JP2016172807A - Liquid composition, recording method, and recording apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid composition excellent in dispersion stability and sublimation property, a recording method, and a recording apparatus.SOLUTION: The liquid composition comprises polymer particles and a dispersion dye having sublimation property and is to be deposited on a transfer recording medium and heated at a heating temperature C (°C). The polymer particle has a core part comprising a resin having a glass transition temperature A (°C) and a shell part covering at least partially the core part and having a glass transition temperature B (°C). The core part contains the above dispersion dye; the glass transition temperature A and the glass transition temperature B satisfy A<B; and the glass transition temperature A and the heating temperature C satisfy A<C.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a liquid composition, a recording method, and a recording apparatus.

In recent years, a recording method for recording a design or a design on a recording medium such as a fabric using sublimation transfer has been widespread. In such a recording method using sublimation transfer, a liquid composition containing a sublimation disperse dye is attached to a sublimation transfer recording medium such as sublimation transfer paper by an ink jet method, and attached to the sublimation transfer recording medium. Recording is performed by sublimation transfer of the liquid composition to a recording medium. And as such a liquid composition, as described in Patent Document 1, for example, a sublimable dye-containing polymer particle in which an ethylenically unsaturated monomer solution in which a sublimable dye is dispersed is dispersed in water. A water-based sublimable dye ink composition containing an aqueous dispersion is known.

JP 2010-83968 A

However, the water-based sublimable dye ink composition described in Patent Document 1 causes the sublimation dyes to aggregate in the ink composition when left for a long period of time, resulting in separation and sedimentation of the sublimation dyes. There was a problem that the performance would be reduced.

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

[Application Example 1] A liquid composition according to this application example includes polymer particles and a disperse dye having sublimation property, and is attached to a recording medium for sublimation transfer and heated at a heating temperature C (unit: ° C). In the liquid composition, the polymer particles include a core part containing a resin having a glass transition temperature A (unit: ° C.) and a glass transition temperature B (unit: covering at least a part of the core part). C.) a shell portion containing a resin, the core portion contains the disperse dye, the glass transition temperature A and the glass transition temperature B satisfy the following formula (1), and The glass transition temperature A satisfies the following formula (2) in relation to the heating temperature C.
A <B (1)
A <C (2)

According to this application example, the polymer particles are composed of a core resin corresponding to the core and a shell resin corresponding to the shell. Such a structure of polymer particles composed of a core part and a shell part is hereinafter referred to as “core-shell type”. And since the glass transition temperature B of the shell part (hereinafter also referred to as “Tg”) is higher than the glass transition temperature A of the core part, the shell part can withstand a higher temperature environment than the core part, and the particles The shape can be maintained. Further, the core portion contains a disperse dye. Since the disperse dye is contained in the core part and surrounded by the shell part that maintains the particle shape, the disperse dye is stabilized in the liquid composition. Accordingly, it is possible to provide a liquid composition that is less likely to cause separation and sedimentation of the disperse dye and has excellent dispersion stability. Moreover, since dissolution of the disperse dye into the liquid component via the shell portion is reduced, precipitation of foreign matters can be prevented and storage stability can be improved.

Then, the liquid composition in a state where the disperse dye is contained in the polymer particles is attached to the recording medium for sublimation transfer, and is heated at a heating temperature C higher than the glass transition temperature A of the core portion, thereby sublimating. In the liquid composition on the surface of the transfer recording medium, a part of the core portion is in a molten state. Also, some liquid components contained in the liquid composition are evaporated, and the liquid composition is dried on the surface of the sublimation transfer recording medium. Accordingly, the disperse dye is mixed with the resin in the core portion, and the disperse dye can be fixed on the surface of the sublimation transfer recording medium.

Application Example 2 The liquid composition described in the above application example is attached to the sublimation transfer recording medium and heated at the heating temperature C, and further, the heating temperature D is applied from the sublimation transfer recording medium to the recording medium. It is a liquid composition that is sublimated and transferred at (unit: ° C.), and the glass transition temperature B preferably satisfies the following formula (3) in relation to the heating temperature D.
B <D (3)

According to this application example, the shell portion melts due to the heating temperature D exceeding the glass transition temperature B of the shell portion, and the core-shell structure of the polymer particles is destroyed. And the glass transition temperature A of the core part
Is lower than the glass transition temperature B of the shell portion, the resin in the core portion is also melted, and the disperse dye mixed with the resin in the core portion is also eluted on the surface of the sublimation transfer recording medium. Furthermore, since the disperse dye sublimates from a solid to a gas at the heating temperature D, it is sublimated from the sublimation transfer recording medium to the recording medium. Therefore, it is possible to provide a liquid composition in which the disperse dye is surely sublimated and excellent in color developability. Further, in the stage before sublimation transfer at the heating temperature D, the disperse dye is not sublimated because it is included in the polymer particles. Accordingly, it is possible to prevent the disperse dye from being sublimated at the stage where the liquid composition is attached to the sublimation transfer recording medium, thereby preventing the work environment from being contaminated or the operator from sucking the disperse dye.

Application Example 3 In the liquid composition described in the application example, the glass transition temperature A is preferably −10 ° C. or more and 50 ° C. or less.

According to this application example, the glass transition temperature A of the core portion is equal to or lower than room temperature or about room temperature.
Further, since the temperature is lower than the heating temperature C, the core portion is in a molten state in the liquid composition on the surface of the sublimation transfer recording medium. Therefore, the disperse dye is mixed with the resin of the core part, and the disperse dye can be further easily eluted.

Application Example 4 In the liquid composition described in the application example, the heating temperature C is 20 ° C. or more and 100
It is preferable that it is below ℃.

According to this application example, some liquid components such as water contained in the liquid composition attached to the sublimation transfer recording medium are evaporated, and the liquid composition is dried on the surface of the sublimation transfer recording medium. Therefore, even if the liquid composition adheres to the sublimation transfer recording medium and is rubbed with another sublimation transfer recording medium or a finger, the disperse dye on the sublimation transfer recording medium is another sublimation transfer recording. The effect that it is excellent in scratch resistance which reduces that it adheres to a medium, a finger | toe, etc. and moves can be acquired. In addition, when the heating temperature C exceeds 100 ° C., the disperse dye may sublime at the stage where the liquid composition adheres to the recording medium for sublimation transfer.
There is a possibility that the color developability of the recording medium after the transfer is lowered. However, according to this application example, since the heating temperature C is 100 ° C. or lower, the disperse dye is difficult to sublime at the stage where the liquid composition adheres to the recording medium for sublimation transfer, and contamination of the working environment and color developability. Decline can be prevented.

Application Example 5 In the liquid composition described in the application example, the heating temperature D is 160 ° C. or higher and 25
It is preferably 0 ° C. or lower.

According to this application example, many liquid components such as an organic solvent contained in the liquid composition attached to the recording medium for sublimation transfer are evaporated, the melted core portion and shell portion are concentrated, and the disperse dye is further added. It tends to be eluted on the surface of the recording medium for sublimation transfer. Therefore, the color developability can be further improved.

Application Example 6 In the liquid composition described in the above application example, it is preferable that at least one of the monomers constituting the polymer particles includes (meth) acrylates, (meth) acrylic acid, and styrene.

According to this application example, since the polymer particles can arbitrarily set the glass transition temperature A and the glass transition temperature B depending on the types of monomers constituting the polymer particles, the liquid composition has excellent temperature responsiveness. Things can be provided.

Application Example 7 In the liquid composition described in the above application example, the content of the polymer particles is preferably 4% by mass or more and 20% by mass or less of the total mass of the liquid composition.

According to this application example, when the content of the polymer particles is 4% by mass or more, the disperse dye is protected by the polymer particles, so that an effect of further improving the scratch resistance can be obtained. And since the disperse dye is contained in the core part, the liquid composition excellent also in color development can be provided. Moreover, when the content of the polymer particles is 20% by mass or less, the disperse dye is stabilized in the liquid composition, and an effect that the dispersion stability and the storage stability are excellent can be obtained.

Application Example 8 In the liquid composition described in the application example, it is preferable that the glass transition temperature B satisfies the following formula (4) in relation to the heating temperature C.
B <C (4)

According to this application example, since the heating temperature C is higher than that of the shell portion, the shell portion melts on the sublimation transfer recording medium, and the core-shell structure of the polymer particles is destroyed. Then, by dissolving a large number of polymer particles, the core part is also eluted and spread on the sublimation transfer recording medium, and a film is formed on the sublimation transfer recording medium. Since the disperse dye is covered with this film, the scratch resistance can be further improved. Further, by forming a film on the surface of the sublimation transfer recording medium, the disperse dye mixes with the melted core portion and shell portion, and is effectively fixed to the sublimation transfer recording medium. Therefore, the recording medium for sublimation transfer does not need to have a fixing layer such as a liquid receiving layer or a liquid absorbing layer, and is not limited to liquid absorptivity, liquid low absorptivity, or liquid non-absorptivity, and the type thereof is not limited. Can be obtained.

[Application Example 9] A recording method according to this application example includes a first step in which a liquid composition is attached to a sublimation transfer recording medium, and a sublimation transfer recording medium to which the liquid composition is attached. A second step of heating at a unit of ° C.), wherein the liquid composition includes polymer particles and a disperse dye having sublimation property, and the polymer particles have a glass transition. A core part including a resin having a temperature A (unit: ° C.) and a shell part including a resin having a glass transition temperature B (unit: ° C.) covering at least a part of the core part. Contains the disperse dye, the glass transition temperature A and the glass transition temperature B satisfy the following formula (5), and the glass transition temperature A is related to the heating temperature C by the following formula ( 6) is satisfied.
A <B (5)
A <C (6)

According to this application example, the liquid composition to be attached to the sublimation transfer recording medium in the first step includes polymer particles, and the polymer particles correspond to the core resin corresponding to the core and the shell. It is comprised from the resin of a shell part. And since the glass transition temperature B of a shell part is higher than the glass transition temperature A of a core part, a shell part can endure a temperature environment higher than a core part, and can maintain a particle shape. Further, the core portion contains a disperse dye. Since the disperse dye is contained in the core part and surrounded by the shell part that maintains the particle shape, the disperse dye is stabilized in the liquid composition. Accordingly, it is possible to provide a recording method in which disperse dyes are not easily separated or settled, and the dispersion stability of the liquid composition is excellent. Moreover, since dissolution of the disperse dye into the liquid component through the shell portion is reduced, precipitation of foreign matters can be prevented, and the storage stability of the liquid composition can be improved.

Then, the sublimation transfer recording medium to which the liquid composition containing the disperse dye is contained in the polymer particles in the second step is heated at a heating temperature C higher than the glass transition temperature A of the core. As a result, in the liquid composition on the surface of the recording medium for sublimation transfer, the core portion is in a molten state. When a part of the liquid component contained in the liquid composition evaporates and a part of the shell part melts due to the concentration of the solvent, etc., a film is easily formed by the melted core part. Can be fixed on the recording medium surface.

Application Example 10 In the recording method described in the application example, the sublimation transfer recording medium to which the liquid composition is attached and heated at the heating temperature C is brought into contact with the recording medium, and the sublimation transfer recording is performed. And a third step of heating the recording medium and / or the recording medium at a heating temperature D (unit: ° C.) to sublimate transfer the liquid composition from the sublimation transfer recording medium to the recording medium. In the recording method, it is preferable that the glass transition temperature B satisfies the following formula (7) in relation to the heating temperature D.
B <D (7)

According to this application example, the shell portion melts due to the heating temperature D exceeding the glass transition temperature B of the shell portion in the third step, and the core-shell structure of the polymer particles is destroyed. Since the glass transition temperature A of the core portion is lower than the glass transition temperature B of the shell portion, the resin in the core portion is also melted, and the disperse dye mixed with the resin in the core portion is eluted on the surface of the sublimation transfer recording medium. . Furthermore, since the disperse dye sublimates from a solid to a gas at the heating temperature D, it is sublimated from the sublimation transfer recording medium to the recording medium. Therefore, it is possible to provide a recording method in which the disperse dye is surely sublimated and excellent in color developability. Further, in the stage before sublimation transfer at the heating temperature D, the disperse dye is not sublimated because it is included in the polymer particles. Accordingly, it is possible to prevent the disperse dye from being sublimated at the stage where the liquid composition is attached to the sublimation transfer recording medium, thereby preventing the work environment from being contaminated or the operator from sucking the disperse dye.

Application Example 11 A recording apparatus according to this application example includes a recording head for attaching a liquid composition to a sublimation transfer recording medium, and a heating temperature C for the sublimation transfer recording medium to which the liquid composition is attached.
The liquid composition includes a polymer particle and a disperse dye having sublimation property, and the polymer particle has a glass transition. Temperature A (
A core portion containing a resin having a unit of ° C) and a shell portion containing a resin having a glass transition temperature B (unit: ° C) covering at least a part of the core portion, It contains a disperse dye, the glass transition temperature A and the glass transition temperature B satisfy the following formula (8), and the glass transition temperature A satisfies the following formula (9) in relation to the heating temperature C: It is characterized by satisfying.
A <B (8)
A <C (9)

According to this application example, the liquid composition that the recording head adheres to the recording medium for sublimation transfer includes polymer particles, and the polymer particles include the core resin corresponding to the core and the shell corresponding to the shell. Part of the resin. And since the glass transition temperature B of a shell part is higher than the glass transition temperature A of a core part, a shell part can endure a temperature environment higher than a core part, and can maintain a particle shape. Further, the core portion contains a disperse dye. Since the disperse dye is contained in the core part and surrounded by the shell part maintaining the particle shape, the disperse dye is stabilized in the liquid composition in the recording head. Therefore, since it is possible to prevent the disperse dye from dissolving in the liquid component via the shell portion in the recording head, it is possible to obtain an effect that the ejection stability is excellent.

The sublimation transfer recording medium to which the liquid composition containing the disperse dye contained in the polymer particles is attached is heated at a heating temperature C higher than the glass transition temperature A of the core. As a result, in the liquid composition on the surface of the sublimation transfer recording medium, the core portion is in a molten state.
When a part of the liquid component contained in the liquid composition evaporates and a part of the shell part melts due to the concentration of the solvent, etc., a film is easily formed by the melted core part. Can be fixed on the recording medium surface.

FIG. 2 is a schematic cross-sectional view illustrating a configuration of a recording apparatus according to the present embodiment. The flowchart of the recording method which concerns on this embodiment.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail with reference to the drawings as necessary. However, the present invention is not limited to this,
Various modifications are possible without departing from the scope of the invention. In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. Further, positional relationships such as up, down, left and right are based on the positional relationships shown in the drawings unless otherwise specified. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios. In the present specification, “(meth) acryl” means “acryl” and “methacryl” corresponding to it, and “(meth) acrylate” means “
“Acrylate” and its corresponding “methacrylate”. Further, having the “core part” and the “shell part” does not have to be strictly in the structure and state. The resin constituting the core part and the resin constituting the shell part exist separately, and the resin constituting the core part only needs to be present so that the resin constituting the shell part covers a certain amount.

[Embodiment]
[Liquid composition]
The liquid composition according to the present embodiment includes polymer particles and a disperse dye having sublimation property,
A liquid composition attached to a recording medium for sublimation transfer and heated at a heating temperature C (unit: ° C.), wherein the polymer particles include a core portion containing a resin having a glass transition temperature A (unit: ° C.), A shell portion containing a resin having a glass transition temperature B (unit: ° C.) covering at least a part of the core portion, the core portion containing a disperse dye, and having a glass transition temperature A and a glass transition temperature B Is the following formula (1
) And the glass transition temperature A satisfies the following formula (2) in relation to the heating temperature C.
A <B (1)
A <C (2)
The liquid composition according to the present embodiment is attached to the sublimation transfer recording medium and heated at the heating temperature C, and further sublimated from the sublimation transfer recording medium to the recording medium at the heating temperature D (unit: ° C.). In the liquid composition to be transferred, the glass transition temperature B preferably satisfies the following formula (3) in relation to the heating temperature D.
B <D (3)

(Polymer particles)
The liquid composition according to this embodiment includes polymer particles. The polymer particles have a glass transition temperature A
It is a core shell type structure which has the core part containing this resin, and the shell part containing the resin of the glass transition temperature B formed in the surface of the core part. Moreover, the core part contains the disperse dye which has sublimation property. And in the glass transition temperature A and the glass transition temperature B, as shown by the said Formula (1), the glass transition temperature B is higher temperature. The glass transition temperature is an index indicating the hardness of the resin, and the higher the glass transition temperature, the harder the resin. Therefore, the shell part exhibits a relatively hard property than the core part, and the shell part can withstand a higher temperature environment than the core part and maintain the particle shape. Since the disperse dye is contained in the core portion and surrounded by a hard shell portion that maintains the particle shape, the disperse dye is stabilized in the liquid composition. Therefore, by using such polymer particles, it is difficult for the disperse dye to be separated and settled, and the disperse dye is hardly dissolved in the liquid component via the shell portion, and the liquid composition is excellent in dispersion stability and storage stability. . Further, the liquid composition in a state where the disperse dye is contained in the polymer particles is attached to the recording medium for sublimation transfer, and is heated at a heating temperature C higher than the glass transition temperature A of the core portion. In the liquid composition on the surface of the transfer recording medium, the core portion is in a molten state. Therefore, the disperse dye tends to be mixed with the resin of the core portion and easily eluted.

(Core part)
The glass transition temperature A of the resin contained in the core part is preferably −10 ° C. or more and 50 ° C. or less,
It is more preferably 10 ° C. or higher and 45 ° C. or lower, and further preferably −10 ° C. or higher and 38 ° C. or lower. When the temperature range of the glass transition temperature A is −10 ° C. or more and 50 ° C. or less, the temperature is below room temperature or about room temperature, and further sublimated because the temperature is lower than the heating temperature C as shown in the above formula (2). In the liquid composition on the surface of the transfer recording medium, the core portion is in a molten state. Therefore, the disperse dye tends to be mixed with the resin in the core portion and the disperse dye tends to be eluted. The heating temperature C higher than the glass transition temperature A of the core is preferably 20 ° C. or higher and 100 ° C. or lower, more preferably 30 ° C. or higher and 80 ° C. or lower, and 40 ° C. or higher and 60 ° C. or lower. More preferably it is. When the heating temperature C is within the above range, some liquid components such as water contained in the liquid composition attached to the sublimation transfer recording medium evaporate, and the liquid composition is formed on the surface of the sublimation transfer recording medium. Dry out. Therefore, the scratch resistance tends to be improved. Further, when the heating temperature C exceeds 100 ° C., part of the disperse dye is likely to sublime at the stage where the liquid composition adheres to the recording medium for sublimation transfer. There is a possibility that the color developability of the recording medium may be deteriorated. However, the heating temperature C
When the temperature is 100 ° C. or lower, since the disperse dye hardly sublimes at the stage when the liquid composition adheres to the recording medium for sublimation transfer, it is possible to prevent contamination of the working environment and deterioration of color development.

The resin contained in the core part and the shell part described later may be a homopolymer or a copolymer. When the resin contained in the core part and the shell part described later is a homopolymer, the Tg of the homopolymer described in various documents (for example, a polymer handbook) can be used. Moreover, when the resin contained in the core part and the shell part described later is a copolymer, the glass transition temperature Tg of the copolymer is the Tg _n (unit: K) of various homopolymers and the mass of the monomer. It can be calculated from the fraction (W _n ) by the following FOX equation.
1 / Tg = W ₁ / Tg ₁ + W ₂ / Tg ₂ +... + W _n / Tg _n
Where W _n ; mass fraction of each monomer
Tg _n : Glass transition temperature of homopolymer of each monomer (unit: K)
Tg: Glass transition temperature of copolymer (unit: K)
n: natural number

In the liquid composition of the present embodiment, at least one of the monomers constituting the polymer particles is (
It preferably contains (meth) acrylates, (meth) acrylic acid, and styrene. Thereby, since the polymer particles can arbitrarily set the glass transition temperature A and the glass transition temperature B depending on the type of monomer constituting the polymer particles, a liquid composition having excellent temperature responsiveness is provided. be able to. Although it does not specifically limit as a homopolymer, For example, 2-ethylhexyl acrylate homopolymer (Tg: -70 degreeC), 2-ethylhexyl methacrylate homopolymer (Tg: -10 degreeC), 2-hydroxyethyl acrylate homopolymer (Tg) : -15 ° C), 2-hydroxyethyl methacrylate homopolymer (Tg: 55)
° C), 2-hydroxybutyl acrylate homopolymer (Tg: -7 ° C), 2-hydroxybutyl methacrylate homopolymer (Tg: 26 ° C), 2-methoxyethyl acrylate homopolymer (Tg: -50 ° C), 4-hydroxy Butyl acrylate homopolymer (
Tg: −80 ° C.), iso-octyl methacrylate homopolymer (Tg: −45 ° C.),
Iso-butyl acrylate homopolymer (Tg: 43 ° C.), iso-butyl methacrylate homopolymer (Tg: 53 ° C.), iso-propyl acrylate homopolymer (Tg
: -3 ° C), iso-propyl methacrylate homopolymer (Tg: 81 ° C), N, N-
Diethylaminoethyl methacrylate homopolymer (Tg: 20 ° C), N, N-dimethylaminoethyl acrylate homopolymer (Tg: 18 ° C), N, N-dimethylaminoethyl methacrylate homopolymer (Tg: 18 ° C), N, N- Dimethylaminopropylacrylamide homopolymer (Tg: 134 ° C.), n-butyl acrylate homopolymer (T
g: -54 ° C), tert-butyl acrylate homopolymer (Tg: 43 ° C), ter
t-Butyl methacrylate homopolymer (Tg: 20 ° C), acrylamide homopolymer (Tg: 179 ° C), acrylic acid homopolymer (Tg: 106 ° C), acrylonitrile homopolymer (Tg: 125 ° C), isoamyl acrylate homopolymer (Tg) : -45 ° C
), Isobutyl acrylate homopolymer (Tg: -26 ° C), isobutyl methacrylate homopolymer (Tg: 48 ° C), isobornyl acrylate homopolymer (Tg: 9)
4 ° C.), isobornyl methacrylate homopolymer (Tg: 155 ° C. to 180 ° C.), itaconic acid homopolymer (Tg: 100 ° C.), ethyl acrylate homopolymer (Tg: −2)
2 ° C to -24 ° C), ethyl carbitol acrylate homopolymer (Tg: -67 ° C),
Ethyl methacrylate homopolymer (Tg: 65 ° C), ethoxyethyl acrylate homopolymer (Tg: -50 ° C), ethoxyethyl methacrylate homopolymer (Tg: 15)
° C), ethoxydiethylene glycol acrylate homopolymer (Tg: -70 ° C), octyl acrylate homopolymer (Tg: -65 ° C), iso-octyl acrylate homopolymer (Tg: -70 ° C), cyclohexyl acrylate homopolymer (Tg: 15 ° C)
-19 ° C), cyclohexyl methacrylate homopolymer (Tg: 66 ° C to 83 ° C), dicyclopentanyl acrylate homopolymer (Tg: 120 ° C), dicyclopentanyl methacrylate homopolymer (Tg: 175 ° C), styrene homopolymer (Tg: 100 ° C.
), Stearyl acrylate homopolymer (Tg: 35 ° C.), tertiary butyl acrylate homopolymer (Tg: 41 ° C.), tertiary butyl methacrylate homopolymer (Tg: 107 ° C.), tetradecyl acrylate homopolymer (Tg: 24 ° C.) Tetradecyl methacrylate homopolymer (Tg: -72 ° C), tetrahydrofurfuryl acrylate homopolymer (Tg: -12 ° C), tetrahydrofurfuryl methacrylate homopolymer (Tg: 60 ° C), nonyl acrylate homopolymer (Tg: 58 ° C) ), Phenoxyethyl acrylate homopolymer (Tg: −22 ° C.), phenoxyethyl methacrylate homopolymer (Tg: 54 ° C.), butyl acrylate homopolymer (Tg: −56 ° C.)
Butyl methacrylate homopolymer (Tg: 20 ° C.), propyl acrylate homopolymer (Tg: 3 ° C.), propyl methacrylate homopolymer (Tg: 35 ° C.), hexadecyl acrylate homopolymer (Tg: 35 ° C.), hexadecyl methacrylate homo Polymer (Tg: 15 ° C), hexyl acrylate homopolymer (Tg: -57 ° C), hexyl methacrylate homopolymer (Tg: -5 ° C, benzyl acrylate homopolymer (T
g: 6 ° C.), benzyl methacrylate homopolymer (Tg: 54 ° C.), pentyl acrylate homopolymer (Tg: 22 ° C.), pentyl methacrylate homopolymer (Tg: −5)
° C), maleic acid homopolymer (Tg: 130 ° C), methacrylic acid homopolymer (Tg:
185 ° C.) carboxyethyl acrylate homopolymer (Tg: 37 ° C.), methyl acrylate homopolymer (Tg: 8 ° C.), methyl methacrylate homopolymer (Tg: 105)
° C), methoxyethyl acrylate homopolymer (Tg: -50 ° C), methoxy methacrylate homopolymer (Tg: -16 ° C), lauryl acrylate homopolymer (Tg:-
3 ° C. to 15 ° C.), lauryl methacrylate homopolymer (Tg: −65 ° C.), and vinyl acetate homopolymer (Tg: 32 ° C.). Tg is not limited to the above because it may vary depending on the homopolymer production method and stereoregularity.

When the resin is a homopolymer, the glass transition temperature A of the resin contained in the core part can be controlled by selecting the homopolymer. Moreover, when resin is a copolymer, it can control by considering Tg of the said homopolymer, and the said FOX formula.

In addition, the resin contained in the core part is not particularly limited. For example, hydrophilic (meta)
Acrylate monomer unit, hydrophobic (meth) acrylate monomer unit having an alkyl group having 3 or more carbon atoms, hydrophobic (meth) acrylate monomer unit having a cyclic structure, (meth) acrylamide monomer unit or N-substituted derivative thereof, aroma A polymer having at least one of an aromatic vinyl compound monomer unit and a carboxylic acid monomer unit is preferred. Among these, a hydrophobic (meth) acrylate having an alkyl group having 3 or more carbon atoms and a polymer having an aromatic vinyl compound are preferable.

The hydrophilic (meth) acrylate monomer is not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, α-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (poly) Examples include ethylene glycol (meth) acrylate, methoxy (poly) ethylene glycol (meth) acrylate, ethoxy (poly) ethylene glycol (meth) acrylate, and (poly) propylene glycol (meth) acrylate. Among these, methyl (meth) acrylate and ethyl (meth) acrylate are preferable. Here, “hydrophilic” means 100 mL of water (20 ° C.)
The solubility with respect to is said to be 0.3 g or more.

As a hydrophobic (meth) acrylate monomer having an alkyl group having 3 or more carbon atoms,
Although not particularly limited, for example, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate,
n-amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth)
Acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth)
Examples thereof include (meth) acrylates having an alkyl group having 3 or more carbon atoms, such as acrylate, stearyl (meth) acrylate, cetyl (meth) acrylate, neopentyl (meth) acrylate, and behenyl (meth) acrylate. Among these, lauryl (meth) acrylate is preferable. Here, “hydrophobic” means that the solubility in 100 mL of water (20 ° C.) is less than 0.3 g.

The hydrophobic (meth) acrylate monomer having a cyclic structure is not particularly limited, and examples thereof include cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclopentenyloxyethyl ( Examples include meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, adamantyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate.

Although it does not specifically limit as a (meth) acrylamide monomer or its N-substituted derivative, For example, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide,
Examples include (meth) acrylamide such as diacetone acrylamide and N, N-dimethylacrylic (meth) amide or N-substituted derivatives thereof.

Although it does not specifically limit as an aromatic vinyl compound monomer, For example, styrene, alpha-
Examples include methylstyrene, p-methylstyrene, vinyl toluene, chlorostyrene, and divinylbenzene.

Although it does not specifically limit as a carboxylic acid monomer, For example, (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid etc. are mentioned. Among these, (meta)
Acrylic acid is preferred. Here, the “carboxylic acid monomer unit” refers to a polymerizable monomer unit having a carboxyl group and a polymerizable unsaturated group.

  The said monomer may be used individually by 1 type, or may use 2 or more types together.

Of all the repeating units constituting the resin contained in the core part, the content of the repeating unit derived from the hydrophobic monomer is preferably 80% by mass or more, and more preferably 90% by mass or more. Since the content of the repeating unit derived from the hydrophobic monomer is in the above range, a hydrophobic film is formed on the surface of the image recorded on the sublimation transfer recording medium by performing a heat treatment, etc. Tend to be more improved.

The resin contained in the core part may be used alone or in combination of two or more. When two or more kinds of resins are contained in the core portion, the glass transition temperature of the resin having the highest glass transition temperature is defined as the glass transition temperature A.

(Disperse dye)
The core part includes a disperse dye having sublimation properties. The disperse dye having a sublimation property is a disperse dye having a property of sublimation by heating, and a dry heat treatment test (Method C) and a contamination (polyester) test in a dye fastness test method for dry processing stipulated in JIS L 0879. Those having a result of grade 3-4 or lower can be preferably used, more preferably those of grade 3 or lower can be used.

As the disperse dye having sublimation property, a disperse dye having the above properties can be used. Specific examples of such disperse dyes include C.I. I. Disperse Yellow 3, 7,
8, 23, 39, 51, 54, 60, 71, 86; I. Disperse Orange 1, 1
: 1, 5, 20, 25, 25: 1, 33, 56, 76; I. Disperse Brown 2
C. I. Disperse thread 11, 50, 53, 55, 55: 1, 59, 60, 65,
70, 75, 93, 146, 158, 190, 190: 1, 207, 239, 240; C
. I. Vat Red 41; I. Disperse Violet 8, 17, 23, 27, 2
8, 29, 36, 57; C.I. I. Disperse Blue 19, 26, 26: 1, 35, 55
56, 58, 64, 64: 1, 72, 72: 1, 81, 81: 1, 91, 95, 108
131, 141, 145, 359; I. Solvent Blue 36, 63, 105, 1
11 etc. are mentioned. These may be used alone or in combination of two or more.

Among these, from the viewpoint of storage stability of the liquid composition, C.I. I. Disperse Yellow 3, 7
8, 23, 51, 54, 60, 71, 86; I. Disperse Orange 20, 25
25: 1, 56, 76; I. Disperse brown 2; C.I. I. Disperse thread 11, 53, 55, 55: 1, 59, 60, 65, 70, 75, 146, 190, 19
0: 1, 207, 239, 240; I. Vat Red 41; I. Disperse violet 8, 17, 23, 27, 28, 29, 36, 57; C.I. I. Disperse Blue 26, 26: 1, 55, 56, 58, 64, 64: 1, 72, 72: 1, 81, 81:
1, 91, 95, 108, 131, 141, 145, 359; I. Solvent blue 36, 63, 105, 111 and the like are more preferable.

(Shell part)
The glass transition temperature B of the resin contained in the shell part is higher than the glass transition temperature A of the resin contained in the core part. And 20 to 230 degreeC is preferable, 25 to 160 degreeC is more preferable, and 30 to 100 degreeC is further more preferable. The glass transition temperature B can be arbitrarily set according to the type of monomer constituting the polymer particles. The heating temperature D exceeding the glass transition temperature B of the shell is preferably 160 ° C. or higher and 250 ° C. or lower, more preferably 170 ° C. or higher and 230 ° C. or lower, and 180 ° C. or higher and 210 ° C. or lower. More preferably. When the heating temperature D is within the above range, many liquid components such as an organic solvent contained in the liquid composition attached to the sublimation transfer recording medium are evaporated, and the melted core portion and shell portion are concentrated. Further, the disperse dye is further easily eluted on the surface of the recording medium for sublimation transfer. Therefore, the color developability can be further improved.

As the resin contained in the shell portion, a resin having a (meth) acrylate monomer unit and a carboxylic acid monomer unit is preferable. By using such a resin, a carboxyl group can be present on the surface of the shell portion. As a result, the dispersion stability and storage stability of the polymer particles are further improved, and the viscosity of the ink composition is relatively low, so that the ejection stability tends to be further improved. The (meth) acrylate monomer unit is not particularly limited. For example, a hydrophilic (meth) acrylate monomer unit, a hydrophobic (meth) acrylate monomer unit having an alkyl group having 3 or more carbon atoms, or a hydrophobic structure having a cyclic structure. (Meth) acrylate monomer unit. Specific examples of the (meth) acrylate monomer unit and the carboxylic acid monomer unit are the same as those described above for the monomer unit constituting the resin contained in the core part. More than one species may be used in combination.

Of all repeating units constituting the resin contained in the shell part, the content of repeating units derived from (meth) acrylic acid ester and unsaturated carboxylic acid is preferably 80% by mass or more, more preferably 90% by mass or more. 95 mass% or more is more preferable.

Of all the repeating units constituting the resin contained in the shell part, the content of the repeating unit derived from the hydrophilic monomer is preferably 80% by mass or more, more preferably 90% by mass or more,
95 mass% or more is more preferable. When the content of the repeating unit derived from the hydrophilic monomer is in the above range, a hydration layer is formed around the shell portion, so that the dispersion stability of the polymer particles in the ink composition tends to be improved. is there. Moreover, since it can suppress more effectively that a polymer particle adheres to a nozzle, it exists in the tendency for the discharge stability from the nozzle of a recording head to become more favorable.

The resin contained in the shell part may be used alone or in combination of two or more. When two or more kinds of resins are contained in the shell portion, the glass transition temperature of the resin having the lowest glass transition temperature is defined as a glass transition temperature B.

The particle diameter φ (unit: nm) of the polymer particles is preferably 30 nm to 500 nm, more preferably 30 nm to 200 nm, and more preferably 30 nm to 15 nm.
More preferably, it is 0 nm or less. When the particle diameter of the polymer particles is in the above range, the dispersion stability of the polymer particles in the ink composition tends to be further improved. In addition,
The particle diameter (φ) of the polymer particles means a volume-based average particle diameter that can be determined by observation with a dynamic light scattering method or a transmission electron microscope.

The ratio (c / s) between the mass (c) of the core part of the polymer particles and the mass (s) of the shell part is:
It is preferably 0.4 or more and 4.0 or less, more preferably 0.5 or more and 2.5 or less, and particularly preferably 0.6 or more and 2.0 or less. In addition, the polymer particles are (c
/S)/φ≧0.01, the balance between the mass of the core portion and the mass of the shell portion becomes good regardless of the size of the polymer particles. Both the scratch resistance of the liquid composition recorded on the medium tend to be improved.

Moreover, it is particularly preferable that the polymers constituting the core part and the shell part of the polymer particles are each non-crosslinked. By being non-crosslinked, the discharge stability tends to be further improved. The degree of cross-linking of the polymer is determined using the gel fraction of the polymer (hereinafter referred to as “T”) using tetrahydrofuran (THF).
Also referred to as “HF gel fraction”. ) Can be quantified. The THF gel fraction of the polymer particles is preferably 10% or less, and more preferably 5% or less. When the THF gel fraction of the polymer particles is within the above range, the scratch resistance of the liquid composition recorded on the sublimation transfer recording medium tends to be further improved.

The THF gel fraction can be measured, for example, as follows. About 10 g of core-shell structure polymer particles are weighed into a Teflon (registered trademark) petri dish and dried at 120 ° C. for 1 hour to form a film. The obtained membrane was immersed in THF at 20 ° C. for 24 hours, filtered through a 100 mesh filter, re-dried at 20 ° C. for 24 hours, and the THF gel fraction (
%).
THF gel fraction (%) = (mass after re-drying / original mass) × 100

The content (in terms of solid content) of polymer particles in the liquid composition is preferably 4% by mass or more and 20% by mass or less, and preferably 4% by mass or more and 16% by mass with respect to the total mass (100% by mass) of the liquid composition. The following is more preferable, and 5% by mass or more and 12% by mass or less is more preferable. The content of polymer particles is 4
Since the disperse dye is protected by the polymer particles when the content is at least mass%, the scratch resistance and the fixability tend to be excellent. And since it contains a disperse dye in the core part,
A liquid composition having excellent color developability can be provided. Further, when the content of the polymer particles is 20% by mass or less, the disperse dye is stabilized in the liquid composition and tends to be more excellent in dispersion stability and storage stability.

Here, the core-shell type polymer particles in the present specification only require that the resin that forms the core portion is localized in the core portion, and the resin that forms the shell portion is localized in the shell portion. It may be a polymer particle whose boundary with the part is not exactly clear.

(Method for synthesizing polymer particles)
The method for synthesizing the polymer particles is not particularly limited, but can be easily synthesized by, for example, a known emulsion polymerization method or an appropriate combination thereof. Specifically, a batch mixing polymerization method, a monomer dropping method, a pre-emulsion method, a seed emulsion polymerization method, a multistage emulsion polymerization method (two-stage emulsion polymerization method, etc.), a phase inversion emulsion polymerization method and the like can be mentioned.

A polymerization method for synthesizing the core part first will be described. First, core particles are synthesized by an ordinary emulsion polymerization method using an aqueous medium. The conditions for emulsion polymerization may be in accordance with known methods. For example, when the total amount of monomers used is 100 parts, usually 100 to 500 parts of water (aqueous medium) is used, and 10 to 1000 parts of sublimation. Polymerization can be performed by adding a disperse dye having a property. The polymerization temperature is preferably -10 to 100 ° C, more preferably -5 to 100 ° C,
90 ° C. is more preferable. The polymerization time is preferably 0.1 to 30 hours, and more preferably 2 to 25 hours. Emulsion polymerization methods include batch method in which monomers are charged all at once, a method in which monomers are divided or continuously supplied, a method in which monomer pre-emulsions are divided or continuously added, or a combination of these methods in stages. Can be adopted. Moreover, the polymerization initiator, molecular weight regulator, emulsifier, etc. which are used for normal emulsion polymerization can be used 1 type, or 2 or more types as needed.

The polymerization initiator is not particularly limited. For example, persulfates such as potassium persulfate and ammonium persulfate; diisopropyl peroxydicarbonate, benzoyl peroxide, lauroyl peroxide, tert-butylperoxy-2-ethylhexanoate Organic peroxides such as: azo compounds such as azobisisobutyronitrile, dimethyl-2,2′-azobisisobutyrate, 2-carbamoylazaisobutyronitrile; radical emulsifying compounds having a peroxide group The redox system which combined reducing agents, such as containing radical emulsifier, sodium hydrogensulfite, and ferrous sulfate, can be used. A polymerization initiator may be used individually by 1 type, or may use 2 or more types together.

Although it does not specifically limit as a molecular weight regulator, For example, n-hexyl mercaptan, n-
Mercaptans such as octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, t-tetradecyl mercaptan, thioglycolic acid; dimethylxanthogen disulfide, diethylxanthogen disulfide, diisopropylxanthogen disulfide Xanthogen disulfides such as tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, etc .; chloroform,
Halogenated hydrocarbons such as carbon tetrachloride, carbon tetrabromide and ethylene bromide; hydrocarbons such as pentaphenylethane and α-methylstyrene dimer; acrolein, methacrolein, allyl alcohol, 2-ethylhexyl thioglycolate, Examples include terpinolene, α-ternepine, γ-ternepine, dipentene, and 1,1-diphenylethylene. A molecular weight regulator may be used individually by 1 type, or may use 2 or more types together.

Although it does not specifically limit as an emulsifier, For example, Anionic surfactants, such as alkyl sulfate ester salt and alkylbenzenesulfonate; Nonionic property, such as alkyl ester of polyethylene glycol, alkyl ether of polyethylene glycol, alkylphenyl ether of polyethylene glycol Surfactants; reactive emulsifiers containing hydrophilic groups, hydrophobic groups and radical reactive groups; polymer emulsifiers in which hydrophilic groups are introduced into polymers such as vinyl polymers and polyester polymers. . An emulsifier may be used individually by 1 type, or may use 2 or more types together. The hydrophilic group is an atomic group having a high affinity for water, and examples thereof include a nitro group, a hydroxyl group, an amino group, a carboxyl group, and a sulfonic acid group. A hydrophobic group is an atomic group having a lower affinity for water than a hydrophilic group. For example, a linear or branched alkyl group, alicyclic group, aromatic ring group, alkylsilyl group, A fluoroalkyl group etc. are mentioned.

Next, the monomer for the shell portion is polymerized in the presence of the obtained core particles (core portion). Specifically, core-shell type polymer particles can be formed by seed polymerizing a monomer for the shell part in a state where the obtained core particles are used as seed particles. For example, the monomer for the shell portion or a pre-emulsion thereof may be added all at once, in a divided manner, or continuously in an aqueous medium in which the core particles are dispersed. It is preferable that the quantity of the core particle used at this time shall be 25-250 mass parts with respect to 100 mass parts of monomers for shell parts. In the case of using a polymerization initiator, a molecular weight regulator, an emulsifier and the like at the time of polymerization, the same ones as in the production of the core particles can be used. Also, for conditions such as polymerization time,
What is necessary is just to make it the same as the time of manufacture of a core particle.

A polymerization method for synthesizing the shell portion first will be described. First, the shell part is synthesized. Specifically, a pre-emulsion solution containing the above-mentioned hydrophilic monomer is prepared using a reactive emulsifier, and the pre-emulsion solution is dropped into an aqueous medium together with a polymerization initiator to synthesize a shell portion. .

Next, using the obtained shell part as a polymerization field, the core part is polymerized to synthesize polymer particles according to this embodiment. Specifically, a monomer mixture containing the above-described hydrophobic monomer and a disperse dye having sublimation property is dropped into an aqueous dispersion medium containing a shell portion, and the core portion is polymerized to obtain polymer particles. In addition, when making a shell part into a polymerization field, since it is not necessary to contain an emulsifier in a monomer mixture, it can be dripped as a monomer oil droplet.

According to such a multi-stage emulsion polymerization method, a shell part can be synthesized using a reactive emulsifier, and a core part can be synthesized without using an emulsifier, so that the content of the emulsifier in the liquid composition can be easily reduced to 0.
It can be set to 01% by mass or less. In the liquid composition, when the content of the emulsifier contained is 0.01% by mass or less, at the liquid interface (the air-liquid interface in the air-liquid, the liquid contact member such as the liquid container, and the solid-liquid interface in the liquid). It is preferable because aggregation of liquid components is suppressed and storage stability is excellent. In the liquid composition, the content of the emulsifier contained is 0.
. Since it is excellent in foaming property and defoaming property as it is 01 mass% or less, the liquid container which has the injection port which can be filled with a liquid can be used preferably. Here, the “liquid storage container having a liquid filling inlet” refers to a liquid storage container having a detachable or openable inlet,
While the user can easily inject the liquid composition, it tends to foam during the injection. In addition, it is preferable that the opening area of the injection port is 20 mm ² or more because filling of the liquid composition becomes easy. Such a liquid container is disclosed in, for example, Japanese Patent Application Laid-Open Nos. 2005-219483 and 2012-51309.

In addition, even when polymer particles are synthesized using a large amount of emulsifier, the content of the emulsifier contained in the liquid composition is reduced to 0. 0 by removing excess emulsifier after the synthesis of the polymer particles.
It is good also as 01 mass% or less.

Finally, a core-shell polymer particle dispersion is obtained by neutralizing with a base such as sodium hydroxide, potassium hydroxide, ammonia, etc., adjusting the pH, and filtering as necessary.

〔water〕
The liquid composition according to this embodiment may include water. When the liquid composition contains water, it functions as a dispersion medium for dispersing a disperse dye having sublimation properties. The water is not particularly limited, and pure water such as ion exchange water, ultrafiltered water, reverse osmosis water, distilled water, or ultrapure water can be used. By containing water, the amount of organic solvent can be reduced, and as a result, an environment-friendly liquid composition can be obtained. The water content is the total mass (100% by mass) of the liquid composition.
15-90 mass% is preferable, 20-85 mass% is more preferable, 25-80 mass% is further more preferable. When the water content is within the above range, dispersion stability, ejection stability, and adhesion tend to be further improved.

〔solvent〕
The liquid composition according to this embodiment preferably further contains a solvent. As a result, the liquid composition quickly penetrates into the sublimation transfer recording medium, and a recorded matter with less image blur can be obtained.

Such a solvent is not particularly limited, and preferred examples thereof include polyhydric alcohols and polyhydric alcohol alkyl ethers (glycol ethers).

The polyhydric alcohol is not particularly limited. For example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol. 1,3-butanediol, 1,4-butanediol, 2,3-butanediol,
, 2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,
6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 3-methyl-1,3-butanediol, 2-methyl-2,4-pentanediol, 3-methyl-
Examples include 1,5-pentanediol, 2-ethyl-1,3-hexanediol, glycerin and the like. Glycerin can be suitably used because of its high moisture retention.

Further, the glycol ether is not particularly limited. For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether. , Diethylene glycol monobutyl ether, diethylene glycol mono-t-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, 1-methyl-1- Methoxy Ethanol, propylene glycol monomethyl ether,
Propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monobutyl ether, etc. Is mentioned.

  A solvent may be used individually by 1 type and may be used in combination of 2 or more type.

The content of the solvent in the liquid composition is 0. 0% with respect to the total mass (100% by mass) of the liquid composition.
1-30 mass% is preferable and 0.5-20 mass% is more preferable. Content is 0.1% by mass
By the above, the penetration degree of the liquid composition into the sublimation transfer recording medium can be increased. On the other hand, when the content is 30% by mass or less, bleeding can be prevented from occurring in the image, and the improvement of the viscosity of the liquid composition tends to be further suppressed.

[Other ingredients]
The liquid composition according to the present embodiment includes a surfactant, a dispersant, a dissolution aid, an antifoaming agent, a viscosity adjuster, a pH adjuster, an antioxidant, an antiseptic, an antifungal agent, a corrosion inhibitor, and an antirust. Various additives such as an agent and a chelating agent for capturing metal ions that affect the dispersion can be appropriately added.

The surfactant is not particularly limited, and examples thereof include acetylene glycol surfactants, fluorine surfactants, and silicone surfactants. When the liquid composition contains these surfactants, the wettability of the liquid composition attached to the recording medium for sublimation transfer tends to be further improved.

Although it does not specifically limit as an acetylene glycol type surfactant, For example, 2, 4,
Alkylene oxide adducts of 7,9-tetramethyl-5-decyne-4,7-diol and 2,4,7,9-tetramethyl-5-decyne-4,7-diol, and 2,4-dimethyl- One or more selected from alkylene oxide adducts of 5-decyn-4-ol and 2,4-dimethyl-5-decyn-4-ol are preferred. Although it does not specifically limit as a commercial item of a fluorochemical surfactant, For example, Olfine 104 series and Olfine E10
E series such as 10 (Air Products Japan, I
nc. ) Product name), Surfinol 465 and Surfinol 61 (Nisshin Chemical Industry (N
issin Chemical Industry CO. , Ltd., Ltd. ) Product name). One acetylene glycol surfactant may be used alone, or two or more acetylene glycol surfactants may be used in combination.

The fluorosurfactant is not particularly limited. For example, perfluoroalkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl phosphate, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl betaine, perfluoroalkyl betaine, A fluoroalkylamine oxide compound is mentioned. Although it does not specifically limit as a commercial item of a fluorochemical surfactant, For example, S-144, S-145 (Asahi Glass Co., Ltd. product);
FC-170C, FC-430, Florard-FC4430 (manufactured by Sumitomo 3M Limited)
FSO, FSO-100, FSN, FSN-100, FS-300 (manufactured by Dupont); FT-250, 251 (manufactured by Neos). Fluorosurfactant
You may use individually by 1 type and may use 2 or more types together.

Examples of silicone surfactants include polysiloxane compounds and polyether-modified organosiloxanes. Although it does not specifically limit as a commercial item of a silicone type surfactant, Specifically, BYK-306, BYK-307, BYK-333, specifically,
BYK-341, BYK-345, BYK-346, BYK-347, BYK-348,
BYK-349 (above trade name, manufactured by Big Chemie Japan Co., Ltd.), KF-351A,
KF-352A, KF-353, KF-354L, KF-355A, KF-615A, K
F-945, KF-640, KF-642, KF-643, KF-6020, X-22
4515, KF-6011, KF-6012, KF-6015, KF-6017 (above trade names, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

The content of the surfactant in the liquid composition is based on the total mass (100% by mass) of the liquid composition.
0.1-5 mass% is preferable and 0.1-3 mass% is more preferable. When the content of the surfactant is within the above range, the wettability of the liquid composition attached to the recording medium for sublimation transfer tends to be further improved.

〔surface tension〕
The surface tension at 25 ° C. of the liquid composition is preferably 20 mN / m or more and 50 mN / m or less, and more preferably 20 mN / m or more and 40 mN / m or less. When the surface tension is within the above range, the wettability of the liquid composition attached to the recording medium for sublimation transfer tends to be further improved. In addition, when the liquid composition is adhered from a recording head of a recording apparatus described later, the ejection stability tends to be good. The surface tension of the liquid composition is, for example, a surface tension meter CBVP-A.
3 (manufactured by Kyowa Interface Science Co., Ltd.) and can be determined by measurement according to JIS K3362.

〔viscosity〕
The viscosity at 25 ° C. of the liquid composition is preferably 20 mPa · s or less, preferably 10 mPa · s.
The following is more preferable. When the viscosity is within the above range, when the liquid composition is adhered from a recording head of a recording apparatus described later, the discharge stability and the discharge response can be made particularly excellent. In addition, the viscosity of a liquid composition can be calculated | required by the measurement based on JISZ8809 using a vibration type viscometer.

[Sublimation recording medium]
The sublimation transfer recording medium to which the liquid composition is attached is not particularly limited.
Examples thereof include an absorbing sublimation transfer recording medium, a low-absorbing sublimation transfer recording medium, and a non-absorbing sublimation transfer recording medium.

The recording medium for absorbing sublimation transfer is not particularly limited. For example, plain paper such as electrophotographic paper having high liquid composition permeability, inkjet paper, and general offset having relatively low liquid composition permeability Art paper, coated paper, cast paper, etc. used for printing are mentioned. Although it does not specifically limit as inkjet paper, Specifically, it was comprised from hydrophilic polymers, such as the liquid absorption layer comprised from the silica particle and the alumina particle, or polyvinyl alcohol (PVA) and polyvinylpyrrolidone (PVP). Examples of the paper include a liquid absorption layer.

The recording medium for sublimation transfer with low absorption is not particularly limited, and examples thereof include coated paper having a coating layer for receiving the oily liquid composition on the surface. The coated paper is not particularly limited, and examples thereof include printing paper such as art paper, coated paper, and matte paper.

The non-absorbent sublimation transfer recording medium is not particularly limited, and examples thereof include films and plates of plastics such as polyvinyl chloride, polyethylene, polypropylene, and polyethylene terephthalate (PET), iron, silver, copper, aluminum, and the like. Metal plates,
Alternatively, a metal plate produced by vapor deposition of these various metals, a plastic film, a plate made of an alloy such as stainless steel or brass, and the like can be given.

Here, the “low-absorbent sublimation transfer recording medium” and the “non-absorbent sublimation transfer recording medium” have a water absorption of 10 mL / m ² or less from the start of contact to 30 msec in the Bristow method. A recording medium for sublimation transfer. This Bristow method is the most popular method for measuring the amount of liquid absorbed in a short period of time.
(PAN TAPPI). For details of the test method, refer to “JAPAN TAPPI
No. of “Paper Pulp Test Method 2000” 51 "Paper and Paperboard-Liquid Absorbency Test Method-
Bristow method ".

Further, the non-absorbent sublimation transfer recording medium or the low-absorption sublimation transfer recording medium can be classified by the wettability of the recording surface to water. For example, a 0.5 μL water droplet is dropped on the recording surface of a sublimation transfer recording medium, and the contact angle reduction rate (comparison of the contact angle at 0.5 msec and the contact angle at 5 sec after landing) is measured. The recording medium can be characterized. More specifically, as a property of the sublimation transfer recording medium, the non-absorptivity of the “non-absorbing sublimation transfer recording medium” means that the above-mentioned reduction rate is less than 1%, The low absorbency of the “transfer recording medium” means that the reduction rate is 1% or more and less than 5%. Also,
Absorptivity means that the reduction rate is 5% or more. The contact angle is a portable contact angle meter.
It can be measured using PCA-1 (manufactured by Kyowa Interface Science Co., Ltd.) or the like.

By using an absorbent sublimation transfer recording medium, solid components such as polymer particles in the liquid composition remain on the surface of the sublimation transfer recording medium and fix, and some liquid components such as water It penetrates into the recording medium for sublimation transfer. Therefore, the liquid composition can be easily dried on the surface of the recording medium for sublimation transfer, and recording with suppressed bleeding can be performed.

In addition, when a part of the shell part melts on the sublimation transfer recording medium, the liquid composition of the present embodiment forms a film on the surface of the sublimation transfer recording medium by the melted core part having a glass transition temperature lower than that of the shell part. It is formed. The disperse dye mixes with the melted core portion and shell portion, and is effectively fixed to the recording medium for sublimation transfer. Accordingly, it is possible to effectively record on a recording medium for sublimation transfer having low absorption and non-absorption.

Adhesion of the liquid composition to the sublimation transfer recording medium can be suitably performed by using an ink jet method. The liquid composition can be attached by an ink jet method using a known recording apparatus. As a droplet discharge method of the ink jet method, a piezo method, a method of discharging a liquid by bubbles generated by heating ink, or the like can be used. However, it is difficult to alter the liquid composition. From the viewpoint, the piezo method is preferable.

By adhering a liquid composition to a sublimation transfer recording medium by an ink jet method, even if a pattern or design to be recorded has a complicated shape or a fine shape, it can be easily and reliably formed. . In addition, since the ink jet method is excellent in on-demand characteristics, it can be suitably adapted to multi-product production and small-quantity production.

[Recording device]
The recording apparatus according to this embodiment includes a recording head for attaching a liquid composition to a sublimation transfer recording medium, and heating for heating the sublimation transfer recording medium to which the liquid composition is attached at a heating temperature C (unit: ° C.). And the liquid composition includes a polymer particle and a disperse dye having sublimability, and the polymer particle includes a core portion including a resin having a glass transition temperature A (unit: ° C.), and a core. A shell part that covers a resin having a glass transition temperature B (unit: ° C.) that covers at least a part of the part,
The core portion contains a disperse dye, and the glass transition temperature A and the glass transition temperature B are represented by the following formula (8)
And the glass transition temperature A satisfies the following formula (9) in relation to the heating temperature C.
A <B (8)
A <C (9)
The recording apparatus may further include the above-described liquid composition, and the same liquid composition as that described above can be used as the liquid composition.

FIG. 1 is a schematic sectional view of a recording apparatus according to this embodiment. As shown in FIG. 1, a recording apparatus 1 according to this embodiment includes a recording head 2 and a curing heater 5 as a heating unit.

The recording head 2 attaches a liquid composition to a recording medium for sublimation transfer. As the recording head 2, a conventionally known method can be used, and there is a head that ejects droplets by utilizing vibration of a piezoelectric element, that is, a head that forms ink droplets by mechanical deformation of an electrostrictive element.

The heating unit heats the sublimation transfer recording medium to which the liquid composition is adhered at the heating temperature C. Although it does not specifically limit as a heating part, For example, means, such as the curing heater 5, a warm air mechanism (not shown), and a thermostat (not shown), are mentioned. When the heating unit heats the sublimation transfer recording medium to which the liquid composition is adhered, liquid components such as water contained in the liquid composition are quickly evaporated and scattered, and the polymer particles contained in the liquid composition As a result, a film is formed on the surface of the sublimation transfer recording medium. Therefore, the liquid composition is effectively fixed on the recording medium for sublimation transfer, and recording with excellent scratch resistance can be performed.

The above-mentioned “heating the sublimation transfer recording medium” means raising the temperature of the sublimation transfer recording medium to a desired temperature, and is not limited to directly heating the sublimation transfer recording medium.

Although not essential, as shown in FIG. 1, the recording apparatus 1 may include an IR heater 3, a platen heater 4, a cooling fan 6, a preheater 7, and a ventilation fan 8. Good.

When the IR heater 3 is used, the recording medium for sublimation transfer can be heated from the recording head 2 side at the same time as recording is performed by the recording head 2. When the platen heater 4 is used,
The recording medium for sublimation transfer can be heated from the side opposite to the recording head 2 side at the same time when recording is performed by the recording head 2. Thereby, the liquid composition adhering to the recording medium for sublimation transfer is quickly dried, and bleeding can be further suppressed. Further, the viscosity of the liquid composition in the recording head 2 is reduced, and the ejection stability can be improved.

When the cooling fan 6 is used, the liquid composition attached to the sublimation transfer recording medium and heated to the heating temperature C by the heating unit such as the curing heater 5 is cooled, and the polymer particles are deposited on the sublimation transfer recording medium. It tends to be able to form a film with good adhesion.

When the pre-heater 7 is used, the sublimation transfer recording medium is preheated before the liquid composition is attached to the sublimation transfer recording medium, and the non-absorbing and low-absorbing sublimation transfer recording medium is more blurred. There is a tendency that recording can be performed with less.

When the ventilation fan 8 is used, the liquid composition attached to the sublimation transfer recording medium tends to be dried more efficiently.

[Recording medium]
The recording medium is recorded by a recording method described later. As the recording medium, for example, polyester fiber, nylon fiber, triacetate fiber, diacetate fiber,
What was comprised with fibers, such as a polyamide fiber, can be used. Moreover, the blended product of 2 or more types of fibers selected from the above may be sufficient. Moreover, you may use the blended products of these with regenerated fibers, such as rayon, or natural fibers, such as cotton, silk, and wool. In particular, the recording medium is preferably composed of polyester fibers. The recording medium may be a sheet-like material such as a fabric, or may have a three-dimensional shape such as a T-shirt.

〔Recording method〕
The recording method according to the present embodiment is a first method in which a liquid composition is attached to a sublimation transfer recording medium.
And a second step of heating the sublimation transfer recording medium having the liquid composition attached thereto at a heating temperature C (unit: ° C.), wherein the liquid composition comprises polymer particles, sublimation, and the like. The polymer particles include a core part containing a resin having a glass transition temperature A (unit: ° C) and a glass transition temperature B (unit: ° C) covering at least a part of the core part. And the core part contains a disperse dye, and has a glass transition temperature A and a glass transition temperature B.
However, the following formula (5) is satisfied, and the glass transition temperature A satisfies the following formula (6) in relation to the heating temperature C.
A <B (5)
A <C (6)
Further, the recording method according to the present embodiment is such that the sublimation transfer recording medium attached with the liquid composition and heated at the heating temperature C is brought into contact with the recording medium, and the sublimation transfer recording medium and / or the recording medium is contacted. Is heated at a heating temperature D (unit: ° C.), and a third step of sublimating and transferring the liquid composition from the recording medium for sublimation transfer to the recording medium, wherein the glass transition temperature B is In relation to the heating temperature D, it is preferable to satisfy the following formula (7).
B <D (7)
In addition, about the liquid composition, the thing similar to the liquid composition mentioned above can be used.
Further, a recording method when using the recording apparatus 1 of the above-described embodiment will be described below.

(First step)
FIG. 2 shows a flowchart of the recording method according to the present embodiment. As shown in FIG. 2, the recording method according to this embodiment includes a first step and a second step. Moreover, it is preferable to have a 3rd process.

The first step is a step in which the above-described liquid composition is ejected from the recording head 2 to a sublimation transfer recording medium and adhered. As the liquid composition to be attached to the sublimation transfer recording medium in the first step, the same liquid composition as described above can be used. Therefore, it is possible to provide a recording method having excellent dispersion stability of the liquid composition.

In the first step, when the recording medium for sublimation transfer is heated at the same time as recording is performed by the recording head 2, it is preferable to heat the recording medium for sublimation transfer from the recording head 2 side.
When the sublimation transfer recording medium is thick, the liquid composition of the sublimation transfer recording medium using the platen heater 4 or the like is heated by heating the sublimation transfer recording medium from the recording head 2 side using the IR heater 3 or the like. Compared with the case where it heats from the other side of an adhesion surface, a liquid composition can be dried more rapidly. Further, the viscosity of the liquid composition in the recording head 2 is reduced, and the ejection stability can be improved.

(Second step)
The second step is a step of heating the sublimation transfer recording medium to which the above-described liquid composition is adhered at the heating temperature C. In the liquid composition on the surface of the sublimation transfer recording medium, the sublimation transfer recording medium to which the liquid composition is attached is heated at a heating temperature C higher than the glass transition temperature A of the core portion. The core part is in a molten state. When a part of the liquid component contained in the liquid composition evaporates and a part of the shell part melts due to the concentration of the solvent, etc., a film is easily formed by the melted core part. Can be fixed on the recording medium surface.

In addition, when the liquid composition on the sublimation transfer recording medium is cooled by the cooling fan 6 after the second step, the coating tends to be formed on the sublimation transfer recording medium with good adhesion.

The heating temperature C in the second step is preferably 20 ° C. or higher and 100 ° C. or lower, 30
More preferably, the temperature is from 80 ° C. to 80 ° C., more preferably from 40 ° C. to 60 ° C. When the heating temperature C is within the above range, some liquid components such as water contained in the liquid composition attached to the sublimation transfer recording medium evaporate, and the liquid composition is formed on the surface of the sublimation transfer recording medium. Dry out. Therefore, the scratch resistance tends to be improved. Further, when the heating temperature C exceeds 100 ° C., part of the disperse dye is likely to sublime at the stage where the liquid composition adheres to the recording medium for sublimation transfer. There is a possibility that the color developability of the recording medium may be deteriorated. However, the heating temperature C is 100
When the temperature is lower than 0 ° C., the disperse dye hardly sublimates at the stage where the liquid composition adheres to the sublimation transfer recording medium.

(Third step)
In the third step, the sublimation transfer recording medium to which the liquid composition is attached and heated at the heating temperature C is brought into contact with the recording medium, and the sublimation transfer recording medium and / or the recording medium is heated to the heating temperature D.
And the liquid composition is sublimated and transferred from the sublimation transfer recording medium to the recording medium. In addition, by heating at the heating temperature D exceeding the glass transition temperature B of the shell portion, the shell portion is melted and the core-shell structure of the polymer particles is destroyed. And the core resin melts,
The disperse dye mixed with the resin in the core part is also eluted on the surface of the recording medium for sublimation transfer. Furthermore, since the disperse dye sublimates from a solid to a gas at the heating temperature D, it is sublimated from the sublimation transfer recording medium to the recording medium. Therefore, it is possible to provide a recording method in which the disperse dye is surely sublimated and excellent in color developability. Further, in the stage before sublimation transfer at the heating temperature D, the disperse dye is not sublimated because it is included in the polymer particles. Accordingly, it is possible to prevent the disperse dye from being sublimated at the stage where the liquid composition is attached to the sublimation transfer recording medium, thereby preventing the work environment from being contaminated or the operator from sucking the disperse dye.

The heating temperature D in the third step is preferably 160 ° C. or higher and 250 ° C. or lower.
It is more preferably 0 ° C. or higher and 230 ° C. or lower, and further preferably 180 ° C. or higher and 210 ° C. or lower. When the heating temperature D is within the above range, many liquid components such as an organic solvent contained in the liquid composition attached to the sublimation transfer recording medium are evaporated, and the melted core portion and shell portion are concentrated. Further, the disperse dye is further easily eluted on the surface of the recording medium for sublimation transfer. Therefore, the color developability can be further improved.

The heating time in the third step is preferably 30 seconds or longer and 90 seconds or shorter, more preferably 45 seconds or longer and 60 seconds or shorter, although it depends on the heating temperature. Thereby, the disperse dye which has sublimation property can be sublimated and transferred efficiently and reliably.

[Example]
Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. The present invention is not limited in any way by the following examples.

[Material for liquid composition]
The main materials for the liquid compositions used in the following examples and comparative examples are as follows.
〔solvent〕
Glycerin Tetraethylene glycol monomethyl ether (polymer particles)
Polymer particles 1 (produced according to Production Example 1)
Polymer particle 2 (produced according to Production Example 2)
Polymer particles 3 (produced according to Production Example 3)
Polymer particles 4 (produced according to Production Example 4)
Polymer particles 5 (produced according to Production Example 5)
Polymer particles 6 (produced according to Production Example 6)
Polymer particles 7 (produced according to Production Example 7)
Polymer particles 8 (produced according to Production Example 8)
Polymer particles 9 (produced according to Production Example 9)
Polymer particles 10 (produced according to Production Example 10)
The polymer particles 1 to 8 and the polymer particle 10 are C.I. as a disperse dye having sublimability in the core part. I. A disperse thread 60 is included. The polymer particles 9 have C.I. I. The disperse thread 60 is not included. Further, the glass transition temperatures A and B of the polymer particles 1 to 10 and the constituent monomers are shown in Table 1 described later.

[Production Example 1: Polymer particles 1]
To a reaction vessel equipped with a dropping device, a thermometer, a water-cooled reflux condenser, and a stirrer, 100 parts of ion exchange water and 0.2 part of potassium persulfate as a polymerization initiator are added, and 7 parts of ion exchange water. In addition, 0.05 part of sodium lauryl sulfate, 18 parts of n-butyl methacrylate, 12 parts of styrene, 0.02 part of t-dodecyl mercaptan and C.I. I. A monomer solution containing 130 parts of Disper Thread 60 was dropped at 70 ° C. in a nitrogen atmosphere while stirring to react to prepare core particles. Thereafter, 2 parts of 10% ammonium persulfate solution was added and stirred, and 30 parts of ion-exchanged water, 0.2 part of potassium lauryl sulfate, acrylic acid 1
A reaction solution consisting of 0 part, 65 parts of methyl methacrylate, 25 parts of lauryl methacrylate and 0.5 part of t-dodecyl mercaptan was added at 70 ° C. with stirring, and then neutralized with sodium hydroxide, pH 8 to A core-shell polymer particle aqueous dispersion was prepared by adjusting to 8.5 and filtering with a 0.3 μm filter.

[Production Example 2: Polymer particles 2]
To a reaction vessel equipped with a dropping device, a thermometer, a water-cooled reflux condenser, and a stirrer, 100 parts of ion exchange water and 0.2 part of potassium persulfate as a polymerization initiator are added, and 7 parts of ion exchange water. In addition, 0.05 part of sodium lauryl sulfate, 18 parts of n-butyl methacrylate, 12 parts of styrene, 0.02 part of t-dodecyl mercaptan and C.I. I. A monomer solution containing 130 parts of Disper Thread 60 was dropped at 70 ° C. in a nitrogen atmosphere while stirring to react to prepare core particles. Thereafter, 2 parts of 10% ammonium persulfate solution was added and stirred, and 30 parts of ion-exchanged water, 0.2 part of potassium lauryl sulfate, acrylic acid 1
A reaction solution consisting of 0 parts, 42.5 parts of methyl methacrylate, 25 parts of lauryl methacrylate, 22.5 parts of n-butyl methacrylate and 0.5 part of t-dodecyl mercaptan was added at 70 ° C. with stirring to cause polymerization reaction. Thereafter, the mixture was neutralized with sodium hydroxide, adjusted to pH 8 to 8.5, and filtered through a 0.3 μm filter to prepare a core-shell type polymer particle aqueous dispersion.

[Production Example 3: Polymer particles 3]
To a reaction vessel equipped with a dropping device, a thermometer, a water-cooled reflux condenser, and a stirrer, 100 parts of ion exchange water and 0.2 part of potassium persulfate as a polymerization initiator are added, and 7 parts of ion exchange water. In addition, 0.05 part of sodium lauryl sulfate, 18 parts of n-butyl methacrylate, 12 parts of styrene, 0.02 part of t-dodecyl mercaptan and C.I. I. A monomer solution containing 130 parts of Disper Thread 60 was dropped at 70 ° C. in a nitrogen atmosphere while stirring to react to prepare core particles. Thereafter, 2 parts of 10% ammonium persulfate solution was added and stirred, and further 30 parts of ion-exchanged water, 0.2 part of potassium lauryl sulfate, acrylic acid 2
A reaction solution consisting of 0 part, 1-adamantyl methacrylate, and 0.5 part of t-dodecyl mercaptan was added with stirring at 70 ° C., followed by polymerization reaction, and then neutralized with sodium hydroxide to pH 8 to 8.5. And a core-shell type polymer particle aqueous dispersion was prepared by filtration through a 0.3 μm filter.

[Production Example 4: Polymer particles 4]
To a reaction vessel equipped with a dropping device, a thermometer, a water-cooled reflux condenser, and a stirrer, 100 parts of ion exchange water and 0.2 part of potassium persulfate as a polymerization initiator are added, and 7 parts of ion exchange water. In addition, 0.05 part of sodium lauryl sulfate, 20 parts of n-butyl methacrylate, 10 parts of styrene, 0.02 part of t-dodecyl mercaptan and C.I. I. A monomer solution containing 130 parts of Disper Thread 60 was dropped at 70 ° C. in a nitrogen atmosphere while stirring to react to prepare core particles. Thereafter, 2 parts of 10% ammonium persulfate solution was added and stirred, and 30 parts of ion-exchanged water, 0.2 part of potassium lauryl sulfate, acrylic acid 1
A reaction solution consisting of 0 parts, 42.5 parts of methyl methacrylate, 25 parts of lauryl methacrylate, 22.5 parts of n-butyl methacrylate and 0.5 part of t-dodecyl mercaptan was added at 70 ° C. with stirring to cause polymerization reaction. Thereafter, the mixture was neutralized with sodium hydroxide, adjusted to pH 8 to 8.5, and filtered through a 0.3 μm filter to prepare a core-shell type polymer particle aqueous dispersion.

[Production Example 5: Polymer particles 5]
To a reaction vessel equipped with a dropping device, a thermometer, a water-cooled reflux condenser, and a stirrer, 100 parts of ion exchange water and 0.2 part of potassium persulfate as a polymerization initiator are added, and 7 parts of ion exchange water. Sodium lauryl sulfate 0.05 parts, n-butyl methacrylate 5 parts, styrene 2
5 parts, t-dodecyl mercaptan 0.02 part and sublimable C.I. I. A monomer solution containing 130 parts of Disper Thread 60 was dropped at 70 ° C. in a nitrogen atmosphere while stirring to react to prepare core particles. Thereafter, 2 parts of a 10% ammonium persulfate solution was added and stirred, and further 30 parts of ion-exchanged water, 0.2 part of potassium lauryl sulfate, 10 parts of acrylic acid
A reaction liquid consisting of 80 parts of methyl methacrylate, 10 parts of methyl methacrylate, 10 parts of lauryl methacrylate and 0.5 part of t-dodecyl mercaptan was added at 70 ° C. with stirring, followed by neutralization with sodium hydroxide, pH 8-8 The core-shell type polymer particle aqueous dispersion was prepared by adjusting to 0.5 and filtering through a 0.3 μm filter.

[Production Example 6: Polymer particles 6]
To a reaction vessel equipped with a dropping device, a thermometer, a water-cooled reflux condenser, and a stirrer, 100 parts of ion exchange water and 0.2 part of potassium persulfate as a polymerization initiator are added, and 7 parts of ion exchange water. In addition, 0.05 part of sodium lauryl sulfate, 18 parts of n-butyl methacrylate, 12 parts of styrene, 0.02 part of t-dodecyl mercaptan and C.I. I. A monomer solution containing 130 parts of Disper Thread 60 was dropped at 70 ° C. in a nitrogen atmosphere while stirring to react to prepare core particles. Thereafter, 2 parts of 10% ammonium persulfate solution was added and stirred, and 30 parts of ion-exchanged water, 0.2 part of potassium lauryl sulfate, acrylic acid 1
A reaction solution consisting of 0 part, 80 parts of methyl methacrylate, 10 parts of lauryl methacrylate and 0.5 part of t-dodecyl mercaptan was added at 70 ° C. with stirring, and then neutralized with sodium hydroxide, pH 8 to A core-shell polymer particle aqueous dispersion was prepared by adjusting to 8.5 and filtering with a 0.3 μm filter.

[Production Example 7: Polymer particle 7]
To a reaction vessel equipped with a dropping device, a thermometer, a water-cooled reflux condenser, and a stirrer, 100 parts of ion exchange water and 0.2 part of potassium persulfate as a polymerization initiator are added, and 7 parts of ion exchange water. In addition, 0.05 part of sodium lauryl sulfate, 10 parts of n-butyl methacrylate, 25 parts of styrene, 0.02 part of t-dodecyl mercaptan and C.I. I. A monomer solution containing 135 parts of disperse thread 60 was added dropwise at 70 ° C. under a nitrogen atmosphere while stirring to react to prepare core particles. Thereafter, 2 parts of 10% ammonium persulfate solution was added and stirred, and 30 parts of ion-exchanged water, 0.2 part of potassium lauryl sulfate, acrylic acid 1
A reaction solution consisting of 0 part, 80 parts of methyl methacrylate, 10 parts of lauryl methacrylate and 0.5 part of t-dodecyl mercaptan was added at 70 ° C. with stirring, and then neutralized with sodium hydroxide, pH 8 to A core-shell polymer particle aqueous dispersion was prepared by adjusting to 8.5 and filtering with a 0.3 μm filter.

[Production Example 8: Polymer particles 8]
To a reaction vessel equipped with a dropping device, a thermometer, a water-cooled reflux condenser, and a stirrer, 100 parts of ion exchange water and 0.2 part of potassium persulfate as a polymerization initiator are added, and 7 parts of ion exchange water. In addition, 0.05 part of sodium lauryl sulfate, 10 parts of n-butyl methacrylate, 25 parts of styrene, 0.02 part of t-dodecyl mercaptan and C.I. I. A monomer solution containing 135 parts of disperse thread 60 was added dropwise at 70 ° C. under a nitrogen atmosphere while stirring to react to prepare core particles. Thereafter, 2 parts of 10% ammonium persulfate solution was added and stirred, and further 30 parts of ion-exchanged water, 0.2 part of potassium lauryl sulfate, 7 parts of acrylic acid
. A reaction solution comprising 7 parts, 44.8 parts of methyl methacrylate, 25 parts of stearyl acrylate, 22.5 parts of 2-ethylhexyl acrylate, and 0.5 part of t-dodecyl mercaptan was added at 70 ° C. with stirring to cause polymerization reaction. After neutralization with sodium hydroxide, pH 8-8
. The core-shell polymer particle aqueous dispersion was prepared by adjusting to 5 and filtering with a 0.3 μm filter.

[Production Example 9: Polymer particles 9]
To a reaction vessel equipped with a dropping device, a thermometer, a water-cooled reflux condenser, and a stirrer, 100 parts of ion exchange water and 0.2 part of potassium persulfate as a polymerization initiator are added, and 7 parts of ion exchange water. A monomer solution containing 0.05 part of sodium lauryl sulfate, 18 parts of n-butyl methacrylate, 12 parts of styrene, and 0.02 part of t-dodecyl mercaptan was added dropwise at 70 ° C. under a nitrogen atmosphere with stirring to cause a reaction. Particles were made. Thereafter, 2 parts of 10% ammonium persulfate solution was added and stirred, and further 30 parts of ion exchange water, 0 parts of potassium lauryl sulfate.
. 2 parts, acrylic acid 10 parts, methyl methacrylate 65 parts, lauryl methacrylate 25
The reaction solution consisting of 0.5 parts of t-dodecyl mercaptan was added at 70 ° C. with stirring, followed by polymerization reaction, then neutralized with sodium hydroxide and adjusted to pH 8 to 8.5 to adjust to 0.3 μm. A core-shell polymer particle aqueous dispersion was prepared by filtering with a filter.

[Production Example 10: Polymer particle 10]
To a reaction vessel equipped with a dropping device, a thermometer, a water-cooled reflux condenser, and a stirrer, 100 parts of ion exchange water and 0.2 part of potassium persulfate as a polymerization initiator are added, and 40 parts of ion exchange water. , Potassium lauryl sulfate 0.2 part, acrylic acid 13 parts, methyl methacrylate 10
4 parts, 13 parts lauryl methacrylate, 0.5 parts t-dodecyl mercaptan and C.I. I. A reaction solution consisting of 130 parts of Disper Thread 60 is placed under a nitrogen atmosphere.
After stirring at ℃ for polymerization reaction, neutralization with sodium hydroxide and pH 8 to 8.5
And a non-core-shell polymer particle aqueous dispersion was prepared by filtering through a 0.3 μm filter.

[Preparation of liquid composition]
Each material was mixed with the composition (mass%) shown in Table 2 and Table 3 to be described later, and stirred sufficiently to obtain each liquid composition. In addition, a polymer particle shows solid content.

[Evaluation]
(Dispersion stability)
Each liquid composition is sealed in an ink pack, left in a 30 ° C. environment for 10 days, and then 20 m
L was taken out into a glass bottle and left at room temperature for 1 day. And the sample after standing was confirmed visually and dispersion stability was confirmed.

(Evaluation)
(Double-circle): The state in which the powder contained in the prepared dispersion continues to disperse approximately uniformly.
○: A part of the powder contained in the prepared dispersion settles or separates to the liquid surface, but it is uniformly dispersed again by shaking.
X: The state in which the powder contained in the prepared dispersion settles or completely separates on the liquid surface and does not uniformly disperse even when shaken.

[Color development]
Printer Stylus Pro 9900 (Seiko Epson Corporation (Seiko Ep
(Son Corporation)) was partially remodeled so that the sublimation transfer recording medium can be heated and adjusted during and after ink jet recording. Using this printer, sublimation transfer paper Tran, which is a recording medium for sublimation transfer, from the nozzles of the recording head
After each liquid composition was deposited on sjet Classic 831 (made by Charm) to form a solid pattern, the liquid composition was dried by a curing heater having a heating temperature C (° C.) in Tables 2 and 3, and a cooling fan Then, the dried liquid composition was cooled. Thereafter, the recorded sublimation transfer recording medium was made of a polyester fiber as a recording medium using a heat press TP-608M manufactured by Taiyo Seiki Co., Ltd. (woven fabric having dyed objects, warp yarns and weft yarns)
On the other hand, sublimation transfer was performed by heating for 60 seconds at the heating temperature D (° C.) in Table 2 and Table 3 to prepare a sample. And the OD value of the magenta ink was measured with respect to the created sample using a SpectroScan apparatus (manufactured by Gretad Macbeth).

(Evaluation)
A: The OD value of magenta ink is 1.4 or more.
○: The OD value of magenta ink is 1.3 or more and less than 1.4.
X: The OD value of magenta ink is less than 1.3.

[Scratch resistance]
Printer Stylus Pro 9900 (Seiko Epson Corporation (Seiko Ep
(Son Corporation)) was partially remodeled so that the sublimation transfer recording medium can be heated and adjusted during and after ink jet recording. Using this printer, sublimation transfer paper Tran, which is a recording medium for sublimation transfer, from the nozzles of the recording head
Recording resolution 720 * 720 dpi on sjet Classic 831 (Charm)
Each liquid composition was adhered to form an evaluation sample. Then, Table 2 and Table 3
The liquid composition was dried with a curing heater at a heating temperature C (° C.), and the dried liquid composition was cooled with a cooling fan. And Gakushin friction fastness tester (Tester Sangyo (TE
STER SANGYO CO. , LTD. )), And was reciprocated 10 times with a load of 500 g of gold width, and was evaluated as follows from the degree of adhesion to the gold width and scratches on the coated surface.

(Evaluation)
(Double-circle): The state in which there is almost no adhesion to the gold width and the scratches are not on the coating surface.
◯: Ink is attached to a range of less than 10% of the rubbing portion of the gold width, and a range of less than 30% of the coated surface is scratched.
X: The state where the ink has adhered to the range of 10% or more of the scraped portion of the gold width, and the range of 30% or more of the coated surface is scratched.

(Discharge stability)
Printer Stylus Pro 9900 (Seiko Epson Corporation (Seiko Ep
(Son Corporation)) was partially remodeled so that the sublimation transfer recording medium can be heated and adjusted during and after ink jet recording. Using this printer, sublimation transfer paper Tran, which is a recording medium for sublimation transfer, from the nozzles of the recording head
Each liquid composition was made to adhere on sjet Classic831 (made by a charm company), and the solid pattern was formed. Then, the liquid composition was dried with the curing heater of the heating temperature C (degreeC) in Table 2 and Table 3, and the dried liquid composition was cooled with the cooling fan. After 10 hours of continuous recording, the ejection stability was evaluated as follows. In addition, maintenance was performed every time recording was performed for 2 hours.

(Evaluation)
◎: Slight non-ejection or ejection turbulence occurs during ejection, but it returns during ejection and there is almost no problem. ○: Slight non-ejection or ejection turbulence occurs during ejection and does not return during ejection, but maintenance X: State that returns to normal state due to discharge ×: State that does not return during discharge due to a slight non-discharge or discharge disturbance during discharge, and does not return due to maintenance

Tables 2 and 3 show the results of the adjustment of the liquid compositions of the above Examples and Comparative Examples, and the results of the above evaluations. As can be seen from Tables 2 and 3, the liquid compositions of Examples 1 to 18 were excellent in dispersion stability and had good color development, scratch resistance and ejection stability.

In contrast, in the liquid composition of Comparative Example 1, since the temperature relationship between the glass transition temperature A of the core part and the glass transition temperature B of the shell part is reversed, the polymer particles have a particle shape in the liquid composition. It cannot be maintained, and it is assumed that the dispersion stability has decreased. Further, it is assumed that the scratch resistance is inferior because it is difficult to form a film on the sublimation transfer recording medium. In the liquid composition of Comparative Example 2, since the temperature relationship between the glass transition temperature A and the heating temperature C in the core portion is reversed, a film is hardly formed on the recording medium for sublimation transfer, resulting in poor scratch resistance. It is assumed that Since the liquid composition of Comparative Example 3 does not contain a disperse dye in the core part of the polymer particles, it is assumed that the disperse dye is directly contained in the liquid composition and the dispersion stability is lowered. In the liquid composition of Comparative Example 4, since the polymer particles do not have a core-shell structure, it is assumed that the disperse dye is not encapsulated in the polymer particles and the dispersion stability is lowered. Further, since the polymer particles do not have a core-shell structure, it is assumed that a film is difficult to be formed and scratch resistance is poor.

DESCRIPTION OF SYMBOLS 1 ... Recording device, 2 ... Recording head, 3 ... IR heater, 4 ... Platen heater, 5 ... Curing heater, 6 ... Cooling fan, 7 ... Pre-heater, 8 ... Ventilation fan.

Claims (11)

A liquid composition comprising polymer particles and a disperse dye having sublimation property, and is attached to a recording medium for sublimation transfer and heated at a heating temperature C (unit: ° C.),
The polymer particles include a core portion containing a resin having a glass transition temperature A (unit: ° C), and a shell portion containing a resin having a glass transition temperature B (unit: ° C) covering at least a part of the core portion. ,
Have
The core portion contains the disperse dye,
The glass transition temperature A and the glass transition temperature B satisfy the following formula (1), and the glass transition temperature A satisfies the following formula (2) in relation to the heating temperature C: Liquid composition.
A <B (1)
A <C (2) A liquid composition attached to the sublimation transfer recording medium and heated at the heating temperature C, and further sublimated and transferred from the sublimation transfer recording medium to a recording medium at a heating temperature D (unit: ° C.). ,
The liquid composition according to claim 1, wherein the glass transition temperature B satisfies the following formula (3) in relation to the heating temperature D.
B <D (3) The liquid composition according to claim 1, wherein the glass transition temperature A is −10 ° C. or more and 50 ° C. or less. 4. The liquid composition according to claim 1, wherein the heating temperature C is 20 ° C. or more and 100 ° C. or less. 5. 5. The liquid composition according to claim 1, wherein the heating temperature D is 160 ° C. or more and 250 ° C. or less. At least one of the monomers constituting the polymer particles is a (meth) acrylate,
The liquid composition according to claim 1, comprising (meth) acrylic acid and styrene. The liquid composition according to any one of claims 1 to 6, wherein a content of the polymer particles is 4% by mass or more and 20% by mass or less of a total mass of the liquid composition. . The liquid composition according to any one of claims 1 to 7, wherein the glass transition temperature B satisfies the following formula (4) in relation to the heating temperature C.
B <C (4) A first step of attaching the liquid composition to the sublimation transfer recording medium, and a second step of heating the sublimation transfer recording medium to which the liquid composition is attached at a heating temperature C (unit: ° C.). A recording method,
The liquid composition includes polymer particles and a disperse dye having sublimation property,
The polymer particles include a core portion containing a resin having a glass transition temperature A (unit: ° C), and a shell portion containing a resin having a glass transition temperature B (unit: ° C) covering at least a part of the core portion. ,
Have
The core portion contains the disperse dye,
The glass transition temperature A and the glass transition temperature B satisfy the following formula (5), and the glass transition temperature A satisfies the following formula (6) in relation to the heating temperature C: Recording method.
A <B (5)
A <C (6) The sublimation transfer recording medium attached with the liquid composition and heated at the heating temperature C is brought into contact with the recording medium, and the sublimation transfer recording medium and / or the recording medium is heated to the heating temperature D.
A third step of heating at (unit: ° C.) and sublimating and transferring the liquid composition from the sublimation transfer recording medium to the recording medium,
The recording method according to claim 9, wherein the glass transition temperature B satisfies the following formula (7) in relation to the heating temperature D.
B <D (7) A recording apparatus comprising: a recording head that attaches a liquid composition to a sublimation transfer recording medium; and a heating unit that heats the sublimation transfer recording medium to which the liquid composition adheres at a heating temperature C (unit: ° C.). Because
The liquid composition includes polymer particles and a disperse dye having sublimation property,
The polymer particles include a core portion containing a resin having a glass transition temperature A (unit: ° C), and a shell portion containing a resin having a glass transition temperature B (unit: ° C) covering at least a part of the core portion. ,
Have
The core portion contains the disperse dye,
The glass transition temperature A and the glass transition temperature B satisfy the following formula (8), and the glass transition temperature A satisfies the following formula (9) in relation to the heating temperature C: Recording device.
A <B (8)
A <C (9)

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