ethylene group, a propylene group, a butylene group, or the like. p is preferably 1 or more and 450 or less, more preferably 1 or more and 100 or less, and particularly preferably 1 or more and 50 or less.
The compound represented by the above formula (2) used in the present invention is obtained by an addition reaction of two kinds of compounds represented by the following formula. That is, it can be obtained by an addition reaction between a polysiloxane having a hydrogen atom in Si at both ends, a alkene group at one end, and a compound having an ethylene oxide unit and / or a propylene oxide unit. Specifically, it can be obtained by adding an alkene group to a hydrogen atom of polysiloxane. In these formulas, p is from 1 to 450, c is from 1 to 250, and d is from 0 to 100. R is an alkene group having 1 to 20 carbon atoms.

（式（３）で表される変性シロキサン化合物は、重量平均分子量が８，０００以上５０，０００未満、かつＨＬＢが１以上７未満である。式（３）中、Ｒ₅はそれぞれ独立に、水素原子又は炭素数１以上２０以下のアルキル基であり、Ｒ₆は炭素数１以上２０以下のアルキレン基であり、ｑは１以上１００以下、ｒは１以上１００以下、ｅは１以上１００以下、ｆは０以上１００以下である。） [Compound of Formula (3)]

(The modified siloxane compound represented by the formula (3) has a weight average molecular weight of 8,000 or more and less than 50,000 and an HLB of 1 or more and less than 7. In the formula (3), each R ₅ is independently A hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R ₆ is an alkylene group having 1 to 20 carbon atoms, q is 1 to 100, r is 1 to 100, and e is 1 to 100. , F is 0 or more and 100 or less.)

R ₅ is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom, an ethyl group, or a propyl group. R ₆ is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an ethylene group, a propylene group, a butylene group, or the like. e is preferably 1 or more and 100 or less, more preferably 1 or more and 50 or less. f is preferably 1 or more and 100 or less, more preferably 1 or more and 50 or less.
The compound represented by the above formula (3) used in the present invention is obtained by an addition reaction of two kinds of compounds represented by the following formula. That is, it can be obtained by an addition reaction between a polysiloxane having hydrogen atoms in Si at both ends, an alkene group at both ends, and a compound having a structure having an ethylene oxide unit and / or a propylene oxide unit. Specifically, it can be obtained by adding an alkene group to a hydrogen atom of polysiloxane. In these formulas, q is from 1 to 100, r is from 1 to 100, e is from 1 to 100, and f is from 0 to 100. R is an alkene group having 1 to 20 carbon atoms.

  In addition, if the image which has the high level of abrasion resistance which this invention aims at is obtained, the group which consists of said modified | denatured siloxane compound represented by Formula (1), Formula (2), and Formula (3). Any of the at least one modified siloxane compound selected from can be used. However, as a result of detailed studies by the inventors, it is particularly preferable to use a modified siloxane compound having the following weight average molecular weight. Specifically, in the case of the modified siloxane compound represented by the above formula (1), the weight average molecular weight (MW) is 8,000 or more and 30,000 or less, and further 8,500 or more and 30,000 or less. Is particularly preferred. In the case of the modified siloxane compound represented by the above formula (2) or the above formula (3), these weight average molecular weights (MW) are 8,000 or more and less than 50,000, more preferably 8,500 or more and 30,000 or less. It is particularly preferred. In addition, the said weight average molecular weight (MW) is a weight average molecular weight of polystyrene conversion in the molecular weight distribution measured by gel permeation chromatography (GPC). The modified siloxane compound used in the present invention can be obtained as described above, but the polysiloxane used as a raw material and the compound having an alkene group are a mixture of compounds having various molecular weights. The average molecular weight is obtained.

  As a result of the study by the present inventors, it has been found that among the modified siloxane compounds represented by the above formula (1), it is preferable to use a modified siloxane compound having a specific HLB (value calculated by the Griffin method). . That is, the modified siloxane compound represented by the above formula (1) preferably has an HLB of 1 or more and 11 or less, and more preferably 5 or more and 11 or less.

  When the modified siloxane compound represented by the above formula (1) is used in the liquid composition of the present invention, the liquid composition is applied to the recording medium by setting its weight average molecular weight, and further, the HLB in the above range. In addition, the modified siloxane compound penetrating into the recording medium is further reduced. As a result, the modified siloxane compound represented by the above formula (1) tends to remain on the recording medium. Therefore, even when the content of the modified siloxane compound in the liquid composition is small, the dynamic friction coefficient of the image can be effectively reduced. Examples of the modified siloxane compound represented by the above formula (1) that satisfies the above conditions and can be particularly preferably used in the present invention include the following. Examples thereof include FZ-2104, FZ-2130, FZ-2191 (manufactured by Toray Dow Corning), KF-615A (manufactured by Shin-Etsu Chemical), TSF4452 (manufactured by GE Toshiba Silicone), and the like. Of course, the present invention is not limited to these.

  When the modified siloxane compound represented by the above formula (2) is used in the liquid composition of the present invention, when the weight average molecular weight is within the above range, the liquid medium is applied to the recording medium. The modified siloxane compound penetrating into the inside of the resin is further reduced. As a result, the modified siloxane compound represented by the above formula (2) tends to remain on the recording medium. Therefore, even when the content of the modified siloxane compound represented by the above formula (2) in the liquid composition is small, the dynamic friction coefficient of the image can be effectively reduced. Examples of the modified siloxane compound represented by the above formula (2) that satisfies the above conditions and can be particularly preferably used in the present invention include BYK333 (manufactured by BYK Chemie). Of course, the present invention is not limited to these.

  As a result of the study by the present inventors, it was found that among the modified siloxane compounds represented by the above formula (3), it is preferable to use a modified siloxane compound having a specific HLB (value calculated by the Griffin method). . That is, in the present invention, as the modified siloxane compound represented by the above formula (3), one having an HLB of 1 or more and less than 7 is used.

  When the modified siloxane compound represented by the above formula (3) is used in the liquid composition of the present invention, the liquid composition is applied to the recording medium by setting the weight average molecular weight and further the HLB in the above range. In addition, the modified siloxane compound penetrating into the recording medium is further reduced. As a result, the modified siloxane compound represented by the above formula (3) tends to remain on the recording medium. Therefore, even when the content of the modified siloxane compound represented by the above formula (3) in the liquid composition is small, the dynamic friction coefficient of the image can be effectively reduced. Examples of the modified siloxane compound represented by the above formula (3) that satisfies the above conditions and can be particularly preferably used in the present invention include the following. Examples thereof include FZ-2203, FZ-2207, FZ-2222, FZ-2231 (manufactured by Toray Dow Corning). Of course, the present invention is not limited to these.

  As described above, the weight average molecular weight (MW) of the modified siloxane compound can be measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a mobile phase. The measurement method used in the present invention is as follows. In addition, measurement conditions, such as a filter, a column, a standard polystyrene sample, and its molecular weight in this invention, are not restricted to the following.

  First, a sample to be measured is placed in tetrahydrofuran (THF) and allowed to stand for several hours for dissolution to prepare a solution. Thereafter, the solution is filtered with a solvent-resistant membrane filter having a pore size of 0.45 μm (for example, trade name: TITAN2 Syringe Filter, PTFE, 0.45 μm; manufactured by SUN-SRi) to obtain a sample solution. The concentration of the sample in the sample solution is adjusted so that the content of the modified siloxane compound is 0.1% by mass to 0.5% by mass.

For the GPC, an RI detector (Refractive Index Detector) is used. In order to accurately measure a molecular weight range of 10 ^{3 to} 2 × 10 ⁶ , it is preferable to combine a plurality of commercially available polystyrene gel columns. For example, four Shodex KF-806M (manufactured by Showa Denko) can be used in combination, or a corresponding one can be used. A column stabilized in a 40.0 ° C. heat chamber is made to flow THF as a mobile phase at a flow rate of 1 mL / min, and about 0.1 mL of the above sample solution is injected.

The weight average molecular weight of the sample is determined using a molecular weight calibration curve prepared with a standard polystyrene sample. As the standard polystyrene sample, one having a molecular weight of about 10 ^{2 to} 10 ⁷ (for example, manufactured by Polymer Laboratories) is used, and it is appropriate to use at least about 10 kinds of standard polystyrene samples.

  The content (% by mass) of the modified siloxane compound in the liquid composition is 0.2% by mass or more and 5.0% by mass or less, more preferably 0.5% by mass or more and 3.0% by mass, based on the total mass of the liquid composition. It is preferable that it is less than mass%. In particular, when the modified siloxane compound represented by the above formula (2) is used, the content (% by mass) of the modified siloxane compound in the ink may be 1.0% by mass or more and less than 3.0% by mass. Particularly preferred. When the content of the modified siloxane compound is 0.5% by mass or more, the modified siloxane compound can be sufficiently left on the recording medium, and the image scratch resistance is particularly excellent. On the other hand, it is particularly preferable that the content of the modified siloxane compound is less than 3.0% by mass because almost no discharge failure occurs due to the influence of, for example, kogation.

<Resin>
As described above, the resin used in the liquid composition of the present invention is a resin that can remain on the recording medium after the liquid composition is applied to the recording medium and can form a film having a certain degree of strength. Any of these can be used. However, as a result of the study by the present inventors, in order to suppress the discharge port wetting phenomenon caused by the resin, which is particularly problematic when used for inkjet, the resin A and the resin B having the following characteristics are used. It has been found optimal to use at least one resin.

  The “hydrogen bond term (δh) of the resin calculated from the solubility parameter of the monomer constituting the resin” defined in the present invention is specifically a value obtained as follows. First, for each monomer constituting the target resin, the hydrogen bond term (δh) of each monomer constituting the resin is calculated from the solubility parameter specific to the monomer. Next, the value obtained by multiplying the hydrogen bond term (δh) of each monomer constituting the resin obtained above by the composition (mass) ratio of each monomer constituting the resin (composition ratio with the sum being 1), respectively. The hydrogen bond term (δh) of the resin is determined by adding the obtained values.

If the acid value of the resin constituting the liquid composition of the present invention is less than 90 mgKOH / g, the resin may precipitate when the resin cannot be dissolved with an alkali or when the liquid composition is stored for a long period of time. . Further, when the acid value is lower than 90 mgKOH / g, the liquid composition contains a resin having a sufficient content to obtain the intended scratch resistance according to the present invention, and the liquid composition is used as a thermal ink jet method. If it is discharged, it may be difficult to maintain a stable discharge property. For this reason, it is preferable that the acid value of resin is 90 mgKOH / g or more. On the other hand, when the acid value of the resin exceeds 150 mgKOH / g, the resin easily penetrates into the inside of the recording medium together with the aqueous medium in the liquid composition, and the high level of scratch resistance intended by the present invention cannot be obtained. There is a case. Therefore, when the acid value of the resin exceeds 150 mgKOH / g, it is preferable that the hydrogen bond term (δh) of the resin calculated from the solubility parameter of the monomer constituting the resin is ^1.5 cal ^0.5 / cm ^1.5 or less. However, when the acid value of the resin exceeds 200 mgKOH / g, an amount sufficient to obtain the high level of scratch resistance intended by the present invention, no matter how the hydrogen bond term (δh) of the resin is defined. In some cases, this resin cannot be left on the recording medium. For this reason, it is preferable that the acid value of resin is 200 mgKOH / g or less.

Furthermore, when the resin A or resin B constituting the liquid composition of the present invention has a hydrogen bond term (δh) of the resin calculated from the solubility parameter of the monomer constituting the resin below 1.0 cal ^0.5 / cm ^1.5 , In some cases, the wetting phenomenon of the discharge port due to the resin becomes remarkable. As a result, there is a case where the ejection performance is deteriorated, for example, the flying curve of the droplet occurs. For this reason, it is preferable that the hydrogen bond term (δh) of the resin calculated from the solubility parameters of the monomers constituting the resin A and the resin B is 1.0 cal ^0.5 / cm ^1.5 or more. On the other hand, if the hydrogen bond term of the resin calculated from the solubility parameter of the monomer constituting the resin exceeds 3.7 cal ^0.5 / cm ^1.5 , the resin will be contained in the liquid composition no matter how the acid value of the resin is specified. The aqueous medium may easily penetrate into the recording medium. For this reason, the scratch resistance intended by the present invention may not be obtained.

In summary, the optimum resin constituting the liquid composition of the present invention is the resin A and the resin B having the characteristics of combining the acid value and the hydrogen bond term (δh) within the following ranges. At least one resin is used. Resin A has an acid value of 90 mgKOH / g or more and 150 mgKOH / g or less. In addition to this, the resin A has a hydrogen bond term (δh) calculated from the solubility parameter of the monomer constituting the resin of 1.0 cal ^0.5 / cm ^1.5 or more and 3.7 cal ^0.5 / cm ^1.5 or less. It has the characteristic of being within the range. More preferable resin A includes one having a hydrogen bond term (δh) of 1.0 cal ^0.5 / cm ^1.5 or more and 3.2 cal ^0.5 / cm ^1.5 or less calculated from the solubility parameter of the monomer constituting the resin. . In particular, for the resin A, the hydrogen bond term (δh) of the resin calculated from the solubility parameter of the monomer constituting the resin is 1.2 cal ^0.5 / cm ^1.5 or more and 1.8 cal ^0.5 / cm ^1.5 or less. Is preferred. On the other hand, the resin B has an acid value exceeding 150 mgKOH / g and not more than 200 mgKOH / g. In addition to this, the resin B has a hydrogen bond term (δh) calculated from the solubility parameter of the monomer constituting the resin in a range of 1.0 cal ^0.5 / cm ^1.5 or more and ^1.5 cal ^0.5 / cm ^1.5 or less. It has the characteristic that it is in. More preferable resin B includes one having a hydrogen bond term (δh) of 1.2 cal ^0.5 / cm ^1.5 or more and ^1.5 cal ^0.5 / cm ^1.5 or less calculated from the solubility parameter of the monomer constituting the resin. .

  As long as the monomer constituting the resin used in the liquid composition of the present invention can have a resin having an acid value and a hydrogen bond term (δh) of the resin having the above-described characteristics, Any of them can be used. Specifically, as the monomer constituting the resin, the following monomers can be appropriately used.

  Styrene, α-methylstyrene, etc. Ethyl acrylate, n-butyl acrylate, n-hexyl acrylate, methyl methacrylate, benzyl methacrylate and the like. Monomers having a carboxyl group such as acrylic acid, methacrylic acid, crotonic acid, ethacrylic acid, propylacrylic acid, isopropylacrylic acid, itaconic acid and fumaric acid. Monomers having a sulfonic acid group such as styrenesulfonic acid, sulfonic acid-2-propylacrylamide, acrylic acid-2-ethyl sulfonate, methacrylic acid-2-ethyl sulfonate, and butylacrylamide sulfonic acid. Monomers having a phosphonic acid group such as ethyl methacrylate-2-phosphonate and acrylic acid-2-ethyl phosphonate.

  In the present invention, when the resin A is used, it is preferable to include at least one monomer selected from the group consisting of styrene, n-butyl acrylate, and benzyl methacrylate among the monomers listed above. Furthermore, it is more preferable that the monomer constituting the resin A has both styrene and n-butyl acrylate. At this time, among the monomers constituting the resin A, the mass ratio of n-butyl acrylate based on styrene (n-butyl acrylate / styrene) is particularly preferably more than 0.2 and less than 0.35. preferable. Moreover, when using the said resin B, it is preferable that the monomer mentioned above contains at least 1 sort (s) of monomer chosen from the group which consists of styrene and (alpha) -methylstyrene. Furthermore, it is more preferable that the monomer constituting the resin B has both styrene and α-methylstyrene. At this time, among the monomers constituting the resin B, the mass ratio of α-methylstyrene (α-methylstyrene / styrene) based on styrene is particularly preferably 0.90 or less. In the present invention, the use of a monomer having a nonionic group such as ethylene oxide is not preferred because the strength of the film formed on the recording medium may be reduced.

  The weight average molecular weight of the resin (at least one kind of resin A and resin B) is preferably 5,000 or more and 15,000 or less, and more preferably 6,000 or more and 9,000 or less. Resins having a weight average molecular weight in the above range are likely to remain on the recording medium after the liquid composition is applied to the recording medium, and are less susceptible to steric hindrance. For this reason, the resin is easily adsorbed with the modified siloxane compound, and the dynamic friction coefficient of the image can be particularly effectively lowered.

  The content (mass%) of the resin (at least one kind of resin A and resin B) in the liquid composition is 0.5 mass% or more and 5.0 mass% or less based on the total mass of the liquid composition, Furthermore, it is preferable that they are 2.5 mass% or more and 4.0 mass% or less. When the content of the resin is within the above range, an amount of the resin capable of sufficiently obtaining scratch resistance can be left on the recording medium. Furthermore, when the resin content is within the above range, the discharge port wetting phenomenon caused by the resin can be suppressed, and the discharge performance such as the flying curve of the droplets is unlikely to occur.

<Aqueous medium>
In the liquid composition of the present invention, water or an aqueous medium that is a mixed solvent of water and a water-soluble organic solvent can be used. The content (% by mass) of the water-soluble organic solvent in the liquid composition is preferably 3.0% by mass or more and 50.0% by mass or less based on the total mass of the liquid composition.

  The water-soluble organic solvent is not particularly limited as long as it is water-soluble, and those listed below can be used alone or in combination of two or more. Specifically, for example, the following water-soluble organic solvents can be used. Alkanediols such as 1,3-butanediol, 1,5-pentanediol, 1,2-hexanediol, and 1,6-hexanediol. Glycol ethers such as diethylene glycol monomethyl (or ethyl) ether and triethylene glycol monoethyl (or butyl) ether. C1-C4 alkyl alcohols, such as ethanol, isopropanol, n-butanol, isobutanol, secondary butanol, and tertiary butanol. Carboxylic acid amides such as N, N-dimethylformamide and N, N-dimethylacetamide. Ketones or ketoalcohols such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one; Cyclic ethers such as tetrahydrofuran and dioxane. Glycerin. Ethylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol. 1,2- or 1,3-propylene glycol, 1,2- or 1,4-butylene glycol, polyethylene glycol having an average molecular weight of 200 to 1,000, thiodiglycol, 1,2,6-hexanetriol, acetylene glycol Glycols such as derivatives. Heterocycles such as 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylmorpholine. Sulfur-containing compounds such as dimethyl sulfoxide.

  It is preferable to use deionized water (ion exchange water) as the water. The content (% by mass) of water in the liquid composition is preferably 50.0% by mass or more and 95.0% by mass or less based on the total mass of the liquid composition.

<Other ingredients>
In addition to the above components, the liquid composition of the present invention may contain a moisturizing solid content such as urea, urea derivatives, trimethylolpropane, and trimethylolethane. The content (% by mass) of the moisturizing solid content in the liquid composition is 0.1% by mass or more and 20.0% by mass or less, and further 3.0% by mass or more and 10.% by mass based on the total mass of the liquid composition. It is preferable that it is 0 mass% or less.

  Furthermore, it contains various additives such as pH adjusters, rust preventives, antiseptics, antifungal agents, antioxidants, and anti-reducing agents in order to obtain liquid compositions having desired physical properties as required. May be.

[Pigment ink]
Hereinafter, each component constituting the pigment ink used together with the liquid composition of the present invention in the image forming method of the present invention will be described.
<Pigment>
For the ink, a resin dispersion type pigment (resin dispersion type pigment) that disperses the pigment using a dispersant, or a self dispersion type pigment (self dispersion type pigment) in which a hydrophilic group is introduced on the surface of the pigment particle is used. be able to. In addition, pigments (resin-bonded self-dispersing pigments) in which organic groups containing polymers are chemically bonded to the surface of the pigment particles, microcapsule type that increases the dispersibility of the pigment and enables dispersion without using a dispersant Pigments can also be used. Of course, these pigments having different dispersion methods may be used in combination. The content (% by mass) of the pigment in the ink is 0.1% by mass to 15.0% by mass and more preferably 1.0% by mass to 10.0% by mass based on the total mass of the ink. preferable.

  For black ink, it is preferable to use carbon black such as furnace black, lamp black, acetylene black and channel black as a pigment. Specifically, for example, the following commercially available products can be used.

  Ray Van: 1170, 1190 ULTRA-II, 1200, 1250, 1255, 1500, 2000, 3500, 5000 ULTRA, 5250, 5750, 7000 (above, made in Colombia). Black Pearls L, Legal: 330R, 400R, 660R, Mogul L, Monak: 700, 800, 880, 900, 1000, 1100, 1300, 1400, 2000, Vulcan XC-72R (above, manufactured by Cabot). Color Black: FW1, FW2, FW2V, FW18, FW200, S150, S160, S170, Printex: 35, U, V, 140U, 140V, Special Black: 6, 5, 4A, 4 (above, manufactured by Degussa). No. 25, no. 33, no. 40, no. 47, no. 52, no. 900, no. 2300, MCF-88, MA600, MA7, MA8, MA100 (above, manufactured by Mitsubishi Chemical).

  Also, newly prepared carbon black can be used. Of course, the present invention is not limited to these, and any conventional carbon black can be used. Further, the material is not limited to carbon black, and magnetic fine particles such as magnetite and ferrite, titanium black, and the like may be used as a pigment.

In the color ink, it is preferable to use an organic pigment as the pigment. Specifically, for example, the following can be used.
Water-insoluble azo pigments such as Toluidine Red, Toluidine Maroon, Hansa Yellow, Benzidine Yellow, and Pyrazolone Red. Water-soluble azo pigments such as Ritolol Red, Helio Bordeaux, Pigment Scarlet, and Permanent Red 2B. Derivatives from vat dyes such as alizarin, indanthrone and thioindigo maroon. Phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green. Quinacridone pigments such as quinacridone red and quinacridone magenta. Perylene pigments such as perylene red and perylene scarlet. Isoindolinone pigments such as isoindolinone yellow and isoindolinone orange. Imidazolone pigments such as benzimidazolone yellow, benzimidazolone orange, and benzimidazolone red. Pilanthrone pigments such as pyranthrone red and pyranthrone orange. Indigo pigments, condensed azo pigments, thioindigo pigments, diketopyrrolopyrrole pigments. Flavanthrone yellow, acylamide yellow, quinophthalone yellow, nickel azo yellow, copper azomethine yellow, perinone orange, anthrone orange, dianthraquinonyl red, dioxazine violet, etc. Of course, the present invention is not limited to these.

  Moreover, when an organic pigment is shown by a color index (CI) number, the following can be used, for example. C. I. Pigment Yellow: 12, 13, 14, 17, 20, 24, 74, 83, 86, 93, 97, 109, 110, 117, and the like. Same: 120, 125, 128, 137, 138, 147, 148, 150, 151, 153, 154, 166, 168, 180, 185, etc. C. I. Pigment Orange: 16, 36, 43, 51, 55, 59, 61, 71, etc. C. I. Pigment Red: 9, 48, 49, 52, 53, 57, 97, 122, 123, 149, 168, 175 and the like. 176, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 238, 240, 254, 255, 272, etc. C. I. Pigment violet: 19, 23, 29, 30, 37, 40, 50, and the like. C. I. Pigment Blue: 15, 15: 1, 15: 3, 15: 4, 15: 6, 22, 60, 64, and the like. C. I. Pigment Green 7, 36, etc. C. I. Pigment brown 23, 25, 26, and the like. Of course, the present invention is not limited to these.

<Resin>
A resin may be used for the ink. The resin may be used as a dispersant for dispersing the pigment in the aqueous medium, or may be simply added to the ink. Although any resin can be used at this time, it is preferable to use a resin having the following characteristics in order to obtain the scratch resistance which is the object of the present invention. That is, it is preferable to use a resin used for the liquid composition according to the present invention, that is, a resin that can remain on the recording medium after the liquid composition is applied to the recording medium and can form a film having a certain degree of strength. Furthermore, when the liquid composition and the ink are used in combination, it is particularly preferable that the resins used for the liquid composition and the ink are aligned. In particular, the resin used for the liquid composition and the ink is the same, that is, the characteristics of the resin (the hydrogen bond term (δh) of the resin calculated from the acid value and the solubility parameter of the monomer constituting the resin) are the same. It is preferable. In such cases, the resin used in the ink can have the same characteristics as the resin that can be used in the liquid composition of the present invention described above.

  Specific examples of the monomer constituting the resin include the following, and a resin composed of at least two monomers among them is exemplified. At this time, at least one is preferably a hydrophilic monomer. Styrene, vinyl naphthalene, aliphatic alcohol ester of α, β-ethylenically unsaturated carboxylic acid, acrylic acid, maleic acid, itaconic acid, fumaric acid, vinyl acetate, vinyl pyrrolidone, acrylamide, or derivatives thereof. Examples of the resin include a block copolymer, a random copolymer, a graft copolymer, or a salt thereof. Furthermore, natural resins such as rosin, shellac and starch may be used. These resins are soluble in an aqueous solution in which a base is dissolved, and are alkali-soluble resins.

  The resin content (% by mass) in the ink is preferably 0.5% by mass or more and 5.0% by mass or less based on the total mass of the ink. Moreover, it is preferable that the weight average molecular weights of resin are 1,000 or more and 15,000 or less. Further, the acid value of the resin is preferably 90 mgKOH / g or more and 200 mgKOH / g or less.

<Aqueous medium>
For the ink, water or an aqueous medium that is a mixed solvent of water and a water-soluble organic solvent can be used. The content (% by mass) of the water-soluble organic solvent in the ink is preferably 3.0% by mass or more and 50.0% by mass or less based on the total mass of the ink.

  The water-soluble organic solvent is not particularly limited as long as it is water-soluble, and those listed below can be used alone or in combination of two or more. Specifically, for example, the following water-soluble organic solvents can be used. Alkanediols such as 1,3-butanediol, 1,5-pentanediol, 1,2-hexanediol, and 1,6-hexanediol. Glycol ethers such as diethylene glycol monomethyl (or ethyl) ether and triethylene glycol monoethyl (or butyl) ether. C1-C4 alkyl alcohols, such as ethanol, isopropanol, n-butanol, isobutanol, secondary butanol, and tertiary butanol. Carboxylic acid amides such as N, N-dimethylformamide and N, N-dimethylacetamide. Ketones or ketoalcohols such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one; Cyclic ethers such as tetrahydrofuran and dioxane. Glycerin. Ethylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol. Glycols such as 1,2- or 1,3-propylene glycol, 1,2- or 1,4-butylene glycol, polyethylene glycol, thiodiglycol, 1,2,6-hexanetriol, and acetylene glycol derivatives; Heterocycles such as 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylmorpholine. Sulfur-containing compounds such as dimethyl sulfoxide.

  It is preferable to use deionized water (ion exchange water) as the water. The content (% by mass) of water in the ink is preferably 50.0% by mass or more and 95.0% by mass or less based on the total mass of the ink.

<Other ingredients>
In addition to the above components, the ink may contain a moisturizing solid content such as urea, a urea derivative, trimethylolpropane, and trimethylolethane. The content (% by mass) of the moisturizing solid content in the ink is 0.1% by mass or more and 20.0% by mass or less, and further 3.0% by mass or more and 10.0% by mass or less based on the total mass of the ink. It is preferable that

  Furthermore, it contains various additives such as pH adjusters, rust preventives, antiseptics, antifungal agents, antioxidants, anti-reduction agents, etc., in order to obtain inks having desired physical properties as required. Also good.

[Set of liquid composition and ink]
The liquid composition of the present invention can also be used as a set of a liquid composition and an ink in combination with an ink.

[Image forming method]
The image forming method of the present invention comprises (i) a step of applying a liquid composition to a recording medium, and (ii) a step of applying a pigment ink to the recording medium. In particular, it is preferable to perform the above steps (i) and (ii) so that the liquid composition and the pigment ink are in contact with each other on a recording medium. With this configuration, the scratch resistance of the image formed with the ink is excellent at a high level in which the coloring material is not scraped off even when the image is scratched with such a strong pressure that the non-recording portion of the recording medium is scratched. Scratch resistance is achieved.

  Further, when the liquid composition and the ink are applied to the recording medium, the following methods and combinations of these methods can be considered. Specific examples include (a) a method of applying a pigment ink after applying the liquid composition, and (b) a method of applying the liquid composition after applying the pigment ink. In the present invention, these methods can be appropriately selected. However, in view of the object of the present invention to obtain an excellent scratch-resistant image at a high level that has not been obtained in the past, the method (b) is preferred. In this case, the interval from application of the ink to application of the liquid composition is not particularly limited. However, in order to further increase the binding force between the resin in the ink and the resin in the liquid composition, the application interval is determined so that the ink and the liquid composition are in contact with each other and mixed in a liquid state. Is preferred.

  The amount of the liquid composition applied to the recording medium is not particularly limited as long as the effects of the present invention can be obtained. However, considering reduction of beading and improvement of fixing speed, it is preferably 20% or more and 50% or less, more preferably 25% or more and 50% or less, based on the amount of ink applied. Here, beading refers to the following phenomenon. With the fluidity before the ink is fixed on the recording medium, the dots formed with the ink move irregularly in the surface direction on the surface of the recording medium, and the dots and adjacent dots form an aggregate. This is a phenomenon in which the image density is uneven.

  If the liquid composition is applied only to the image area, the difference in scratch resistance may increase between the area where the image is formed and the area where the image is not formed. For this reason, it is particularly preferable to apply the liquid composition to a wider area including the image area. However, when the applied amount of the liquid composition is 20% or more and 50% or less based on the applied amount of the ink, it may be difficult to apply the liquid composition in a wider range including the image area. . Here, in general, when a liquid having a high surface tension and a liquid having a low surface tension come into contact with each other, the liquid having a large surface tension moves toward a liquid having a low surface tension. Accordingly, the liquid composition is applied in a wider range including the image area as the liquid composition application amount of 20% to 50%, more preferably 25% to 50%, based on the ink application amount. In order to effectively impart the above, it is preferable to do as follows. That is, it is preferable to make the surface tension of the liquid composition higher than the surface tension of the ink. By doing in this way, when an ink and a liquid composition contact each other, a liquid composition spreads over the whole area | region to which the ink was provided.

  In the image forming method of the present invention, the method for applying the ink or the liquid composition to the recording medium is not particularly limited, but it is particularly preferable to apply not only the ink but also the liquid composition to the recording medium by an inkjet method. This is because according to the ink jet recording method, it is easy to accurately apply the liquid composition to the image area, and it is easy to adjust the application amount of the liquid composition as described above. Because. The amount of ink and liquid composition applied in the ink jet method can be adjusted by appropriately determining the recording duty and the like.

[Inkjet recording method]
The liquid composition of the present invention is particularly preferably applied to an ink jet recording method in which recording is performed on a recording medium by discharging the ink and the liquid composition by an ink jet method. The ink jet recording method includes a recording method in which ink and liquid composition are ejected by applying mechanical energy to the ink and liquid composition, and ink and liquid composition are applied by applying thermal energy to the ink and liquid composition. There are recording methods for discharging. In particular, the liquid composition of the present invention can be particularly preferably applied to an ink jet recording method using thermal energy.

[cartridge]
The cartridge of the present invention is provided with a liquid composition storage unit that stores the liquid composition, and the liquid composition stored in the liquid composition storage unit is the liquid composition of the present invention. It is characterized by that.

[Recording unit]
The recording unit of the present invention is a recording unit comprising a liquid composition storage unit that stores a liquid composition and a recording head that discharges the liquid composition, and is stored in the liquid composition storage unit. The liquid composition is the above-described liquid composition of the present invention. In particular, the recording head is more preferably a recording unit that discharges the liquid composition by applying thermal energy to the liquid composition.

[Inkjet recording apparatus]
An ink jet recording apparatus according to the present invention is an ink jet recording apparatus including a liquid composition storage unit that stores a liquid composition and a recording head that discharges the liquid composition, and the liquid stored in the storage unit The composition is a liquid composition of the present invention. In particular, the recording head is more preferably an ink jet recording apparatus that discharges a liquid composition by applying thermal energy to the liquid composition.

  An example of the ink jet recording apparatus will be described below. First, an example of the configuration of a recording head, which is a main part of an ink jet recording apparatus using thermal energy, is shown in FIGS. 2 is a cross-sectional view of the recording head 13 along the ink flow path, and FIG. 3 is a cross-sectional view taken along the line AB of FIG. The recording head 13 includes a member having an ink flow path (nozzle) 14 and a heating element substrate 15. The heating element substrate 15 includes a protective layer 16, electrodes 17-1 and 17-2, a heating resistor layer 18, a heat storage layer 19, and a substrate 20.

  When pulsed electric signals are applied to the electrodes 17-1 and 17-2 of the recording head 13, the region indicated by n of the heating element substrate 15 rapidly generates heat, and bubbles are generated in the ink 21 in contact with the surface. Will occur. Then, the meniscus 23 protrudes due to the pressure of the bubbles, and the ink 21 is ejected as an ink droplet 24 from the ejection port 22 of the nozzle 14 toward the recording medium 25.

  FIG. 4 is an external view of an example of a multi-head in which a large number of recording heads shown in FIG. 2 are arranged. The multi-head includes a glass plate 27 having multi-nozzles 26 and a recording head 28 similar to that shown in FIG.

  FIG. 5 is a perspective view showing an example of an ink jet recording apparatus incorporating a recording head. The blade 61 is a wiping member, one end of which is held by a blade holding member, and forms a cantilever. The blade 61 is disposed at a position adjacent to the recording area by the recording head 65 and is held in a form protruding in the moving path of the recording head 65.

  Reference numeral 62 denotes a cap on the ejection port surface of the recording head 65, which is disposed at a home position adjacent to the blade 61, moves in a direction perpendicular to the moving direction of the recording head 65, abuts on the ink ejection port surface, and performs capping. The structure to perform is provided. An ink absorber 63 provided adjacent to the blade 61 is held in a form protruding in the moving path of the recording head 65, similarly to the blade 61. The ejection recovery unit 64 includes a blade 61, a cap 62, and an ink absorber 63. The blade 61 and the ink absorber 63 remove moisture, dust, and the like from the discharge port surface.

  Reference numeral 65 denotes a recording head which has discharge energy generating means and performs recording by discharging ink onto a recording medium facing the discharge port surface where the discharge port is arranged. Reference numeral 66 denotes a movement of the recording head 65 by mounting the recording head 65. It is a carriage for performing. The carriage 66 is slidably engaged with the guide shaft 67, and a part of the carriage 66 is connected to a belt 69 (not shown) driven by a motor 68. As a result, the carriage 66 can move along the guide shaft 67, and the recording area by the recording head 65 and the area adjacent thereto can be moved.

  Reference numeral 51 denotes a paper feeding unit for inserting a recording medium, and 52 denotes a paper feed roller driven by a motor (not shown). With these configurations, the recording medium is fed to a position facing the ejection port surface of the recording head 65 and discharged to a paper discharge unit having a paper discharge roller 53 as recording progresses. When recording by the recording head 65 is completed and the recording head returns to the home position, the cap 62 of the ejection recovery unit 64 is retracted from the moving path of the recording head 65, but the blade 61 protrudes into the moving path. Yes. In this way, the ejection port of the recording head 65 is wiped.

  When the cap 62 is in contact with the ejection port surface of the recording head 65 to perform capping, the cap 62 moves so as to protrude into the moving path of the recording head. When the recording head 65 moves from the home position to the recording start position, the cap 62 and the blade 61 are in the same position as in the wiping. As a result, the ejection port surface of the recording head 65 is wiped even during this movement. The recording head moves to the home position adjacent to the recording area at a predetermined interval not only when the recording is completed or when the ejection is recovered, but also while the recording head moves the recording area for recording. However, wiping is also performed with this movement

  FIG. 6 is a diagram illustrating an example of an ink cartridge 45 that contains ink supplied to the recording head via an ink supply member, for example, a tube. Here, reference numeral 40 denotes an ink container, for example, an ink bag, in which supply ink is stored, and a rubber plug 42 is provided at the tip thereof. By inserting a needle (not shown) into the stopper 42, the ink in the ink bag 40 can be supplied to the recording head. An ink absorber 44 receives waste ink.

  In the present invention, the recording unit is not limited to one in which the recording head and the ink cartridge are separated, and a unit in which they are integrated as shown in FIG. 7 can be suitably used. In FIG. 7, reference numeral 70 denotes a recording unit, in which an ink storage portion that stores ink, for example, an ink absorber is stored, and the recording head portion in which the ink in the ink absorber has a plurality of ejection openings. 71 is ejected as ink droplets. Alternatively, a structure in which the ink container is an ink bag with a spring or the like inside without using an ink absorber may be used. Reference numeral 72 denotes an atmosphere communication port for communicating the inside of the cartridge with the atmosphere. The recording unit 70 is used in place of the recording head 65 shown in FIG. 5 and is detachable from the carriage 66.

  Next, an ink jet recording apparatus using mechanical energy will be described. A nozzle forming substrate having a plurality of nozzles, a pressure generating element composed of a piezoelectric material and a conductive material, and ink that fills the surroundings of the pressure generating element are provided. The pressure generating element is displaced by an applied voltage, and ink droplets are ejected from ejection ports. It has a feature of having a recording head. FIG. 8 is a schematic diagram showing an example of the configuration of the recording head. The recording head includes an ink flow path 80 communicating with an ink chamber, an orifice plate 81, a vibration plate 82 that applies pressure to ink, a piezoelectric element 83 that is bonded to the vibration plate 82 and is displaced by an electric signal, the orifice plate 81, and the vibration plate. It is comprised with the board | substrate 84 which supports and fixes 82 etc. The distortion stress generated by applying a pulsed voltage to the piezoelectric element 83 deforms the vibration plate bonded to the piezoelectric element 83 and pressurizes the ink in the ink flow path 80, thereby causing the discharge port of the orifice plate 81 to discharge. Ink droplets are ejected from 85. Such a recording head can be used by being incorporated in an ink jet recording apparatus similar to that shown in FIG.

  The liquid composition of the present invention can be applied by replacing “ink” with “liquid composition” in the above description. That is, the cartridge of the present invention uses the liquid composition of the present invention for the liquid composition stored in the liquid composition storage section as a cartridge comprising a liquid composition storage section for storing the liquid composition. preferable. Further, the recording unit of the present invention is a liquid stored in the liquid composition storage unit as a recording unit including a liquid composition storage unit that stores the liquid composition and a recording head that discharges the liquid composition. It is preferable to use the liquid composition of the present invention for the composition. The ink jet recording apparatus of the present invention is housed in the liquid composition housing section as an ink jet recording apparatus including a liquid composition housing section that stores a liquid composition and a recording head that discharges the liquid composition. It is preferable to use the liquid composition of the present invention as the liquid composition.

  Hereinafter, the present invention will be described in more detail with reference to Examples, Comparative Examples, and Reference Examples. The present invention is not limited in any way by the following examples as long as the gist thereof is not exceeded. “Part” or “%” is based on mass unless otherwise specified.

<Preparation of aqueous resin solution>
Ion exchange water is added to each of the resins 1 to 28 obtained by copolymerization with the monomer composition described in Table 1 (the weight average molecular weight of each resin is described in Table 1), and the solid content concentration of each resin is 10 mass. % Resin aqueous solutions 1 to 28 were prepared. In addition, each resin used what was obtained by neutralizing a copolymer with 10 mass% potassium hydroxide aqueous solution. Although the monomers in the table are abbreviated, the following are shown respectively.
St: styrene α-MSt: α-methylstyrene BZMA: benzyl methacrylate nBA: n-butyl acrylate MMA: methyl methacrylate
MAA : Methacrylic acid AA: Acrylic acid

<Hydrogen bond term (δh) of resin calculated from solubility parameter of monomer constituting resin>
The “hydrogen bond term (δh) of the resin calculated from the solubility parameter of the monomer constituting the resin” was determined as follows. First, for each monomer constituting the target resin, the hydrogen bond term (δh) of each monomer constituting the resin is calculated from the solubility parameter specific to the monomer. Next, a value obtained by multiplying the hydrogen bond term (δh) of each monomer constituting the resin obtained above by the composition (mass) ratio of each monomer constituting the resin (composition ratio with the sum being 1) is obtained. . Next, by adding these values, the hydrogen bond term of the resin calculated from the solubility parameter of the monomer constituting the resin can be obtained. Table 2 shows the value of the hydrogen bond term (δh) of each monomer calculated from the solubility parameter specific to the monomer constituting the resin for each resin used in the preparation of the aqueous resin solution.

The resin calculated from the solubility parameter of the monomer constituting the resin, taking as an example the resin 1 which is a copolymer of styrene-methyl methacrylate-acrylic acid (composition (mass) ratio = 28: 58: 14). The method for obtaining the hydrogen bond term (δh) will be specifically described. From Table 2 below, the hydrogen bond term (unit: cal ^0.5 / cm ^1.5 ) of each monomer calculated from the solubility parameters of styrene, methyl methacrylate, and acrylic acid, which are monomers constituting the resin 1, is 0.00. 3.93, and 5.81. Therefore, the hydrogen bond term (δh) of the resin 1 calculated from the solubility parameter of the monomer constituting the resin 1 is obtained by the following equation.

  Table 3 shows the value of the hydrogen bond term (δh) of the resin obtained by the above method for each resin in the previously prepared resin aqueous solution. Table 3 shows the values of the acid value and the weight average molecular weight of the resin. Furthermore, Table 3 also includes values of mass ratios of n-butyl acrylate or α-methyl styrene based on styrene in a resin having styrene and n-butyl acrylate or styrene and α-methyl styrene as monomers. Show.

（*1）樹脂を構成するモノマーの溶解度パラメーターより算出される樹脂の水素結合項（δｈ）
（*2）樹脂における、スチレンを基準としたｎ−ブチルアクリレートの質量比率
（*3）樹脂における、スチレンを基準としたα−メチルスチレンの質量比率

(* 1) Hydrogen bond term of resin (δh) calculated from solubility parameter of monomer constituting resin
(* 2) Mass ratio of n-butyl acrylate based on styrene in resin (* 3) Mass ratio of α-methyl styrene based on styrene in resin

<Preparation of pigment dispersion>
(Preparation of pigment dispersion 1)
Pigment: 10 parts, 11 parts of a resin composed of the monomers listed in Table 1, and 85 parts of ion-exchanged water are mixed and dispersed in a batch type vertical sand mill for 3 hours to prepare pigment dispersion 1. did. The pigment includes C.I. I. Pigment Blue 15: 3 was used. Resin 11 was obtained by neutralizing the copolymer with a 10% by mass aqueous potassium hydroxide solution. The obtained dispersion was subjected to pressure filtration with a filter having a pore size of 2.5 μm (product name: HDCII; manufactured by Nihon Pall). Water was added to this dispersion to prepare a pigment dispersion 1 having a pigment concentration of 10% by mass and a resin concentration of 5% by mass.

(Preparation of pigment dispersion 2)
A pigment dispersion 2 having a pigment concentration of 10% by mass and a resin concentration of 5% by mass was prepared in the same manner as in the pigment dispersion 1, except that the resin 13 composed of the monomers shown in Table 1 was used instead of the resin 11. did.

(Preparation of pigment dispersion 3)
A pigment dispersion 3 having a pigment concentration of 10% by mass and a resin concentration of 5% by mass was prepared in the same manner as in the pigment dispersion 1, except that the resin 18 composed of the monomers shown in Table 1 was used instead of the resin 11. did.

<Synthesis of modified siloxane compound>
According to the following synthesis examples, compounds 1 to 12, which are modified siloxane compounds, were synthesized.

(Compound 1)
Compound 1 was synthesized as follows using a glass container equipped with a thermometer and stirring means. Using the polysiloxane compound represented by the following formula (A) and the polyoxyethylene compound represented by the following formula (B) as main raw materials in the container, an addition reaction was carried out in the presence of a platinum catalyst to give compound 1 Synthesized. The obtained compound 1 corresponds to the modified siloxane compound represented by the formula (1), and has a weight average molecular weight of 8,500, HLB5 (theoretical value), and solubility in water of 1% or less. Compound 1 has a structure in formula (1) where m = 73, n = 6, R ₁ = propylene group, a = 8, b = 0, and R ₂ = hydrogen atom.

(Compound 2)
Compound 2 was synthesized as follows using a glass container equipped with a thermometer and stirring means. Using the polysiloxane compound represented by the following formula (C) and the polyoxyethylene compound represented by the following formula (D) as main raw materials in the container, an addition reaction was carried out in the presence of a platinum catalyst to give compound 2 Synthesized. The obtained compound 2 corresponded to the modified siloxane compound represented by the formula (1), and had a weight average molecular weight of 29,400, HLB5 (theoretical value), and solubility in water of 1% or less. Compound 2 has a structure in formula (1) where m = 245, n = 28, R ₁ = propylene group, a = 6, b = 0, and R ₂ = hydrogen atom.

(Compound 3)
Compound 3 was synthesized as follows using a glass container equipped with a thermometer and stirring means. Using the polysiloxane compound represented by the following formula (E) and the polyoxyethylene compound represented by the following formula (B) as main raw materials in the container, an addition reaction was carried out in the presence of a platinum catalyst to give compound 3 Synthesized. The obtained compound 3 was a comparative compound of the modified siloxane compound represented by the formula (1), and had a weight average molecular weight of 7,400, HLB5 (theoretical value), and solubility in water of 1% or less. Compound 3 has a structure in formula (1) where m = 65, n = 5, R ₁ = propylene group, a = 8, b = 0, and R ₂ = hydrogen atom.

(Compound 4)
Using a glass container equipped with a thermometer and stirring means, Compound 4 was synthesized as follows. Using the polysiloxane compound represented by the following formula (F) and the polyoxyethylene compound represented by the following formula (G) as main raw materials in the container, an addition reaction was carried out in the presence of a platinum catalyst to give compound 4 Synthesized. The obtained compound 4 corresponds to the modified siloxane compound represented by the formula (2), and had a weight average molecular weight of 47,000, HLB9 (theoretical value), and solubility in water of 1% or less. The compound 4 has a structure in which p = 349, R ₃ = hydrogen atom, R ₄ = propylene group, c = 240, d = 0 in the formula (2).

(Compound 5)
Compound 5 was synthesized as follows using a glass container equipped with a thermometer and stirring means. Using the polysiloxane compound represented by the following formula (H) and the polyoxyethylene compound represented by the following formula (I) as main raw materials in the container, an addition reaction was carried out in the presence of a platinum catalyst to obtain a compound 5 Synthesized. The obtained compound 5 was a comparative compound of the modified siloxane compound represented by the formula (2), and had a weight average molecular weight of 7,700, HLB7 (theoretical value), and solubility in water of 1% or less. Compound 5 has a structure of p = 64, R ₃ = hydrogen atom, R ₄ = propylene group, c = 30, d = 0 in the formula (2).

(Compound 6)
Compound 6 was synthesized as follows using a glass container equipped with a thermometer and stirring means. Using the polysiloxane compound represented by the following formula (J) and the polyoxyethylene compound represented by the following formula (K) as the main raw materials in the container, an addition reaction was carried out in the presence of a platinum catalyst to obtain the compound 6 Synthesized. The obtained compound 6 was a comparative compound of the modified siloxane compound represented by the formula (2), and had a weight average molecular weight of 50,400, HLB7 (theoretical value), and solubility in water of 1% or less. Compound 6 has a structure of p = 439, R ₃ = hydrogen atom, R ₄ = propylene group, c = 200, d = 0 in the formula (2).

(Compound 7)
Compound 7 was synthesized as follows using a glass container equipped with a thermometer and stirring means. Using the polysiloxane compound represented by the following formula (L) and the polyoxyethylene compound represented by the following formula (M) as main raw materials in the container, an addition reaction was carried out in the presence of a platinum catalyst to obtain a compound 7 Synthesized. The obtained compound 7 corresponded to the modified siloxane compound represented by formula (3), and had a weight average molecular weight of 49,000, HLB6 (theoretical value), and solubility in water of 1% or less. The compound 7 has a structure of q = 7, R ₅ = propylene group, R ₆ = propylene group, e = 6, f = 0, r = 52 in the formula (3).

(Compound 8)
Compound 8 was synthesized as follows using a glass container equipped with a thermometer and stirring means. Using the polysiloxane compound represented by the following formula (N) and the polyoxyethylene compound represented by the following formula (O) as main raw materials in the container, an addition reaction was carried out in the presence of a platinum catalyst to obtain a compound 8 Synthesized. The obtained compound 8 corresponds to the modified siloxane compound represented by the formula (3), and has a weight average molecular weight of 8,800, HLB6 (theoretical value), and solubility in water of 1% or less. The compound 8 has a structure of q = 23, R ₅ = propylene group, R ₆ = propylene group, e = 18, f = 0, r = 3 in the formula (3).

(Compound 9)
Compound 9 was synthesized as follows using a glass container equipped with a thermometer and stirring means. Using the polysiloxane compound represented by the following formula (P) and the polyoxyethylene compound represented by the following formula (O) as main raw materials in the container, an addition reaction was carried out in the presence of a platinum catalyst to obtain the compound 9 Synthesized. The obtained compound 9 was a comparative compound of the modified siloxane compound represented by the formula (3), and had a weight average molecular weight of 49,000, HLB7 (theoretical value), and solubility in water of 1% or less. The compound 9 has a structure of q = 18, R ₅ = propylene group, R ₆ = propylene group, e = 18, f = 0, r = 21 in the formula (3).

(Compound 10)
Compound 10 was synthesized as follows using a glass container equipped with a thermometer and stirring means. Using the polysiloxane compound represented by the following formula (Q) and the polyoxyethylene compound represented by the following formula (O) as main raw materials in the container, an addition reaction was carried out in the presence of a platinum catalyst to give compound 10 Synthesized. The obtained compound 10 was a comparative compound of the modified siloxane compound represented by the formula (3), and had a weight average molecular weight of 55,000, HLB6 (theoretical value), and solubility in water of 1% or less. The compound 10 has a structure in the formula (3) where q = 24, R ₅ = propylene group, R ₆ = propylene group, e = 18, f = 0, r = 20.

(Compound 11)
Compound 11 was synthesized as follows using a glass container equipped with a thermometer and stirring means. Using the polysiloxane compound represented by the following formula (R) and the polyoxyethylene compound represented by the following formula (S) as the main raw materials in the container, an addition reaction was carried out in the presence of a platinum catalyst to obtain the compound 11 Synthesized. The obtained compound 11 corresponds to the modified siloxane compound represented by the formula (3), and has a weight average molecular weight of 8,800, HLB1 (theoretical value), and solubility in water of 1% or less. The compound 11 has a structure of q = 16, R ₅ = propylene group, R ₆ = propylene group, e = 2, f = 0, r = 6 in the formula (3).

(Compound 12)
Compound 12 was synthesized as follows using a glass container equipped with a thermometer and stirring means. Using the polysiloxane compound represented by the following formula (T) and the polyoxyethylene compound represented by the following formula (U) as the main raw materials in the container, an addition reaction was carried out in the presence of a platinum catalyst to obtain the compound 12 Synthesized. The obtained compound 12 was a comparative compound of the modified siloxane compound represented by the formula (3), and had a weight average molecular weight of 7,800, HLB6 (theoretical value), and solubility in water of 1% or less. The compound 12 has a structure in the formula (3) where q = 8, R ₅ = propylene group, R ₆ = propylene group, e = 7, f = 0, r = 7.

  In addition, the weight average molecular weight of each compound obtained above was measured as follows. The modified siloxane compound to be measured was placed in tetrahydrofuran (THF) and allowed to stand for several hours to dissolve, so that the concentration of the sample was 0.1% by mass to prepare a solution. Thereafter, the solution was filtered through a solvent-resistant membrane filter having a pore size of 0.45 μm (trade name: TITAN2 Syringe Filter, PTFE, 0.45 μm; manufactured by SUN-SRi) to obtain a sample solution. Using this sample solution, the weight average molecular weight was measured under the following conditions.

Apparatus: Alliance GPC 2695 (manufactured by Waters)
Column: 4-column column of Shodex KF-806M (Showa Denko)
・ Mobile phase: Tetrahydrofuran (special grade)
・ Flow rate: 1.0 mL / min
・ Oven temperature: 40.0 ℃
-Sample solution injection volume: 0.1 mL
・ Detector: RI (refractive index)
Polystyrene standard samples: PS-1 and PS-2 (manufactured by Polymer Laboratories)
(Molecular weight: 17 types of 750000, 2560000, 841700, 377400, 320000, 210500, 148000, 96000, 59500, 50400, 28500, 20650, 10850, 5460, 2930, 1300, 580)

<Preparation of liquid composition>
Each liquid composition was prepared using each component shown in the following Tables 4-1 to 4-16 including the resin aqueous solution prepared above and the synthesized modified siloxane compound or the commercially available modified siloxane compound. Specifically, each component shown in Tables 4-1 to 4-16 was mixed in the composition shown in the table, stirred sufficiently, and then added with a filter (product name: HDCII; manufactured by Pall) having a pore size of 2.5 μm. Each liquid composition was prepared by performing pressure filtration. In Tables 4-1 to 4-16, MW refers to the weight average molecular weight.

<Preparation of ink>
The components shown in Table 5 below were mixed and sufficiently stirred, and then pressure filtration was performed with a filter (product name: HDCII; manufactured by Pall) having a pore size of 2.5 μm to prepare inks 1 to 3.

  About the liquid composition and ink which were obtained above, the surface tension in 25 degreeC was measured with Kyowa CBVP type surface tension meter A-1 type (made by Kyowa Kagaku). As a result, the surface tension of all the liquid compositions was higher than the surface tension of all the inks.

<Evaluation>
(Storage stability)
Each liquid composition obtained above was put in a Teflon (registered trademark) container and stored at a temperature of 60 ° C. for one month. Thereafter, the state of the liquid composition returned to room temperature and the state of the liquid composition before storage were visually confirmed, and storage stability was evaluated. The evaluation criteria for storage stability are as follows. The results are shown in Tables 6-1 to 6-4.
A: The transparency of the liquid composition did not change before and after storage.
B: The transparency of the liquid composition did not change before and after storage, but there was some suspended matter in the liquid composition after storage.
C: After storage, precipitates were generated in a Teflon (registered trademark) container.

(Discharge characteristics: face surface condition, discharge stability)
Each liquid composition obtained above was filled in an ink cartridge for an ink jet recording apparatus (trade name: PIXUS850i; manufactured by Canon), and the ink jet recording apparatus was remodeled and set at a cyan ink position. Three images of 18 cm × 24 cm were recorded in the default mode on an office planner (manufactured by Canon) with a recording duty of 50%. At this time, the recording head surface was cleaned using a PIXUS 850i wiper blade once per recording. Thereafter, a nozzle check pattern of PIXUS850i was recorded on CF102 (made by Canon). The state of the recording head surface at this time was visually confirmed, and the state of the face surface was evaluated. The evaluation criteria for the state of the face are as follows. The results are shown in Tables 6-1 to 6-4. Moreover, the nozzle check pattern obtained above was visually confirmed, and the discharge stability was evaluated. The evaluation criteria for ejection stability are as follows. The evaluation results are shown in Tables 6-1 to 6-4.

[Face state]
A: There was almost no liquid composition around the discharge port.
B: There were some liquid composition droplets around the discharge port.
C: A liquid film of the liquid composition was present in a band shape around the discharge port.

(Discharge stability)
A: The nozzle check pattern was not disturbed and was recorded normally.
B: The nozzle check pattern was slightly disturbed, but there was no non-ejection.
C: The nozzle check pattern had clear non-ejection and disturbance, and recording could not be performed normally.

(Abrasion resistance)
Each liquid composition and each ink obtained above were used in combination as shown in the following Tables 6-1 to 6-4, and an image (reference evaluation image) was formed as follows. The liquid composition and the ink are respectively filled in an ink cartridge for an ink jet recording apparatus (trade name: BJF900; manufactured by Canon), and the liquid composition is placed at the position of the yellow ink of the ink jet recording apparatus, and the ink is placed at the position of the magenta ink. I set it. Then, an ink having an ejection amount of 4.5 ng, a resolution of 1,200 dpi × 1,200 dpi, and eight-pass unidirectional printing was used to form an image with a recording duty of 100%. In addition, after applying ink to the recording medium as described above, recording is performed with an ejection amount of 4.5 ng, a resolution of 1,200 dpi × 1,200 dpi, and eight-pass unidirectional recording on and around the image area formed with the ink. The liquid composition was applied with a duty of 50%. The obtained recorded matter was allowed to stand at room temperature for 1 day, and then the image was scratched with a nail under such a strong pressure that the non-recorded portion of the recording medium was scratched. The recorded matter was visually confirmed to evaluate scratch resistance. The evaluation criteria for scratch resistance are as follows. The results are shown in Tables 6-1 to 6-4.
A: No nail mark was left on the surface of the image.
B: Although nail marks remain on the surface of the image, the color material was not scraped off from the recording medium.
C: Nail marks remained on the surface of the image, and the color material was slightly scraped off from the recording medium.
D: Although the surface of the recording medium is not exposed, the color material is clearly scraped off.
E: It is a level where there is no problem as long as the image is lightly touched, but when scratched with such a strong pressure as to scratch the non-recording portion of the recording medium, the color material was scraped off to such an extent that the surface of the recording medium could be seen.

(Dynamic friction coefficient)
The dynamic friction coefficient in the image area of the recorded matter (reference evaluation image) obtained above was measured as follows. Specifically, the dynamic friction coefficient of polymethyl methacrylate (PMMA) with respect to the resin ball in the image area of this reference evaluation image is measured using a surface property tester (product name: Haydon Tribogear TYPE14DR; manufactured by Shinto Kagaku). did. The vertical load applied to the PMMA resin ball is 50 g, the moving speed is 2 mm / sec, the horizontal force acting in the moving direction of the PMMA resin ball during movement is measured by the load cell, and the ratio of the horizontal force to the vertical load force is the dynamic friction coefficient. Calculated. The values of the obtained dynamic friction coefficients are shown in Tables 6-1 to 6-4.

  The evaluation results of the ejection stability of Examples 8 and 9 were both B, but the state of the nozzle check pattern was slightly less in Example 8. At this time, when the state of the kogation on the heater was observed with an optical microscope, the occurrence of kogation was less in Example 8.

  The evaluation results of the ejection stability in Examples 29 and 30 were both B ranks, but the ink of Example 29 was slightly better in check pattern disturbance. A good reason is that Example 29 was better when the burnt state on the heater was confirmed with an optical microscope.

  The evaluation results of the ejection stability of Examples 54 and 55 are both B, but the state of the nozzle check pattern is slightly less in Example 54. At this time, when the state of kogation on the heater was observed with an optical microscope, Example 54 produced less kogation.

  Each liquid composition obtained above and each ink were used in combination as shown in Table 7 below, and an image (reference evaluation image) was formed as follows. The liquid composition and the ink are respectively filled in an ink cartridge for an ink jet recording apparatus (trade name: BJF900; manufactured by Canon), and the liquid composition is placed at the position of the yellow ink of the ink jet recording apparatus, and the ink is placed at the position of the magenta ink. I set it. Then, an ink having an ejection amount of 4.5 ng, a resolution of 1,200 dpi × 1,200 dpi, and eight-pass unidirectional printing was used to form an image with a recording duty of 100%. In addition, after applying ink to the recording medium as described above, recording is performed with an ejection amount of 4.5 ng, a resolution of 1,200 dpi × 1,200 dpi, and eight-pass unidirectional recording on and around the image area formed with the ink. The liquid composition was applied with a duty of 25%. The obtained recorded material was evaluated for scratch resistance and dynamic friction coefficient by the same method and evaluation criteria as described above. The results are shown in Table 7.

  Each liquid composition obtained above and each ink were used in combination as shown in Table 8 below, and an image (reference evaluation image) was formed as follows. The liquid composition and the ink are respectively filled in an ink cartridge for an ink jet recording apparatus (trade name: BJF900; manufactured by Canon), and the liquid composition is placed at the magenta ink position of the ink jet recording apparatus, and the ink is placed at the yellow ink position. I set it. Then, before applying ink to the recording medium, liquid is discharged at an area of the image formed by the ink and the periphery thereof with a discharge amount of 4.5 ng, a resolution of 1,200 dpi × 1,200 dpi, and eight-pass unidirectional recording with a 50% duty. The composition was applied. In addition, after applying the liquid composition to the recording medium as described above, the ejection amount is 4.5 ng, the resolution is 1,200 dpi × 1,200 dpi, 8-pass unidirectional recording, and the recording duty is 100%. An image was formed. The obtained recorded material was evaluated for scratch resistance and dynamic friction coefficient by the same method and evaluation criteria as described above. The results are shown in Table 8.

It is a schematic diagram which shows the concept of a scratch resistance test. FIG. 2 is a longitudinal sectional view of a recording head. It is a cross-sectional view of the recording head. FIG. 2 is a perspective view of a recording head in which the recording head shown in FIG. It is a perspective view which shows an example of an inkjet recording device. It is a longitudinal cross-sectional view of an ink cartridge. It is a perspective view which shows an example of a recording unit. FIG. 3 is a schematic diagram illustrating an example of a configuration of a recording head.

Explanation of symbols

2-1: Sample fixing operation stage 2-2: Sample 2-3: Friction object 2-4: Weight 2-5: Balance mechanism 2-6: Load cell 13: Recording head 14: Nozzle 15: Heating element substrate 16: Protection Layers 17-1, 17-2: Electrode 18: Heating resistor layer 19: Heat storage layer 20: Substrate 21: Ink 22: Discharge port 23: Meniscus 24: Ink droplet 25: Recording medium 26: Multi-nozzle 27: Glass plate 28 : Recording head 40: Ink bag 42: Plug 44: Ink absorber 45: Ink cartridge 51: Paper feed unit 52: Paper feed roller 53: Paper discharge roller 61: Blade 62: Cap 63: Ink absorber 64: Ejection recovery unit 65: recording head 66: carriage 67: guide shaft 68: motor 69: belt 70: recording unit 71: recording head 72: atmosphere communication port 80: ink flow path 81: Orifice plate 82: vibrating plate 83: piezoelectric element 84: substrate 85: discharge port

Claims (15)

A liquid composition containing at least a modified siloxane compound and a resin,
The modified siloxane compound is selected from the group consisting of a modified siloxane compound represented by the following formula (1), a modified siloxane compound represented by the following formula (2), and a modified siloxane compound represented by the following formula (3). At least one kind
The resin has an acid value of 90 mgKOH / g or more and 150 mgKOH / g or less, and the hydrogen bond term (δh) of the resin calculated from the solubility parameter of the monomer constituting the resin is 1.0 cal ^0.5 / cm ^1.5 or more 3 Resin A which is 0.7 cal ^0.5 / cm ^1.5 or less, and a hydrogen bond term of the resin having an acid value of more than 150 mg KOH / g and 200 mg KOH / g or less and calculated from the solubility parameter of the monomer constituting the resin ( δh) is at least one resin of Resin B having 1.0 cal ^0.5 / cm ^1.5 or more and ^1.5 cal ^0.5 / cm ^1.5 or less ,
The resin is selected from the group consisting of at least one monomer of acrylic acid and methacrylic acid, and styrene, α-methylstyrene, benzyl methacrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, and n-hexyl acrylate. A liquid composition, which is a resin copolymerized using at least one monomer .

(The weight average molecular weight of the modified siloxane compound represented by the formula (1) is 8,000 or more and 30,000 or less, and in the formula (1), R ₁ is an alkylene group having 1 to 20 carbon atoms; ₂ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, m is 1 to 250, n is 1 to 100, a is 1 to 100, and b is 0 to 100.

(The weight average molecular weight of the modified siloxane compound represented by the formula (2) is 8,000 or more and less than 50,000. In the formula (2), each R ₃ is independently a hydrogen atom or a carbon number of 1 or more and 20 or less. R ₄ is an alkylene group having 1 to 20 carbon atoms, p is 1 to 450, c is 1 to 250, and d is 0 to 100.)

(The modified siloxane compound represented by the formula (3) has a weight average molecular weight of 8,000 or more and less than 50,000 and an HLB of 1 or more and less than 7, and in the formula (3), each R ₅ is independently A hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R ₆ is an alkylene group having 1 to 20 carbon atoms, q is 1 to 100, r is 1 to 100, and e is 1 to 100. , F is 0 or more and 100 or less.) The liquid composition according to claim 1, which does not contain a coloring material. The liquid composition according to claim 1 or 2 , wherein the modified siloxane compound represented by the formula (1) has an HLB of 5 or more and 11 or less. The liquid composition according to any one of claims 1 to 3, wherein the monomer constituting the resin A includes at least one monomer selected from the group consisting of styrene, n-butyl acrylate, and benzyl methacrylate. The liquid composition according to any one of claims 1 to 4 , wherein the monomer constituting the resin B includes at least one monomer selected from the group consisting of styrene and α-methylstyrene. Amount contained in the liquid composition of the resin (% by weight), based on the total mass of the liquid composition, 2.5 or less mass% to 4.0 mass% in any one of claims 1 to 5 The liquid composition as described. The liquid according to any one of claims 1 to 6 , wherein a content (% by mass) of the modified siloxane compound is 0.5% by mass or more and less than 3.0% by mass based on the total mass of the liquid composition. Composition. The liquid composition further contains water, and the content (% by mass) of the water in the liquid composition is 50.0% by mass or more and 95.0% by mass or less based on the total mass of the liquid composition. The liquid composition according to any one of claims 1 to 7 . An image forming method comprising: applying a pigment ink to a recording medium; and applying a liquid composition to the recording medium,
Wherein as the liquid composition, an image forming method which comprises using a liquid composition according to any one of claims 1 to 8. The image forming method according to claim 9 , wherein the step of applying the liquid composition to the recording medium is performed after the step of applying the pigment ink to the recording medium. Examples pigment ink, pigment, and an image forming method according to claim 9 or 10 using an ink acid value containing 90 mgKOH / g or more 200 mg KOH / g or less of the resin. The image forming method according to any one of claims 9 to 11 to impart said pigment ink and said liquid composition on a recording medium by an inkjet method. A cartridge comprising a liquid composition container for containing a liquid composition,
Cartridge wherein liquid composition contained the liquid composition contained in the unit, characterized in that it is a liquid composition according to any one of claims 1 to 8. A recording unit comprising a liquid composition container that contains a liquid composition and a recording head that discharges the liquid composition,
Recording unit where the liquid composition contained the liquid composition contained in the unit, characterized in that it is a liquid composition according to any one of claims 1 to 8. An ink jet recording apparatus comprising: a liquid composition storage unit that stores a liquid composition; and a recording head that discharges the liquid composition,
An ink jet recording apparatus wherein the liquid composition contained the liquid composition contained in the unit is a liquid composition according to any one of claims 1 to 8.

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