JP2019018448A - Transfer body, image recording method and image recording device - Google Patents

Abstract

To provide a transfer body having target application characteristic of reaction liquid and transfer property of an intermediate image in repeated use.SOLUTION: An image formation surface of a transfer body for transfer type image recording using ink and reaction liquid containing a component increasing the viscosity of the ink and a fluorine-based surfactant is formed by a surface layer part 2 containing at least one kind of a reaction product of a fluorinated alkyl chemical compound expressed by the general formula (1) (in the general formula (1), R represents a straight chain or branch shaped fluoroalkyl group of 2 to 29 fluorine atoms and 1 to 14 carbon atoms, L represents a linker group, and a substituted or unsubstituted bivalent group of 1 to 20 carbon atoms, X represents a reactive functional group containing an alkoxysilyl group, hydroxysilyl group, vinyl group, (meth)acrylic group or cyclic ether group of 2 to 3 carbon atoms).SELECTED DRAWING: Figure 1

Description

  The present invention relates to a transfer-type image recording transfer body using an ink and a reaction liquid containing a component that increases the viscosity of the ink, and an image recording method and an image recording apparatus using the transfer body.

As an image recording method using ink, a transfer type image in which ink is applied to an image forming surface of a transfer body to form an intermediate image, and the formed intermediate image is transferred to a recording medium to form the image on the recording medium. Recording methods are known. The transfer body used in this image recording method preferably has a property that the intermediate image can be easily peeled off on the surface thereof, that is, a good transfer property of the intermediate image.
It has been considered that it is important to lower the surface free energy of the transfer body in order to obtain good transferability of the intermediate image from the transfer body to the recording medium. Therefore, a material having a low surface free energy, in other words, a high water repellency, such as a fluororesin or a silicone resin, has been used for the surface (surface layer portion) of the transfer body (see Patent Document 1). The surface free energy on the surface of the transfer body formed of such a material is approximately 110 degrees when expressed as a “typical contact angle with respect to pure water”.
On the other hand, a transfer-type image recording method is proposed in which a curable solution layer is formed on the transfer body using ultraviolet rays having ink affinity and fixability in advance for holding and transferring the intermediate image on the transfer body. (See Patent Document 2). In this image recording method, an intermediate image is formed by applying ink to the curable solution layer on the transfer body, and the ultraviolet curable solution layer holding the intermediate image is transferred from the transfer body to the recording medium. The image is completed by irradiating with ultraviolet rays.
On the other hand, in order to improve the transferability of the intermediate image on the transfer body, a transfer body including a polymer layer prepared from a double-end reactive siloxyfluorocarbon has been proposed (see Patent Document 3). Since this transfer body has a surface energy as low as 10 to 40 mN / m and an elastomeric characteristic, it is considered to have excellent transferability.

JP 2003-182064 A JP 2010-228193 A Japanese Unexamined Patent Publication No. 2014-231223

An intermediate image can be formed by applying a reaction liquid containing ink and a component that increases the viscosity of the ink to the image forming surface of the transfer body. At this time, in order to further improve the image forming performance on the image forming surface of the transfer body and the transferability of the intermediate image, the intermediate image is recorded on the recording medium while the image forming surface maintains appropriate wettability with respect to the ink and the reaction liquid. It is required to transfer the film well.
However, according to the study by the present inventors, in contrast to the required performance for the above-mentioned transfer body, the transfer body described in Patent Document 1 has more wettability with respect to ink and reaction liquid on the formed image forming surface in some cases. It turns out that it needs to be good.
In addition, when the transfer body described in Patent Document 2 is used, image retention can be obtained by the ink absorbing and fixing the curable solution layer. However, in the image recording method disclosed in Patent Document 2, the curable solution layer itself is also transferred to the recording medium side together with the ink during transfer. Therefore, when the transfer body is used repeatedly, the formation of the curable solution layer on the transfer body and the peeling from the transfer body are repeatedly performed, and the hydrophilicity of the transfer body with respect to the curable solution layer is lowered and cured. May affect the good formation of the aqueous solution layer. Further, in the image formation using the transfer body described in Patent Document 2, every time image formation is performed, the material for the curable solution layer is consumed and the number of image formation processes increases, so that the image production cost increases. In some cases.
When the transfer material described in Patent Document 3 is used, transferability is improved by the presence of the fluorine component. However, in the transfer body of Patent Document 3, the water repellency becomes too high and the wettability with respect to the ink or reaction liquid applied to the image forming surface is not sufficient, and the image is repelled on the transfer body at the time of ink application, which is good. It has been found that images may not be obtained. In addition, the transferability is not only the magnitude of the surface energy, but also the followability to the paper on the surface of the transfer body, that is, the flexibility of the surface, may be considered in improving the transferability. However, it has also been found that by introducing a double-end reactive fluorine skeleton, the surface layer having the image forming surface of the transfer body may not be able to obtain flexibility for improving transferability.
Accordingly, an object of the present invention is to provide a transfer body having a desired reaction liquid application characteristic and intermediate image transfer property even in repeated use, and an image recording method and an image recording apparatus using the transfer body. And

A transfer body for transfer type image formation using an ink and a reaction liquid containing a component for increasing viscosity of the ink and a fluorine-based surfactant,
The surface layer portion of the image forming surface to which the ink and the reaction liquid of the transfer body are applied,

(In general formula (1),
R represents a linear or branched fluoroalkyl group having 2 to 29 fluorine atoms and 1 to 14 carbon atoms,
L is a linker group and represents a substituted or unsubstituted divalent group having 1 to 20 carbon atoms,
X represents a reactive functional group including an alkoxysilyl group, a hydroxysilyl group, a vinyl group, a (meth) acryl group, or a cyclic ether group having 2 to 3 carbon atoms. )
Comprising at least one reaction product of a fluorinated alkyl compound represented by:
It is characterized by that.
An image recording method according to the present invention includes:
A reaction liquid applying step for applying a reaction liquid containing a component for increasing the viscosity of the ink and a fluorosurfactant to the image forming surface of the transfer body, and forming an intermediate image by applying ink to the image forming surface of the transfer body. An ink application process, and an image forming process comprising:
A transfer step of transferring the intermediate image from the transfer member to a recording medium;
An image recording method comprising:
The transfer body is a transfer body having the configuration described above.
An image recording apparatus according to the present invention includes:
A transcript,
A reaction liquid applying device that applies a reaction liquid containing a component that increases the viscosity of ink and a fluorosurfactant to the image forming surface of the transfer body, and an intermediate image by applying ink to the image forming surface of the transfer body. An image forming unit comprising:
A transfer unit for transferring the intermediate image from the transfer member to a recording medium;
An image recording apparatus comprising:
The transfer body is a transfer body having the configuration described above.

  According to the present invention, it is possible to provide a transfer body having the desired reaction liquid application characteristics and intermediate image transfer property even in repeated use, and an image recording method and an image recording apparatus using such a transfer body. .

It is a schematic diagram of the structure of the transfer body of this invention. It is a schematic diagram of the structure of the inkjet recording device which can be utilized for the transfer type image recording method of the present invention.

  The transfer body according to the present invention is for transfer type image formation using an ink and a reaction liquid containing a component for increasing the viscosity of the ink and a fluorine-based surfactant. The surface layer portion of the image forming surface to which the ink and reaction liquid of the transfer body according to the present invention are applied contains at least one reaction product of a fluorinated alkyl compound represented by the following general formula (1).

  In the general formula (1), R represents a linear or branched fluoroalkyl group having 2 to 29 fluorine atoms and 1 to 14 carbon atoms, L is a linker group, Twenty substituted or unsubstituted divalent groups are represented. Furthermore, X represents a reactive functional group including an alkoxysilyl group, a hydroxysilyl group, a vinyl group, a (meth) acryl group, or a cyclic ether group having 2 to 3 carbon atoms.

Hereinafter, the present invention will be described in detail with reference to embodiments. In the present invention, an image recording apparatus and an image recording apparatus that apply ink by an inkjet method can be referred to as an inkjet recording apparatus and an inkjet recording method, respectively. In addition, an ink jet recording apparatus including a transfer body is hereinafter referred to as a transfer type ink jet recording apparatus for convenience, and an ink jet recording method using the transfer body is hereinafter referred to as a transfer type ink jet recording method for convenience. Further, a transfer type image forming transfer body is hereinafter simply referred to as a transfer body.
[Transcript]
FIG. 1 shows a schematic perspective view of the configuration of a transfer body for transfer type inkjet recording as an embodiment of the present invention.
A transfer body 1 shown in FIG. 1A has a surface layer portion 2. The image forming surface of the transfer body 1 is on the surface layer portion 2 (surface side). An intermediate image is formed by applying a reaction liquid and ink to the image forming surface.
The transfer body in the present invention preferably has moderate elasticity in order to transfer the intermediate image by pressing the intermediate image onto a recording medium such as paper. For this reason, for example, when plain paper is used as the recording medium, it is preferable that at least a part of the transfer body is formed of an elastic material. The portion made of this elastic material preferably has a durometer type A hardness (based on JIS K6253) of 10 degrees or more and 100 degrees or less, and more preferably 30 degrees or more and 70 degrees or less.
The transfer body may have a single-layer structure or a multi-layer structure including a plurality of layers.
As a single layer structure, the structure which utilizes the surface of the base layer 3 as the surface layer part 2 can be mentioned as shown to the schematic cross section of FIG.1 (b). As the multi-layer structure, as shown in the schematic cross-sectional views of FIGS. 1C and 1D, the surface layer 2 is provided on the base layer 3 having a single-layer structure or a two-layer structure (3a, 3b). 2 may be a surface layer portion 2 constituting the image forming surface. The base layer 3 can also have a multi-layer structure of three or more layers.
The transfer body can be compressed by pressurization to make the pressure uniform when transferring to the recording medium, and it can be compressed with elasticity that can return to its original shape when the pressure is released. You may have an elastic layer.
Such an elastic layer can be used for at least the base layer 3 shown in FIGS. 1B, 1C, and 1D.

Further, the transfer body may have at least one of a compression layer, a resin layer, a base fabric layer, a metal layer and the like in addition to the elastic layer in order to give elastic properties, strength, thermal properties, and the like. Good.
As a material for forming the elastic layer, various rubber materials or various elastomer materials can be used from the viewpoint of processing characteristics, etc., and the elastic layer can be provided in the form of a continuous layer or a porous layer.
Examples of elastomer materials and rubber materials include silicone rubber, fluorosilicone rubber, phenyl silicone rubber, fluorine rubber, chloroprene rubber, nitrile rubber, ethylene propylene rubber, natural rubber, styrene rubber, isoprene rubber, butadiene rubber, and ethylene / propylene / butadiene. And copolymers of nitrile butadiene and the like. In particular, silicone rubber, fluorosilicone rubber, phenyl silicone rubber, fluorine rubber, and chloroprene rubber are preferably used in terms of dimensional stability, durability, heat resistance, and the like.
The thickness of the elastic layer is not particularly limited and can be appropriately selected according to the layer structure of the transfer body, the printing medium or the process conditions, etc., preferably 5 to 500 μm, more preferably 50 to 300 μm, and still more preferably. 100-200 μm.
The size of the transfer body 1 can be freely selected according to the target print image size. FIG. 1 illustrates a sheet-shaped transfer body 1, but the overall shape of the transfer body is not limited to this, and in addition to the sheet shape, a roller shape, a drum shape, a belt shape, an endless web shape, and the like. Is mentioned.

<Surface layer of transfer body>
The surface layer portion of the transfer body of the present invention has a reaction product (hereinafter referred to as “fluoroalkyl group-containing reaction product”) obtained by reacting at least one of the fluorinated alkyl compounds represented by the general formula (1) described above. Also referred to as "thing".
The fluoroalkyl group (R) in the general formula (1) may be a linear or branched fluoroalkyl group having 2 to 29 fluorine atoms and 1 to 14 carbon atoms, and each carbon has at least one carbon atom. Bonded with the above fluorine.
The linker group (L) in the general formula (1) may be a substituted or unsubstituted divalent group having 1 to 20 carbon atoms. Examples of the unsubstituted divalent group include an alkylene group, an oxyalkylene group, and an alkyl ether group (—R—O—R′—: R and R ′ each independently represent an alkylene group), a divalent group, An aromatic functional group, a urethane bond, a carbonyl group, etc. are mentioned. These divalent groups may be used alone or in combination of two or more. A part of the hydrogen may be substituted with a halogen atom such as a fluorine atom or an iodine atom. As carbon number, 1-8, Furthermore, 1-4 are preferable. Specifically, from the standpoint of industrial availability, it is difficult to hinder the reactivity of X, and alkylene groups such as methylene group, ethylene group, dimethyl ether group (—CH ₂ —O—CH ₂ —), methyl Alkyl ether groups such as ethyl ether group (—CH ₂ —O—C ₂ H ₄ —), oxymethylene group (—CH ₂ —O—), oxyethylene group (—C ₂ H ₄ —O—), oxypropylene An oxyalkylene group such as a group (—C ₃ H ₆ —O—) is preferred.
The alkoxysilyl group of the general formula (1) is a group in which the Si atom has at least one alkoxy group, and preferred alkoxysilyl groups include groups represented by the following general formula (2).

(In the formula, R30 represents a non-hydrolyzable alkyl group, R31 represents a hydrolyzable group, and t is an integer of 0 to 2.)
As a non-hydrolyzable alkyl group, a C1-C10 alkyl group can be mentioned. Examples of the hydrolyzable group include an alkyloxy group, and examples of the alkyl group of the alkyloxy group include a methyl group and an ethyl group.
Specific examples of the group of the general formula (2) include the following groups.
・ Methyltrimethoxysilyl group, methyltriethoxysilyl group, dimethyldimethoxysilyl group, dimethyldiethoxysilyl group, diethyldiethoxysilyl group, trimethylmethoxysilyl group, trimethylethoxysilyl group, propyltrimethoxysilyl group, propyltriethoxysilyl group Group, hexyltrimethoxysilyl group, hexyltriethoxysilyl group, decyltrimethoxysilyl group, decyltriethoxysilyl group and the like.
The hydroxysilyl group of the general formula (1) is a group in which the Si atom has at least one hydroxyl group, and examples thereof include a group in which the alkyloxy group of the group represented by the general formula (2) is substituted with a hydroxyl group. .
Examples of the reactive functional group containing a C2-C3 cyclic ether group as X in the general formula (1) include an epoxy group, a 2-methyl epoxy group, a 2,2-dimethyl epoxy group, an oxetanyl group, and the like. Can do.

In order to develop good transferability, it is generally necessary to lower the surface energy of the image forming surface of the transfer body, in other words, to increase the water repellency. As one of the methods, it is widely known to use a fluororesin such as fluororubber or polytetrafluoroethylene (PTFE) in the surface layer part or to contain a fluorine compound. In some cases, image quality deteriorates.
As a result of intensive studies, the present inventors have newly found a material for forming a surface layer part that can keep the retention of the reaction liquid good while reducing the surface energy of the transfer body. That is, the surface layer portion of the transfer body contains the above-described fluoroalkyl group-containing reaction product, and the reaction liquid can be more appropriately held by the image forming surface by adding a fluorosurfactant to the reaction liquid. I found it possible. Although this reason is not certain, it is presumed that the fluorine in the surface layer portion of the transfer body and the fluorine in the reaction solution interact.
Further, the fluoroalkyl compound represented by the general formula (1) is a one-terminal reaction type. This one-terminal reactive fluorinated alkyl compound has a non-reactive one end of the fluoroalkyl group and a reactive functional group represented by X at the other end.
Since the fluorinated alkyl compound represented by the general formula (1) is a one-terminal reaction type, the fluoroalkyl group is incorporated as a side chain instead of the main chain of the fluoroalkyl group-containing reaction product. Does not interfere with the molecular mobility of the chain. Therefore, regardless of the length of the fluoroalkyl group (the carbon number of R in the general formula (1)), the influence of the fluoroalkyl group on the flexibility of the surface layer portion is small. That is, the surface energy control by the fluoroalkyl group and the flexibility control by other parts can be performed separately, so that the flexibility of the surface layer part that affects the transferability can be controlled by other parts other than the fluoroalkyl group. Can be designed freely. For example, in Examples described later, flexibility is designed by using compounds B1, B2, B3, C, and the like.
Furthermore, the non-reactive end of the fluoroalkyl group is not fixed (bonded) and is a free end, and the fluoroalkyl group having a low surface energy is oriented on the surface of the surface layer that is in contact with air, that is, the outermost surface. It becomes easy and it becomes possible to lower the surface energy of the outermost surface more effectively. In addition, the number of fluorine atoms of the fluoroalkyl group is preferably 25 or less from the viewpoint of performing the polymerization reaction efficiently.
Further, when the transfer body is repeatedly used, the wettability of the image forming surface with the reaction liquid may change. When the wettability of the image forming surface changes, the state of the applied reaction liquid changes, and the image quality to be formed may be different between the initial transfer and the transfer after repetition. As described above, it is important for the transfer body to suppress the change in wettability of the image forming surface of the transfer body when repeatedly used.

The fluoroalkyl group-containing reaction product contained in the surface layer portion in the present invention contains a fluoroalkyl group in the molecular skeleton. In the present invention, “in the skeleton” means a state in which a fluoroalkyl group is covalently bonded to another component as a constituent component of the surface layer portion of the transfer body, and is fixed and adhering to the surface layer portion. Or, it is different from the state where it only penetrates.
Thus, the fluoroalkyl group is fixed in the molecular skeleton of the fluoroalkyl group-containing reaction product contained in the surface layer portion. As a result, the surface layer component is not transferred to the recording medium and disappears during the transfer of the intermediate image, does not ooze out due to changes over time, and disappears due to movement to the reaction liquid or ink. Therefore, it is possible to suppress a change in wettability with the reaction liquid when the transfer body is repeatedly used.
Whether the fluoroalkyl group is incorporated and fixed in the surface layer portion can be confirmed by the following method. First, the surface layer portion of the transfer body is formed as a layer on the substrate, and the surface layer portion is peeled from the substrate to prepare an analysis sample. A weight change of this analytical sample before and after immersion in a good solvent such as methanol and benzene, and a ¹³ C-NMR spectrum after immersion are obtained and used as analysis results. Regarding ¹³ C-NMR, for example, in the case of a compound having a fluoroalkyl group, the presence of the fluoroalkyl group can be confirmed by the presence or absence of a peak of the fluoroalkyl group (—CF ₂ —, σ = 100 to 115 ppm).
The content of the fluoroalkyl group-containing reaction product in the surface layer portion of the transfer body of the present invention varies depending on the type of fluoroalkyl group, but can be 0.1% by mass or more. In addition, you may form a surface layer part only from this reaction product. Furthermore, the content of the reaction product in the case of forming the surface layer portion from the reaction product and other materials is, for example, 0.5% by mass or more and 90% by mass or less, and further 1% by mass or more and 50% by mass. You can select from the following ranges.
Moreover, it is preferable that content of the fluorine of the surface layer part in this invention is 0.1 to 20 mass%. By adjusting to this range, it is possible to achieve both an appropriate reaction liquid application characteristic and transferability.

In addition, the fluoroalkyl group (R) in the general formula (1) is the kind and amount ratio of other compounds in the case of combining the compound of the general formula (1) and other compounds, or the physical properties of the reaction liquid or ink, It is preferable to select appropriately in consideration of process conditions and the like. As described above, since the terminal of the fluoroalkyl group in the general formula (1) is non-reactive, it is arranged as a side chain of the fluoroalkyl group-containing reaction product, and the main chain molecule of the reaction product. The fluoroalkyl group can be effectively oriented on the outermost surface without impeding mobility. Furthermore, from the viewpoint of this orientation, the fluorine number of the fluoroalkyl group is preferably 6 or more. When the number of fluorine is small, the orientation to the surface is slightly small, and the effect of reducing the surface energy may not be sufficiently exhibited. On the other hand, if the fluorine number is long, the compatibility of the monomer with other components will be low, which may cause problems such as uneven distribution of the fluoroalkyl group on the surface due to the cloudiness of the condensate during synthesis. Therefore, the number of fluorine is preferably 25 or less, and more preferably 17 or less.
Moreover, it is preferable to use at least 1 sort (s) of the compound whose X is an alkoxysilyl group or a hydroxysilyl group as a compound of General formula (1). Further, when at least one compound in which X in the general formula (1) is a group other than an alkoxysilyl group and a hydroxysilyl group is used, at least one compound in which X is an alkoxysilyl group or a hydroxysilyl group is used. It is preferable to use it additionally.
The condensation reaction for obtaining at least one condensate of the compound of the general formula (1) wherein X is an alkoxysilyl group or a hydroxysilyl group is carried out by heating in the presence of water, It can be carried out by advancing the condensation reaction. As a result, siloxane bonds are formed. The compound of general formula (1) is selected as a monomer for obtaining the desired condensate, and the hydrolysis and condensation reaction are appropriately controlled by temperature, time, pH, etc. as required, so that the desired surface layer is obtained. A condensate for imparting surface physical properties, mechanical strength, and the like can be obtained. In addition, an acid catalyst or an alkali catalyst may be used.
In the case of radical polymerization type (meth) acrylic group or cationic polymerization type epoxy group, the reaction takes place as soon as the energy beam is irradiated, so the molecule is fixed before the movement, that is, the orientation in the layer. There is a case. However, in the case of a non-photoreactive functional group such as a condensed alkoxysilyl group, the condensation polymerization proceeds gradually with heat to form a condensate, so that the fluoroalkyl group tends to be oriented on the surface during that time. In the case of an alkoxysilyl group or a hydroxysilyl group, a siloxane bond is formed after condensation, so that the surface layer portion is excellent in heat resistance and transferability.
Whether or not siloxane bonds are incorporated and fixed in the surface layer portion is determined by, for example, forming the surface layer portion of the transfer body as a layer on the substrate, and then removing methanol and benzene from the analytical sample peeled off from the formed layer. It can confirm from the weight change before and behind immersion in good solvents, such as, and the ¹³ C-NMR spectrum after immersion. ^{For 13} C-NMR, for example, when a fluoroalkyl compound having a dimethylsilyl group as X is used, the terminal structure of a siloxane bond (—O—Si—CH ₃ , σ = 0.0 to 0.2) The presence or absence of a peak can confirm the presence of a siloxane bond in the surface layer.

Moreover, in this invention, it is preferable to use 2 or more types of compounds from which the fluorine number of R differs as a fluorinated alkyl compound of General formula (1). In the present invention, the reaction liquid is applied to the image forming surface formed on the surface layer portion. This reaction liquid contains a component that increases the viscosity of the ink and contributes to the formation of a good image. On the other hand, depending on its composition and process conditions, it can penetrate into the surface layer and change the characteristics of the transfer body. May end up. Therefore, it is preferable to suppress the penetration of the reaction solution as much as possible. The effect of suppressing internal penetration of the reaction liquid into the surface layer is presumed to be obtained by the following action.
When two or more kinds of fluorinated alkyl compounds having different R fluorine numbers in the general formula (1) are used, a compound having a large fluorine number is oriented on the surface due to the difference in orientation performance. The tendency to exist more inside the layer becomes higher. That is, the water repellency inside the surface layer can be increased. As a result, it is possible to suppress the penetration of the liquid into the surface layer, and the repeatability is further improved.
As a preferable combination of different fluorine numbers when the compounds of general formula (1) having different fluorine numbers of R are used in combination, the difference in fluorine numbers is preferably 5 or more from the viewpoint of the difference in orientation, and 9 or more It is more preferable that Moreover, as a mixing ratio of these compounds, the ratio of the compound having a small number of fluorines / the compound having a large number of fluorines is preferably 1 to 80, more preferably 1 to 50, and further preferably 3 to 15.
The contact angle of the image forming surface of the transfer body of the present invention with respect to pure water is preferably 80 degrees or more and 110 degrees or less, although it varies depending on the characteristics of the reaction solution. Further, it is more preferably 90 degrees or more and 105 degrees or less. As the contact angle with pure water is larger, better transferability can be obtained. In addition, the contact angle with respect to liquids, such as a pure water, can be measured using a general contact angle meter.
In the present invention, the “surface layer portion” means a portion on the surface side of the transfer body. In the present invention, the surface layer portion on the surface of the transfer body to which ink is applied contains a fluoroalkyl group-containing reaction product. The material constituting the surface layer portion is formed from at least such a reaction product, and this reaction product is fixed to the surface layer portion. The surface layer portion only needs to be a portion exposed on the surface of the transfer body, and is not necessarily provided as a layer separated from the substrate. The transfer body is formed as a single layer (one layer), and the surface region thereof is the above fluoroalkyl. It may be formed as a surface layer portion made of a material containing a group-containing reaction product. When the transfer body has a single layer structure, the entire transfer body may be formed from a material containing a fluoroalkyl group-containing reaction product, or only the surface layer portion of the substrate is made of a material containing a fluoroalkyl group-containing reaction product. It may be formed. The method of forming the layer constituting the surface layer part when provided as a layer includes a coating liquid containing a fluoroalkyl group-containing reaction product, or a fluoroalkyl group-containing reaction product component, and a fluoroalkyl group after coating. A method of applying a coating solution capable of forming a contained reaction product is preferred.
The thickness of the surface layer portion is not particularly limited, but the thickness of the surface layer portion is preferably 0.01 μm or more and 10.000 μm or less, more preferably 0.1 μm or more and 10.0 μm or less, and still more preferably It is 1.0 μm or more and 6.0 μm or less. In particular, when the surface layer portion is formed by application of a coating solution, if the thickness of the surface layer portion is within the above range, more sufficient film strength can be obtained, and the entire transfer body during the intermediate image transfer step It is possible to suppress the occurrence of cracks, delamination, and the like in the surface layer caused by stress due to elastic deformation. Furthermore, moderate elastic deformation can be obtained in the surface layer portion, and better transferability following the surface shape of the recording medium can be obtained.

  In addition, providing a surface layer portion as described above and providing the surface layer portion with flexibility suppresses deterioration in transferability by suppressing cracks and delamination in the surface layer portion, and improves followability to the recording medium. This is preferable because it leads to an improvement in transferability. In the fluoroalkyl group-containing reaction product used for forming the surface layer portion, when X is a polymerizable functional group, flexibility is imparted to the surface layer portion by a linear unit introduced by polymerization of X. It is also possible. Furthermore, when X is an alkoxysilyl group or a hydroxysilyl group, a linear unit can be introduced by using, for example, a bifunctional siloxane compound. Or what has a linear unit as linker group L can be used, or it can also be set as a mixed reaction product with the compound which has another linear unit. In particular, when a bifunctional siloxane compound is used, a siloxane bond is formed by condensation, so that the surface layer portion is excellent in heat resistance and transferability.

When the surface layer portion is provided on the substrate as a layer, the surface layer portion and the substrate adjacent to the surface layer portion are sufficiently adhered in addition to the thickness of the surface layer portion in order to suppress cracks, delamination, and transferability degradation. It is preferable to have the property. In order to improve the adhesion, it is preferable to perform a surface treatment on the surface of the substrate adjacent to the surface layer portion (portion where the surface layer portion is provided).
Examples of the surface treatment include flame treatment, corona treatment, plasma treatment, polishing treatment, roughening treatment, active energy ray irradiation treatment (UV, IR, RF, etc.), ozone treatment, surfactant treatment, and the like. Moreover, you may perform surface treatment combining these two or more. In order to further improve adhesion and coatability, it is also preferable to add a silane coupling agent, a sulfur-containing compound or the like to the coating solution for forming the surface layer portion. The coating liquid for forming the surface layer portion can be applied by various conventionally known coating methods. Examples thereof include die coating, blade coating, gravure coating, and a coating method in which an offset roller is combined with these.
The surface layer portion of the transfer body in the present invention contains the above-described fluoroalkyl group-containing reaction product. As a fluorinated alkyl compound of the general formula (1), when obtaining a reaction product as a polymer polymerized by a polymerizable group such as a vinyl group or a cyclic ether group as X, Accordingly, it is preferable to use a polymerization initiator.
As a polymerization initiator in the case of using cationic polymerization for polymerization, for example, a photocationic polymerization initiator that generates cationic species or Bronsted acid by light irradiation, or a thermal cationic polymerization initiator that generates cationic species or Bronsted acid by heat Is mentioned.
Specific examples include onium salts, borate salts, triazine compounds, azo compounds, and peroxides. In terms of sensitivity, stability, reactivity, and solubility, aromatic sulfonium salts and aromatic iodonium salts are preferably used. A cationic polymerization initiator can be used individually or in combination of 2 or more types.
As a polymerization initiator in the case of using radical polymerization for polymerization, a photo radical polymerization initiator that generates radical species by light irradiation or a thermal radical polymerization initiator that generates radical species by heat can be used. Examples of the radical polymerization initiator include organic peroxides such as dialkyl peroxides, diacyl peroxides, ketone peroxides, peroxyketals, hydroperoxides, peroxyesters, azo compounds, and benzophenones. And benzophenone compounds, acetophenone compounds, benzoin and benzoin ether compounds, aminocarbonyl compounds, carbonyl compounds such as thioxanthones, sulfides, peroxides and the like. A radical polymerization initiator can be used individually or in combination of 2 or more types.

In the case where X is used to form a condensate using at least one compound of the general formula (1) having an alkoxysilyl group or a hydroxysilyl group, as a material not containing Si, a cationic polymerizable resin and / or radical polymerization Can be used in addition to the formation of the surface layer portion.
The cationic polymerizable resin as a material not containing Si is a resin containing a compound having a cationic polymerizable group, such as a vinyl group or a cyclic ether group. Among them, a resin having an epoxy group or an oxetanyl group is preferably used. When the oxetane compound or the oxacene resin is used in combination with the epoxy resin, the curing reaction of the surface layer portion is promoted. Specific examples of epoxy resins include bisphenol-A-diglycidyl ether, bisphenol-F-diglycidyl ether, bisphenol-type epoxy resins composed of monomers or oligomers having a bisphenol skeleton, phenol novolac-type epoxy resins, cresol novolac-type epoxy resins. And resins having an alicyclic epoxy structure such as trisphenolmethane type epoxy resin and 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate.
The radical polymerizable resin as a material not containing Si is a resin containing a compound having a vinyl group which is a radical polymerizable group. Among these, resins having an acryloyl group, a methacryloyl group, and a styryl group are preferably used. Examples of the radical polymerizable resin include a polymer of the following polymerizable monomers, a mixture of polymers of the polymerizable monomers alone, or a copolymer of two or more kinds of polymerizable monomers. Can be mentioned.
Examples of the (meth) acrylate monomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , (Meth) acrylic acid-2-ethylhexyl and the like.
Examples of the styrene monomer include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, α-methyl styrene, vinyl naphthalene, 2-ethyl styrene, 3-ethyl styrene, 4-ethyl styrene, and the like. Is mentioned.
When a cationic polymerizable resin and / or a radical polymerizable resin as a material not containing Si is contained, a resin having a large functional group equivalent or a linear skeleton is provided in order to impart sufficient flexibility to the surface layer portion. Such a conventionally known resin is preferably used. These resins are preferably 5% by mass or more and 50% by mass or less with respect to the surface layer part. In addition to the optimal configuration that can handle various types of recording media, image retention on the transfer body, image transfer efficiency to the recording medium during transfer, image quality of the transferred image, etc. The thickness, hardness, elastic modulus, etc. are appropriately selected.
When forming the surface layer of the transfer body using a polymerizable material, the surface layer is thin and uniform and has excellent mechanical strength by using a curing process by irradiation with active energy rays or a heating process. Can do. This is also a factor for improving transferability. Furthermore, since it is excellent also in adhesiveness with the layer adjacent to a surface layer part, it is excellent also in durability. As the active energy ray, an electron beam, an X-ray or the like can be used, but ultraviolet rays are preferably used from the viewpoint of workability and the like.
When coating the coating liquid that forms the surface layer part, an additive such as a surfactant or a co-catalyst that accelerates curing is appropriately contained in the coating liquid for the purpose of improving the coating property. Is also preferable. Moreover, it is good also as a structure which does not contain a solvent and hardens all the coating films.
Further, in order to improve the formation of the intermediate image on the image forming surface of the surface layer portion of the transfer body and to improve the retention of the intermediate image on the transfer body, the average surface roughness Ra of the image forming surface is 0. It is preferably 001 μm or more and 3.00 μm or less.

(Image recording method)
The image recording method using the transfer body according to the present invention includes the following steps.
(A) A reaction liquid applying step for applying a reaction liquid containing a component for increasing the viscosity of the ink and a fluorosurfactant to the image forming surface of the transfer body, and an intermediate image by applying ink to the image forming surface of the transfer body. And an ink application step for forming an image.
(B) A transfer step of transferring the intermediate image from the transfer body to the recording medium.
<Reaction solution>
In the present invention, a reaction liquid is applied to the surface layer portion of the transfer body, and the reaction liquid contains a component for increasing the viscosity of the ink and a fluorosurfactant. Generally, since the reaction liquid stably holds an ink image, the surface energy is adjusted to be 20 mN / m or more and 50 mN / m or less. Since the fluorosurfactant has a fluoroalkyl chain in the hydrophobic portion, the fluorosurfactant interacts with a fluoroalkyl group in the surface layer portion of the transfer body, and good imparting characteristics can be obtained even on a transfer body having a low surface energy.
Examples of the fluorine-based surfactant suitably used in this case include FSO100, FSN100, FS3100 (all are trade names, manufactured by Du Pont), F444 (trade names, manufactured by DIC), and the like.
From the viewpoint of obtaining better imparting characteristics while maintaining the reactivity with the ink, the content of the fluorosurfactant is preferably 0.5% by mass or more, preferably 20% by mass with respect to the total mass of the reaction solution. The following is preferable. More preferably, it is 1 mass% or more and less than 10 mass% with respect to the reaction liquid total mass.
One type selected from the above-mentioned fluorosurfactants or a combination of two or more types can be appropriately selected and used.
The application of the reaction liquid is preferably performed before the application of the ink. By applying ink to the image forming surface of the transfer body to which the reaction liquid has been applied, it is possible to effectively increase the viscosity of the ink by the reaction liquid and stably hold a better image. The ink and the reaction liquid are applied to the image forming surface of the transfer body so that at least a part of them overlaps.
The reaction liquid contains a component that increases the viscosity of the ink. Such components have the effect of reducing the fluidity of at least a part of the ink on the transfer body and suppressing bleeding, beading, and the like, which are ink bleeding and mixing. That is, in image formation using an ink jet device, the amount of ink applied per unit area may be large. In such a case, bleeding and beading are likely to occur. However, since the reaction liquid is applied onto the transfer body, the fluidity is lowered when an image is formed with ink, so that bleeding and beading hardly occur, and as a result, the image is formed and maintained satisfactorily. .
The component for increasing the viscosity of the ink is preferably selected appropriately depending on the type of ink used for image formation. For example, a reaction liquid containing a polymer flocculant is preferably used for dye-based ink. Alternatively, for a pigment-based ink in which pigment particles are dispersed, it is preferable to use a reaction liquid containing a polyvalent metal ion or a reaction liquid containing a pH adjusting agent such as an acid buffer. As another example of the ink viscosity increasing component, a compound having a plurality of ionic groups such as a cationic polymer may be used. It is also effective to use two or more of these compounds in combination. Specific examples of the polymer flocculant that can be used as an ink thickening component include a cationic polymer flocculant, an anionic polymer flocculant, a nonionic polymer flocculant, and an amphoteric polymer flocculant. Is mentioned.
Examples of the metal ions used as components for increasing the viscosity of the ink include divalent metal ions such as Ca ²⁺ , Cu ²⁺ , Ni ²⁺ , Mg ²⁺ , Sr ²⁺ , Ba ^2+, and Zn ²⁺ , Fe ³⁺ , and Cr ^3+. , Y ³⁺ and Al ^{3+ and the} like. When applying a reaction solution containing these metal ions, it is preferably applied as a metal salt aqueous solution. Examples of the anion of the metal salt include Cl ⁻ , NO ₃ ⁻ , CO ₃ ²⁻ , SO ₄ ²⁻ , I ⁻ , Br ⁻ , ClO ₃ ⁻ , HCOO ⁻ , RCOO ⁻ (R is an alkyl group) and the like. However, it is not limited to these. The metal salt concentration of the metal salt aqueous solution is preferably 0.01% by mass or more, and more preferably 0.1% by mass or more. Moreover, 20 mass% or less is preferable.
As the pH adjuster used as a component for increasing the viscosity of the ink, an acidic solution having a pH lower than 7.0 is preferably used. Examples include inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, boric acid, succinic acid, polyacrylic acid, acetic acid, glycolic acid, malonic acid, malic acid, maleic acid, ascorbic acid, succinic acid, glutaric acid, fumaric acid Organic acids such as citric acid, tartaric acid, lactic acid, pyrrolidone carboxylic acid, pyrone carboxylic acid, pyrrole carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumaric acid, thiophene carboxylic acid, and nicotinic acid. In addition, derivatives of these compounds or solutions of these salts can also be preferably used.
Further, an acid buffer solution (buffer) having a pH buffering ability is preferably used because the change in pH is small even when the apparent reaction solution concentration is lowered by the ink, and the reactivity with the ink is hardly lowered. In order to obtain pH buffering capacity, it is preferable to contain a buffer in the reaction solution. As the buffer, for example, acetate such as sodium acetate, potassium acetate and lithium acetate, hydrogen phosphate, hydrogen carbonate, or hydrogen salt of polyvalent carboxylic acid such as sodium hydrogen phthalate or potassium hydrogen phthalate is used. be able to. Examples of polyvalent carboxylic acids include, besides phthalic acid, malonic acid, maleic acid, succinic acid, fumaric acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, adipic acid, sebacic acid, dimer acid, pyromellitic acid And trimellitic acid. Other than this, any conventionally known compound that exhibits a buffering effect on pH when added can be preferably used.

The reaction liquid may be obtained by dissolving a component for increasing the viscosity of the ink as described above in an aqueous medium. Examples of the aqueous medium include water or a mixed solvent of water and a water-soluble organic solvent. The content of the aqueous medium in the reaction liquid is not particularly limited, and can be selected according to the type of active ingredient for aggregation of the reaction liquid, the coating method, the type of recording medium, and the like.
Specific examples of the water-soluble organic solvent include 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; Alkyl alcohols having 1 to 4 carbon atoms 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 such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one, or keto alcohol. Cyclic ethers such as tetrahydrofuran and dioxane. Glycerin. Alkylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2- or 1,3-propylene glycol, 1,2- or 1,4-butylene glycol, polyethylene glycol; Polyhydric alcohols such as thiodiglycol, 1,2,6-hexanetriol, and acetylene glycol derivatives; Sulfur-containing compounds such as 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and dimethyl sulfoxide are preferably used. Two or more kinds of compounds can be selected and mixed from these. Since the reaction solution has desired properties as necessary, in addition to the above components, an antifoaming agent, an antiseptic agent, an antifungal agent and the like can be appropriately added.
Various resins can be added to the reaction solution in order to improve transferability or to improve the fastness of the finally formed image. By adding a resin, it is possible to increase the adhesion to the recording medium during transfer or to increase the mechanical strength of the intermediate image. In addition, depending on the type of resin, improvement in water resistance of the final image on the recording medium can be expected. The resin to be added is not particularly limited as long as it can coexist with the ink thickening component. For example, organic polymers such as polyvinyl alcohol and polyvinyl pyrrolidone are preferably used. A resin that reacts with a component contained in the ink and crosslinks is also preferable. For example, polyoxazoline and polycarbodiimide which react with a carboxylic acid frequently used for dispersing a coloring material in the ink and crosslink. These resins may be used by dissolving in a reaction solution solvent, or may be added in an emulsion state or a suspension state.

<Ink>
As the ink, an ink containing a color material and a liquid medium can be used. When an ink jet device is used as the ink applying device, ink widely used as ink for ink jet, specifically, various inks in which a coloring material such as dye, carbon black, or organic pigment is dissolved and / or dispersed in a liquid medium Can be used. Among them, a pigment ink containing carbon black or an organic pigment is preferable because an image having good weather resistance and color developability can be obtained. The pigment ink may contain a dye as a coloring material as necessary.
As the ink, an aqueous ink containing water is preferable. In particular, an ink containing 45.0% by mass or more of moisture in the component is preferable. The color material content of the ink is preferably 0.1% by mass or more, and more preferably 0.2% by mass or more. Moreover, it is preferable that it is 15.0 mass% or less, and it is more preferable that it is 10.0 mass% or less.
The ink can contain a dye and / or pigment as a coloring material, and a polymer compound or a resin component as a dispersant for a pigment added as necessary. As the color material, a conventionally known color material as described in JP 2008-018719 A can be used.
Further, in order to improve the fastness of the image finally formed on the recording medium, a resin component such as a water-soluble resin or a water-soluble crosslinking agent can be added to the ink. The material used is not limited as long as it can coexist with the ink component.
When water-based ink containing a water-soluble organic solvent is used, the ink that forms the intermediate image when the intermediate image is transferred to the recording medium is free of volatile components such as moisture. The main component is a material component and a water-soluble organic solvent. When a water-soluble organic solvent is contained in the ink forming the intermediate image at the time of transferring the intermediate image to the recording medium, the peelability of the ink from the image forming surface of the transfer body becomes better, and the intermediate image Transferability can be improved. In order to obtain the effect of improving transferability, a water-soluble organic solvent having a high boiling point and a low vapor pressure is preferable. Examples of such water-soluble organic solvents include the following water-soluble organic solvents.
Alkanediols such as 1,3-butanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, and the like. Glycol ethers such as diethylene glycol monomethyl (or ethyl) ether and triethylene glycol monoethyl (or butyl) ether; Alkyl alcohols having 1 to 4 carbon atoms 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 such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one, or keto alcohol. Cyclic ethers such as tetrahydrofuran and dioxane. Glycerin. Alkylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2- or 1,3-propylene glycol, 1,2- or 1,4-butylene glycol, polyethylene glycol; Polyhydric alcohols such as thiodiglycol and 1,2,6-hexanetriol; Heterocycles such as 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylmorpholine, and sulfur-containing compounds such as dimethyl sulfoxide.
Two or more kinds of compounds can be selected and mixed from these.
When using these water-soluble organic solvents having a high boiling point and a low vapor pressure, the content in the ink is preferably selected from the range of up to 30% by mass.
The ink contains various additives such as a pH adjuster, a rust inhibitor, an antiseptic, an antifungal agent, an antioxidant, a reduction inhibitor, a water-soluble resin neutralizer, and a salt as necessary. Also good. If necessary, the surface tension of the ink may be appropriately adjusted by adding a surfactant. The surfactant is not limited as long as it does not greatly affect the storage stability of the ink. For example, anionic surfactants such as fatty acid salts, higher alcohol sulfates, liquid fatty oil sulfates, alkylallylsulfonates, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, acetylene alcohols, acetylene Nonionic surfactants such as glycols are listed. Two or more of these can also be selected and used as appropriate.
The mixing ratio of the components constituting the ink may be selected according to the method of applying the ink to the transfer body, and in the case of using the inkjet method for applying the ink, from the ejection force of the selected inkjet head, the nozzle diameter, etc. What is necessary is just to prepare suitably in the range which can discharge.

<Transfer type image recording apparatus (transfer type ink jet recording apparatus)>
An image recording apparatus according to the present invention includes a transfer member, an image forming unit that forms an intermediate image on an image forming surface of the transfer member, and a transfer unit that transfers the intermediate image from the transfer member to a recording medium. The image forming unit applies a reaction liquid applying device for applying a reaction liquid containing a component for increasing the viscosity of ink and a fluorosurfactant to the image forming surface of the transfer body, and applying ink to the image forming surface of the transfer body. Having an ink applying device for forming an intermediate image by
FIG. 2 shows an embodiment of a transfer type image recording apparatus (transfer type ink jet recording apparatus) according to the present invention. This apparatus includes a transfer body 11 having an image forming surface, an ink jet device 15 as an ink application apparatus, an application roller 14 as a reaction liquid application apparatus, and a pressing roller 18. The pressing roller 18 forms an intermediate image transfer unit together with the transfer body 11. The inkjet device 15 has a configuration for ejecting ink from an inkjet recording head.
Image recording (image formation) by this apparatus can be performed by the following operation. An intermediate image is formed by applying ink using the inkjet device 15 to the image forming surface on the transfer body 11 to which the reaction liquid has been applied by the application roller 14. Then, the intermediate image formed on the transfer body is pressed against the recording medium 17 by the pressure roller 18 to transfer the intermediate image to the recording medium.
The transfer body of the present invention can be installed on the support member 12. The support member 12 is driven to rotate in the direction of the arrow about the shaft 13, and each device arranged in the periphery operates in synchronization with the rotation.
The support member is required to have a certain degree of structural strength from the viewpoint of conveyance accuracy and durability. For the material of the support member, metal, ceramic, resin or the like is preferably used. In particular, in addition to rigidity and dimensional accuracy that can withstand pressurization during transfer, in order to reduce inertia during operation and improve control responsiveness, the following are preferably used. For example, aluminum, iron, stainless steel, acetal resin, epoxy resin, polyimide, polyethylene, polyethylene terephthalate, nylon, polyurethane, silica ceramic, alumina ceramic, and the like. It is also preferable to use these in combination. As the support member, for example, a roller-like or belt-like one can be preferably used in accordance with the form of the recording apparatus to be applied or a transfer mode to the recording medium. The use of a drum-shaped support member or a belt-shaped endless web structure support member makes it possible to repeatedly use the same transfer body, which is extremely preferable from the viewpoint of productivity.
Hereinafter, each process of the transfer type image recording method will be described.
<Reaction liquid application process>
A reaction liquid is applied to the transfer body 11 before ink is applied. As a method for applying the reaction solution, various conventionally known methods can be appropriately used. Examples include die coating, blade coating, gravure coating, and a method combining these with an offset roller. Moreover, it is also preferable to use the inkjet method as a method that can be applied at high speed and high accuracy.
<Intermediate image forming process>
Ink is applied to the image forming surface to which the reaction liquid of the transfer body 11 has been applied using the inkjet device 15. As an ink discharge method for an inkjet device, for example, a method of discharging ink by forming a bubble by causing film boiling in the ink with an electro-thermal converter, a method of discharging ink with an electro-mechanical converter, or using static electricity Then, there is a method of ejecting ink. From the viewpoint of high-speed and high-density printing, a method using an electro-thermal converter is preferably used.
There is no restriction | limiting in particular as a form of the whole inkjet device. The form of the recording head is not particularly limited, and a line head type head in which the ink discharge ports are linearly arranged in the width direction of the image forming surface of the transfer body or a scanning on the image forming surface in a predetermined direction. Any shuttle type head that applies ink can also be suitably used.
<Drying process>
In FIG. 2, the liquid content is reduced from the intermediate image by the heater 16. If the liquid content in the intermediate image is excessive, excess liquid may overflow or overflow in the next transfer process. As a result, the intermediate image may be disturbed or the transferability may be lowered. As the method for removing the liquid component, any of various conventionally used methods can be preferably applied. For example, a method using heating, a method of blowing low-humidity air, a method of reducing pressure, a method of contacting an absorber that absorbs liquid, a method of combining these, and the like can be given. Or it is also possible to dry by natural drying.

<Transfer process>
After the drying step, the intermediate image is pressure-bonded to the recording medium, and the intermediate image is transferred from the image forming surface of the transfer body to the recording medium, thereby obtaining a printed matter on which the final image is recorded. The recording medium includes not only plain paper and glossy paper used in general printing, but also widely includes cloth, plastic, film and other printing media. In press-bonding, it is preferable to apply pressure from both sides of the transfer body and the recording medium using the pressure roller 18 because an intermediate image is efficiently transferred and formed. It is also preferable to apply pressure in multiple stages because good transferability can be obtained.
<Washing process>
In some cases, the transfer body 11 is repeatedly and continuously used from the viewpoint of productivity. In this case, it is preferable to clean and regenerate the surface with the cleaning roller 19 or the like before the next image formation. As the method for washing and regenerating, any of various methods conventionally used can be preferably applied. For example, a method of applying a cleaning liquid in the form of a shower, a method of wiping a wet Molton roller in contact with the surface, a method of contacting the surface of the cleaning liquid, a method of scraping with a wiper blade, a method of applying various energy, and the like. A plurality of these may be combined.

Examples of the present invention and comparative examples will be described below.
First, transfer type inkjet recording transfer bodies, which are examples and comparative examples of the present invention, were prepared by the following method.
(Examples 1-20, Comparative Examples 1-4)
<Synthesis of condensate>
First, each condensate was synthesized by the following procedure.
In Examples 1 to 20 and Comparative Examples 1 to 4, the fluorinated alkyl compounds shown in Table 1 and the compounds B1, B2 and B3 were mixed so as to have the molar composition of the condensate shown in Table 2, and water and catalyst As a result, acetic acid was added to 500 ppm based on the total weight, and the mixture was refluxed for 24 hours or more to obtain a solution containing a condensate having a fluoroalkyl group.
<Preparation of transfer body>
Then, the transfer body was produced using the solution containing each obtained condensate.
Compound C was mixed with each solution so as to have a molar composition shown in Table 1, and diluted with an ethanol / methyl isobutyl ketone mixed solvent (mass ratio: 4/1) so that the solid content was 25% by mass. Cationic polymerization initiator CPI-410S (trade name, manufactured by San Apro) was added in an amount of 3% by mass with respect to the solid content to prepare each coating solution for forming the surface layer portion.
Subsequently, a silicone rubber having a rubber hardness of 40 degrees (durometer type A hardness) is coated on a PET (polyethylene terephthalate) film having a thickness of 0.05 mm as a main body of the transfer body to a thickness of 0.2 mm. Prepared. After the atmospheric pressure plasma treatment was performed on the main body, coating and film formation were performed by spin coating using each of the above coating solutions, and a surface layer having the main body as a base layer was provided. After providing the surface layer, the surface layer portion is exposed by irradiating with a UV lamp (exposure amount: 1.74 J / m ² ) and heated at 150 ° C. for 2 hours to cure the surface layer to constitute the image forming surface. To obtain each transfer member. The thickness of the surface layer portion thus obtained was 5.0 μm in any transfer body.
On the other hand, in Comparative Examples 1 and 2, fluororubber having a thickness of 300 μm (hardness 60A, manufactured by Rubber Tsusha) was used as a transfer member.
The fluorine content of each surface layer was determined by fluorescent X-ray analysis of the surface layer. In addition, since hydrogen is not detected in the fluorescent X-ray analysis, the weight ratio other than the hydrogen content is obtained.

<Preparation of reaction solution>
Next, the reaction liquids R1 to R4, which are examples and comparative examples in the present invention, were mixed at the compositions shown in Table 3 (parts by mass) to prepare each.
<Evaluation>
Each of the above transfer members was evaluated using the transfer type inkjet recording apparatus shown in FIG. A cylindrical drum made of an aluminum alloy was used as a support member for each transfer member. The reaction liquid was applied to the surface (image forming surface) of the transfer member at 0.6 g / m ² using a roller type coating device. Next, the ink for image formation was ejected from the ink jet device to the image forming surface of the transfer body to form an intermediate image (image that was mirror-inverted) on the transfer body. As the ink jet device, a device of an ink discharge type using an on-demand method using an electro-thermal converter was used. As the ink, a resin-dispersed pigment ink having the following composition was used.
Pigment (CI Pigment Blue 15: 3): 3.0 parts by massStyrene-acrylic acid-ethyl acrylate copolymer (acid value 240, weight average molecular weight 5000): 1.0 part by massGlycerin: 10.0 parts by mass, ethylene glycol: 5.0 parts by mass, acetylenol E100 (trade name, manufactured by Kawaken Fine Chemical Co., Ltd.): 0.5 parts by mass, ion-exchanged water: 80.5 parts by mass A final image was formed by pressing and transferring the intermediate image formed by the above-described method to a recording medium using high-quality paper (trade name: OK Prince, manufactured by Oji Paper Co., Ltd.). After transfer of the intermediate image, the image forming surface was regenerated by washing, and the application property and transferability as the reaction liquid application characteristics after repeated and continuous intermediate image formation and transfer were evaluated 50000 times.
(Reaction liquid applicability)
About the transfer body before and after performing 50000 times of transfer, the uniformity of the reaction liquid provided on the surface of the transfer body was visually evaluated using the following criteria.
A: Uniformly applied to the surface of the transfer body.
B: Almost uniformly applied to the surface of the transfer body.
C: Not uniformly applied on the surface of the transfer body.
D: There is a portion where the reaction liquid is repelled and not applied on the surface of the transfer body.
(Transferability)
For the transfer body before and after the transfer of 50000 times, the image quality of the transfer body after the transfer and the final image was observed with an optical microscope and evaluated according to the following criteria.
A: The rest of the image was not confirmed on the transfer body, and the final image was also formed satisfactorily.
B: The rest of the image was slightly confirmed on the transfer body, but the quality of the final image had no practical problem.
C: The rest of the image was slightly confirmed on the transfer body, and a part of the final image was not sufficiently transferred.
D: The rest of the image was confirmed on the transfer body, and the final image was not fully transferred.
The above evaluation results are shown in Table 2.

In Table 2, B1 to B3 and C represent the following compounds.
B1: 3-glycidoxypropylmethyldiethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-402)
B2: Dimethyldiethoxysilane (manufactured by Shin-Etsu Chemical Co., KBE-22)
B3: Methyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., KBE-13)
C: Bis (triethoxysilylpropyl) polyethylene oxide (manufactured by Gelest, SIB1824.84)

As a result, Example 1 using a reaction liquid containing a transfer body having a surface layer portion made of a cured product of an organosiloxane compound (condensate) having a one-end reaction type fluoroalkyl group in the skeleton and a fluorosurfactant. In -20, the coating properties of the reaction solution were all good without repelling, and the transferability was also good.
On the other hand, in Comparative Examples 1 and 4 in which the reaction solution of the present invention was not used, repelling of the reaction solution occurred or coating uniformity was not sufficient, and good image formation could not be performed. Further, in Comparative Examples 2 and 3 in which the transfer body of the present invention was not used, the coatability of the reaction system was good, but the transferability was insufficient and a good printed matter could not be obtained.

1 Transfer Material 2 Surface Layer 3 Base Layer

Claims (10)

A transfer body for transfer type image formation using an ink and a reaction liquid containing a component for increasing viscosity of the ink and a fluorine-based surfactant,
The surface layer portion of the image forming surface to which the ink and the reaction liquid of the transfer body are applied,

(In general formula (1),
R represents a linear or branched fluoroalkyl group having 2 to 29 fluorine atoms and 1 to 14 carbon atoms,
L is a linker group and represents a substituted or unsubstituted divalent group having 1 to 20 carbon atoms;
X represents a reactive functional group including an alkoxysilyl group, a hydroxysilyl group, a vinyl group, a (meth) acryl group, or a cyclic ether group having 2 to 3 carbon atoms. )
Comprising at least one reaction product of a fluorinated alkyl compound represented by:
A transfer body characterized by that.   The transfer body according to claim 1, wherein a content of fluorine in the surface layer portion is 0.1% by mass or more and 20% by mass or less.   The transfer body according to claim 1 or 2, wherein, in the general formula (1), the fluorine number of R is 6 or more and 17 or less.   The transfer body according to claim 1, wherein, in the general formula (1), X is an alkoxysilyl group.   The transfer according to any one of claims 1 to 4, wherein the reaction product includes a reaction product of a compound represented by the general formula (1) having at least two different fluorine numbers for R. body. The transfer body according to any one of claims 1 to 5, wherein the ink is applied to the image forming surface by an inkjet method. A reaction liquid applying step for applying a reaction liquid containing a component for increasing the viscosity of the ink and a fluorosurfactant to the image forming surface of the transfer body, and forming an intermediate image by applying ink to the image forming surface of the transfer body. An ink application process, and an image forming process comprising:
A transfer step of transferring the intermediate image from the transfer member to a recording medium;
An image recording method comprising:
An image recording method, wherein the transfer body is the transfer body according to any one of claims 1 to 6. The image recording method according to claim 7, wherein the ink is applied to the image forming surface by an ink jet method. A transcript,
An intermediate image is formed by applying a reaction liquid applying device for applying a reaction containing a component that increases the viscosity of the ink and a fluorosurfactant to the image forming surface of the transfer body, and applying ink to the image forming surface of the transfer body. An image forming unit having an ink applying device to be formed;
A transfer unit for transferring the intermediate image from the transfer member to a recording medium;
An image recording apparatus comprising:
An image recording apparatus, wherein the transfer body is the transfer body according to any one of claims 1 to 6. The image recording apparatus according to claim 9, wherein the ink applying apparatus includes an inkjet device.

Images