JP6476588B2 - RESIN COMPOSITION FOR FORMING RECORDING LAYER OF RECORDING MEDIUM, RECORDING MEDIUM, IMAGE RECORDED MATERIAL, AND IMAGE FORMING METHOD - Google Patents

Description

  The present invention relates to a resin composition for forming a recording layer of a recording medium, a recording medium, an image recording material, and an image forming method.

  The heat fixing energy and the power consumption for the image forming apparatus of the electrophotographic system are not only an environmental load but also a major factor that limits the installation environment and use environment of the image forming apparatus.

  As a means for reducing heat fixing energy, a method of pressure fixing at room temperature without using a heating means has been proposed (for example, Patent Document 1). In addition, means for imparting pressure fixability to a transfer medium such as paper has been proposed (for example, Patent Documents 2 to 4).

JP 2010-145440 A JP 2013-025207 A JP 2012-203667 A JP 2009-244857 A

  An object of the present invention is to provide a resin composition for forming a recording layer of a recording medium capable of suppressing double feeding in a high temperature and high humidity environment and fixing a toner image at a low pressure.

The above problem is solved by the following means. That is,
The invention according to claim 1
Wherein the resin, and the volume average particle size of the 50μm smaller particles than 1 [mu] m, meet the following equation (1),
The resin includes at least two kinds of resins having different glass transition temperatures,
Of the two types of resins, the temperature having the higher glass transition temperature is 40 ° C. or more and less than 60 ° C., and the temperature having the lower glass transition temperature is −100 ° C. or more and less than 10 ° C.,
A resin composition for forming a recording layer of a recording medium.
Equation _{(1) 20 ℃ ≦ T 1} -T 10 ≦ 120 ℃
In the formula (1), T ₁ represents a temperature at which the viscosity becomes 10 ⁴ Pa · s at an applied pressure of 1 MPa, which is measured using a flow tester after preparing a solid sample of the resin from the resin composition. . T ₁₀ represents a temperature at which the viscosity becomes 10 ⁴ Pa · s at an applied pressure of 10 MPa, which was measured by using a flow tester by preparing a solid sample of the resin from the resin composition.

Delete

The invention according to claim 2
2. The resin composition for forming a recording layer of a recording medium according to claim 1 , wherein the two kinds of resins differ in glass transition temperature by 30 ° C. or more.

The invention according to claim 3
At least one of the two resins is a recording layer forming resin composition of the recording medium according to claim 1 or claim 2 having a glass transition temperature of 40 ° C. or higher.

The invention according to claim 4
A substrate;
A recording layer formed on the substrate using the resin composition for forming a recording layer of a recording medium according to any one of claims 1 to 3 ,
Is a recording medium.

The invention according to claim 5
The recording medium according to claim 4 , wherein a volume average particle diameter of the particles is larger than a thickness of the recording layer.

The invention according to claim 6
A recording medium according to claim 4 or claim 5 ,
A toner image formed using an electrostatic charge image developing toner on the recording layer of the recording medium and fixed without being embedded in its entirety;
A peelable image information hiding layer that covers at least a portion of the toner image;
Are recorded images in order.

The invention according to claim 7 provides:
A charging step for charging the surface of the image carrier;
An electrostatic charge image forming step of forming an electrostatic charge image on the surface of the charged image carrier;
A developing step of developing an electrostatic image formed on the surface of the image carrier as a toner image with an electrostatic image developer containing an electrostatic image developing toner;
A transfer step of transferring to the surface of the recording layer of the recording medium according to the toner image formed on the surface of the image carrier to claim 4 or claim 5,
A fixing step of fixing the toner image transferred to the surface of the recording layer of the recording medium to the recording layer of the recording medium by pressure without embedding the entire toner image;
Is an image forming method.

The invention according to claim 8 provides:
Further, a covering step of covering at least a part of the toner image fixed on the recording layer of the recording medium with a peelable image information hiding layer;
An adhesion step of adhering the image information hiding layer to the recording layer of the recording medium by pressure;
The image forming method according to claim 7 , comprising:

  According to the invention according to claim 1, the volume average particle size does not include particles having a particle size of 1 μm or more and 50 μm or less, and compared with a case where the above formula (1) is not satisfied, the double feeding in a high temperature and high humidity environment is suppressed, A resin composition for forming a recording layer of a recording medium on which a toner image can be fixed at a low pressure can be provided.

According to the first aspect of the present invention, it is possible to provide a resin composition for forming a recording layer of a recording medium on which a toner image can be fixed at a lower pressure than when the two kinds of resins are not included.

According to the second aspect of the present invention, compared to the case where the difference between the glass transition temperatures of the two kinds of resins is less than 30 ° C., the recording layer of the recording medium capable of fixing the toner image at a low pressure is formed. A resin composition can be provided.

According to the invention of claim 3 , there is provided a resin composition for forming a recording layer of a recording medium having excellent storability as compared with the case where any of the two types of resins has a glass transition temperature of less than 40 ° C. Can be provided.

According to the invention of claim 4 , compared with the case where a recording layer forming resin composition not containing particles having a volume average particle diameter of 1 μm or more and 50 μm or less and not satisfying the above formula (1) is applied. It is possible to provide a recording medium that can suppress double feeding under an environment and fix a toner image at a low pressure.

According to the invention which concerns on Claim 5 , compared with the case where the volume average particle diameter of particle | grains is smaller than the thickness of a recording layer, the recording medium which suppresses generation | occurrence | production of the double feed in a high temperature, high humidity environment can be provided.

According to the sixth aspect of the present invention, the image information concealment is performed as compared with the case where the recording layer forming resin composition that does not include the particles having a volume average particle diameter of 1 μm to 50 μm and does not satisfy the formula (1) is applied. It is possible to provide an image recorded matter having excellent layer peelability.

According to the seventh aspect of the invention, compared with the case where a recording layer forming resin composition that does not satisfy the above formula (1) and does not include particles having a volume average particle diameter of 1 μm or more and 50 μm or less is used. It is possible to provide an image forming method capable of suppressing double feeding under an environment and fixing a toner image with a low pressure.

According to the eighth aspect of the present invention, the image information concealment is performed as compared with the case where a recording layer forming resin composition that does not include the particles having a volume average particle diameter of 1 μm or more and 50 μm or less and does not satisfy the formula (1) is applied. It is possible to provide an image forming method capable of producing an image recorded matter having excellent layer peelability.

It is sectional drawing which shows an example of the image recorded matter which concerns on this embodiment. FIG. 3 is a cross-sectional view illustrating an example of a recording medium in which a toner image is transferred to the surface of a recording layer. FIG. 3 is a cross-sectional view illustrating an example of a recording medium in which a toner image is fixed on a recording layer. FIG. 3 is a cross-sectional view showing an example of a recording medium in which a toner image is transferred to the surface of a recording layer of the recording medium and the toner image and the recording layer are further covered with an image information hiding layer.

  Hereinafter, an embodiment which is an example of the present invention will be described in detail.

<Resin composition>
The resin composition for forming a recording layer of a recording medium according to the present embodiment includes a resin and particles having a volume average particle diameter of 1 μm or more and 50 μm or less (hereinafter referred to as “protrusion imparting particles” for the sake of convenience). Is satisfied.
Equation _{(1) 20 ℃ ≦ T 1} -T 10 ≦ 120 ℃
In the formula (1), T ₁ represents a temperature at which the viscosity becomes 10 ⁴ Pa · s at an applied pressure of 1 MPa, which is measured using a flow tester after preparing a solid sample of the resin from the resin composition. . T ₁₀ represents a temperature at which the viscosity becomes 10 ⁴ Pa · s at an applied pressure of 10 MPa, which was measured by using a flow tester by preparing a solid sample of the resin from the resin composition.

  The recording layer resin composition of the recording medium according to the present embodiment (hereinafter sometimes referred to as “resin composition”) has a high temperature and high humidity environment (for example, a temperature of 28 ° C. and a humidity of 80 RH%). The recording layer of the recording medium capable of fixing the toner image at a low pressure (for example, 0.2 MPa or more and 2 MPa or less) is formed. Although this mechanism is not clear, it is estimated as follows.

  When the resin composition according to the present embodiment satisfies the above configuration, the recording layer formed using the resin composition according to the present embodiment exhibits a plastic behavior with respect to pressure even in a state where it is not heated. Even in a state where a moderately low pressure (for example, 0.2 MPa or more and 2 MPa or less) is applied, fluidity is exhibited in a normal temperature region (for example, 10 ° C. or more and 40 ° C. or less). For this reason, the recording layer formed using the resin composition according to the present embodiment has a relatively low pressure applied during image formation on the recording medium, and the recording layer of the recording medium can be used without heating. The toner image transferred onto the surface of the toner can be fixed. That is, the fluidity is imparted to the recording layer by the applied pressure, so that a part of the toner is embedded in the surface layer portion of the recording layer. When the pressure is released in this state, the fluidity of the recording layer is lost, and the toner is held on the surface layer portion of the recording layer. Through this process, the toner image is fixed to the recording layer.

  In addition, when the resin composition according to the present embodiment satisfies the above configuration, the recording layer does not exhibit fluidity in a state where no pressure is applied. That is, the recording layer is less likely to exhibit fluidity in processes other than the fixing process in which pressure is applied. For this reason, the recording medium provided with the recording layer is attached to the recording medium, that is, the recording medium due to the fluidity of the recording layer of the recording medium in a paper feeding process such as paper feeding, conveyance, and paper discharging. It is presumed that the recording medium hardly sticks to a member of the image forming apparatus and can continuously feed the paper.

  However, in a high-temperature and high-humidity environment such as a summer environment, even if the recording medium includes the recording layer, for example, when it is continuously transported in a state where several hundred sheets are stacked, double feeding may occur. . This double feed causes a paper jam (jam). In particular, for example, when an image is recorded under the traveling condition of a recording medium of 30 sheets / minute or more, the recording medium is likely to be double-fed.

  On the other hand, when the resin composition according to this embodiment satisfies the above-described configuration, protrusions due to the protrusion-providing particles are provided on the surface of the recording layer. When protrusions are provided on the surface of the recording layer, when a recording medium having the recording layer is overlaid, the adhesion between the recording layer and another recording medium in contact with the recording layer is reduced. For this reason, for example, even in a state where several hundred sheets are stacked in a high temperature and high humidity environment, double feeding is suppressed.

  As described above, the resin composition according to this embodiment suppresses double feeding in a high temperature and high humidity environment, and forms a recording layer of a recording medium on which a toner image can be fixed at a low pressure.

  Furthermore, the recording layer formed of the resin composition according to the present embodiment fixes the toner image by pressure. For this reason, the image forming method to which the recording medium having the recording layer is applied does not require a heat fixing step, and the image forming apparatus can be reduced in size and power consumption.

  Hereinafter, the resin composition according to the present embodiment will be described in detail.

  The resin composition according to the present embodiment includes at least a resin and protrusion-providing particles, may include a plurality of different types of resins, and may include other additives as necessary.

  The resin composition according to the present embodiment is, for example, a composition in which protrusion-providing particles are included in a solid, powder, solution, or the like containing one type of resin; ), A powder, a solution or the like containing the protrusion-providing particles; a liquid composition obtained by dissolving or dispersing one or more types of resins in a solvent, or the like; is there.

The resin composition according to this embodiment satisfies the following formula (1).
Equation _{(1) 20 ℃ ≦ T 1} -T 10 ≦ 120 ℃
In the formula (1), T ₁ represents a temperature at which the viscosity becomes 10 ⁴ Pa · s at an applied pressure of 1 MPa, which is measured using a flow tester after preparing a solid sample of the resin from the resin composition. . T ₁₀ represents a temperature at which the viscosity becomes 10 ⁴ Pa · s at an applied pressure of 10 MPa, which was measured by using a flow tester by preparing a solid sample of the resin from the resin composition.

The temperature difference ΔT (T ₁ −T ₁₀ ) is 20 ° C. or higher and 120 ° C. or lower, preferably 40 ° C. or higher and 100 ° C. or lower, and more preferably 60 ° C. or higher and 80 ° C. or lower. When the temperature difference ΔT is less than 20 ° C., the toner image is not sufficiently embedded in the recording layer, and sufficient fixability cannot be obtained. When the temperature difference ΔT exceeds 120 ° C., the recording layer becomes too soft and the entire toner image may be embedded in the recording layer. In addition, the recording medium may stick to another recording medium or a member of the image forming apparatus, and may be difficult to use in the electrophotographic process.

The temperature difference ΔT is calculated by the following method. This is performed by a method using a flow tester (for example, Shimadzu flow tester CFT-500, manufactured by Shimadzu Corporation). When the resin composition is a dispersion, the dispersion is evaporated to dryness to produce a resin solid sample (pellet-shaped sample). When the resin composition is powder or solid, the powder or solid is compressed and solidified to produce a pellet-shaped sample. The prepared sample is set in a flow tester, and the measurement temperature is gradually heated from 50 ° C. within the range of 50 ° C. to 150 ° C. (temperature increase rate of + 1 ° C./min), and a constant extrusion pressure is applied. Measure the viscosity of the sample. The applied pressure is fixed at 1 MPa, and the viscosity with respect to the temperature at 1 MPa is measured. From the obtained viscosity graph, the temperature T ₁ when the viscosity becomes 10 ⁴ Pa · s at an applied pressure of 1 MPa is determined. T ₁₀ is determined in the same manner as T ₁ except that the applied pressure 1 MPa is set to 10 MPa. The temperature difference ΔT (T ₁ −T ₁₀ ) is calculated by taking the difference from the obtained T ₁ and T ₁₀ .

  Below, two desirable forms of the resin composition concerning this embodiment are explained.

[First Embodiment]
The resin composition according to this embodiment desirably includes at least two kinds of resins having different glass transition temperatures from the viewpoint of easily exhibiting plastic behavior when a film is formed and pressure is applied. When the resin composition according to the present embodiment includes at least the two kinds of resins, the recording layer formed using the resin composition can easily form a phase separation structure. Therefore, it is considered that the recording layer can easily fix the toner image at a low pressure.

  When the resin composition which concerns on this embodiment contains 3 or more types of resin, the glass transition temperature of at least 2 types of resin should just differ among 3 or more types of resin.

In the resin composition according to this embodiment, the glass transition temperatures of the two resins are preferably different by 30 ° C. or more, and more preferably different by 35 ° C. or more. When the glass transition temperatures of the two kinds of resins are different by 30 ° C. or more, the recording medium having a recording layer formed from a resin composition containing these two kinds of resins can easily fix the toner image at a low pressure.
The resin composition according to the present embodiment may include three or more kinds of resins. In that case, it is desirable that two of them have the above relationship.

  Of the two types of resins, the content of the resin having a high glass transition temperature relative to the total mass of the two types of resins is preferably 5% by mass to 70% by mass, and preferably 10% by mass to 60% by mass, 20 mass% or more and 50 mass% or less are more preferable. When the content of the resin having a high glass transition temperature is 5% by mass or more and 70% by mass or less, fixing at a low pressure is easily performed, and the fixing degree of an image is hardly deteriorated.

  When the resin composition according to the present embodiment includes three or more types of resins, the content of the two types of resins with respect to the total mass of the three or more types of resins is 80% by mass or more and 99% by mass or less. 85 mass% or more and 95 mass% or less are preferable, and 85 mass% or more and 95 mass% or less are more preferable. When the content of the two kinds of resins is 80% by mass or more and 99% by mass or less, fixing at a low pressure is easily performed as described above.

  At least one of the two types of resins having different glass transition temperatures preferably has a glass transition temperature of 40 ° C. or higher, more preferably 45 ° C. or higher, and even more preferably 50 ° C. or higher. When the glass transition temperature is 40 ° C. or higher, it becomes easy to form a recording layer of a recording medium having excellent storage properties.

  The content of the resin having a glass transition temperature of 40 ° C. or higher is preferably 5% by mass or more and 70% by mass or less, and preferably 10% by mass or more and 60% by mass or less with respect to the mass of two types of resins having different glass transition temperatures. Preferably, 20 mass% or more and 50 mass% or less are more preferable.

  Of the two types of resins, the higher glass transition temperature is preferably 40 ° C. or higher, preferably 40 ° C. or higher and lower than 60 ° C., more preferably 40 ° C. or higher and lower than 55 ° C. When the temperature is less than 60 ° C., the fixing behavior due to pressure at normal temperature (the printer internal temperature of 50 ° C. or less) is easily exhibited.

  Of the two types of resins, the lower temperature of the glass transition temperature is preferably less than 10 ° C, preferably from -100 ° C to less than 10 ° C, and more preferably from -80 ° C to less than 10 ° C. When the temperature is less than 10 ° C., fixing at a low pressure is easily performed.

  The resin composition according to this embodiment may include three or more types of resins, in which case the glass transition temperatures of the two types of resins are different by 30 ° C. or more, and at least one of the glass transitions thereof. It is desirable that the temperature is 40 ° C. or higher.

The aspect described above for “two types of resins having different glass transition temperatures” also applies to “two types of resins having different melting temperatures” and “amorphous resins and crystalline resins having different glass transition temperatures and melting temperatures”. There is a case.
The glass transition temperature can be controlled mainly by the density of rigid units such as aromatic rings and cyclohexane rings in the main chain of the resin. That is, if the density of methylene group, ethylene group, oxyethylene group, etc. in the main chain is high, the glass transition temperature decreases, and if the aromatic ring or cyclohexane ring increases, it increases. Furthermore, when the density of side chains such as aliphatic is increased, the glass transition temperature is lowered. By taking these into consideration, resins having various glass transition temperatures can be obtained.
Similarly, the melting temperature can be controlled by the density of rigid units.

Hereinafter, when the two types of resins are two types of amorphous resins having different glass transition temperatures, the higher glass transition temperature is referred to as “high Tg resin”, and the lower glass transition temperature is referred to as “low Tg”. This will be described as “resin”.
When the two types of resins are two types of crystalline resins having different melting temperatures, the higher melting temperature is referred to as “high melting point resin” and the lower melting temperature is referred to as “low melting point resin”. To do.
When the two kinds of resins are an amorphous resin and a crystalline resin having different glass transition temperatures and melting temperatures, and the glass transition temperature is higher than the melting temperature, they are referred to as “high Tg resin” and “low melting point resin” When the transition temperature is lower than the melting temperature, it will be described as “low Tg resin” or “high melting point resin”.

  As an aspect in which the resin composition according to the present embodiment includes a high Tg resin and a low Tg resin, an aspect capable of forming a phase separation structure that easily exhibits plastic behavior when a film is formed and pressure is applied is preferable. Examples of the embodiment include a mixture containing both a high Tg resin and a low Tg resin; a resin particle in which a high Tg resin and a low Tg resin form a sea-island structure, or a composition containing the same; a high Tg resin Examples thereof include resin particles that form a core / shell structure with a low Tg resin, or compositions containing the same.

The resin composition according to the present embodiment may be an aspect including a high melting point resin and a low melting point resin, an aspect including a high Tg resin and a low melting point resin, and an aspect including a low Tg resin and a high melting point resin. Except for changing the type of the resin, it is the same as the above-described embodiment including the high Tg resin and the low Tg resin.
The example of the aspect of the resin composition which concerns on this embodiment is demonstrated in detail below by making into an example the aspect containing high Tg resin and low Tg resin.

  As a mixture containing both a high Tg resin and a low Tg resin, when the resin composition is a dispersion, a resin particle dispersion in which particles of a high Tg resin are dispersed and a resin particle dispersion in which particles of a low Tg resin are dispersed A resin particle dispersion obtained by mixing a liquid; when the resin composition is a powder, a powder obtained by mixing a powder containing a high Tg resin and a powder containing a low Tg resin; , A solid material obtained by melting and mixing a solid material containing a high Tg resin and a solid material containing a low Tg resin.

  The resin particles in which the high Tg resin and the low Tg resin form a sea-island structure form a phase separation structure in which an island phase exists in the sea phase. The resin particles forming the sea-island structure may have a high Tg resin as a sea phase and a low Tg resin as an island phase, a high Tg resin as an island phase, and a low Tg resin as a sea phase. However, it is preferable that the high Tg resin is the sea phase and the low Tg resin is the island phase.

  The sea-island structure of the resin particles contained in the resin composition is confirmed by the following method. After embedding the resin particles in epoxy resin, a section is prepared with a diamond knife or the like, the prepared section is stained with osmium tetroxide in a desiccator, and the stained section is observed with a transmission electron microscope. Check the structure of the resin particles. Here, the sea phase and the island phase of the sea-island structure are distinguished by shading caused by the degree of resin staining with osmium tetroxide.

  The major axis of the island phase is preferably 150 nm or less. When the high Tg resin is the sea phase and the low Tg resin is the island phase, the low Tg resin phase that is the island phase is preferably finely distributed. In such a case, the diameter of the island phase is preferably 150 nm or less, preferably 5 nm or more. 150 nm or less is more preferable, 50 nm or more and 140 nm or less is more preferable, and 100 nm or more and 130 nm or less is particularly preferable. When the diameter of the island phase is 150 nm or less, the pressure plastic behavior tends to be sufficient, and the toner image is easily fixed at the time of pressure fixing. When the island phase diameter is 5 nm or more, the high Tg resin and the low Tg resin are not mixed and dissolved, and it is easy to form a sea-island structure, and the cake is formed because it is plasticized even at room temperature without pressure. (Blocking) is less likely to occur.

  The major axis of the island phase can be calculated by the following method. After embedding the resin particles in an epoxy resin, a section is prepared with a diamond knife or the like, and the obtained section is observed with a transmission electron microscope. The major axis of the island phase can be calculated by arbitrarily selecting 100 island phases observed in the section and calculating the average major axis using a Luzex image analyzer.

The ratio of the mass of the resin that forms the island phase to the mass of the resin that forms the sea phase is preferably 0.25 or more.
In order to develop an appropriate pressure plastic behavior, for example, when the high Tg resin is the sea phase and the low Tg resin is the island phase, the mass ratio of the low Tg resin is 0. 0 relative to the mass of the high Tg resin. 3 or more are preferable, 0.4 or more are more preferable, and 0.5 or more are more preferable.
The mass ratio of the low Tg resin is preferably less than 1.5 with respect to the mass of the high Tg resin. When it is less than 1.5, plasticization at normal temperature hardly occurs.

  As a resin that can be used for forming the sea-island structure, for example, an addition polymerization type resin and a polycondensation resin are preferable.

  The resin particles in which the high Tg resin and the low Tg resin form a core / shell structure are resin particles having a core part (core particle) and a coating layer (shell layer) covering the core part.

  The high Tg resin may be the core and the low Tg resin may be the coating layer, or the high Tg resin may be the coating layer and the low Tg resin may be the core, but the high Tg resin is the clothing layer and the low Tg resin. Is preferably a core.

  The diameter of the core is preferably 10 nm or more and 200 nm or less, and more preferably 20 nm or more and 150 nm or less. The thickness of the coating layer is preferably 10 nm to 100 nm, and preferably 20 nm to 80 nm.

  The core / shell structure is confirmed by the following method. After embedding the resin particles in an epoxy resin, a section is prepared with a diamond knife or the like, and the obtained section is observed with a transmission electron microscope to confirm the structure of the resin particles.

  As a resin that can be used for forming the core / shell structure, for example, an addition polymerization type resin and a polycondensation resin are preferable.

[Second Embodiment]
The resin composition according to the present embodiment desirably includes a resin having two glass transition temperatures in one molecule from the viewpoint of easily exhibiting plastic behavior when a film is formed and pressure is applied. When the resin composition according to this embodiment includes the resin, the recording layer formed using the resin composition can easily form a phase separation structure. Therefore, it is considered that the recording layer can easily fix the toner image at a low pressure.

  The resin having two glass transition temperatures in one molecule preferably has two glass transition temperatures different from each other by 30 ° C. or more and 50 ° C. or more from the viewpoint that the toner is easily fixed to the recording layer at a lower pressure. More preferred.

  When the resin has two glass transition temperatures in one molecule, the resin is preferably a block copolymer or a graft copolymer of resins having different glass transition temperatures. In this case, a segment derived from a resin having a higher glass transition temperature is referred to as a “high Tg segment”, and a segment derived from a resin having a lower glass transition temperature is referred to as a “low Tg segment”.

  The proportion of the high Tg segment in the resin is preferably 5% by mass to 70% by mass, and more preferably 10% by mass to 60% by mass. When the ratio of the high Tg segment is 5% by mass or more and 70% by mass or less, fixing at a low pressure is easily performed, and the fixing degree of the image is not easily deteriorated.

  The resin preferably has a glass transition temperature of 40 ° C. or higher, more preferably 45 ° C. or higher, and further preferably 50 ° C. or higher. When the glass transition temperature is 40 ° C. or higher, it becomes easy to form a recording layer of a recording medium having excellent storage properties.

As long as the block copolymer exhibits a plastic behavior when a pressure is applied, the connecting form of the constituent segments may be any.
As the block copolymer, for example, when the high Tg segment is A and the low Tg segment is B, AB type, ABA type, BAB type, (AB) _n type, (AB) _n A type, B (AB) Examples include an _n- type block copolymer.

  The phase-separated structure formed by the block copolymer has a thermodynamically most stable structure depending on the type and molecular weight of the constituent segments. In general, in a copolymer composed of a C segment and a D segment, Regardless of the type of connection, it depends only on the C / D composition ratio. As the C / D ratio increases, C is a spherical domain, D is a matrix (C sphere D matrix) (sea island), and C is a rod-like domain. Is a matrix (cylinder), C and D are nested (gyroid), C / D alternating layers (lamellar), D is a rod-like domain, C is a matrix (cylinder), D and C are nested (gyroid), D Is a spherical domain and C systematically changes into a matrix (D sphere C matrix) (sea island).

  However, when a film is formed by a wet coating method, the phase separation state can be arbitrarily controlled by the solvent used, the drying speed, and the like. For example, even when a C / D ratio is large and thermodynamically a D sphere C matrix is used, if a solvent that is a good solvent for D and a poor solvent for C is selected as a coating solvent, the C sphere D matrix structure Can be obtained.

  Further, when both C and D good solvents are used and the solvent is rapidly removed, a phase separation structure (modulation structure) frozen in a spinodal decomposition state can be obtained. When a polymer having a large C / D ratio and thermodynamically taking a D sphere C matrix is added with a polymer compatible with only D, C is compatible only with spheres, D and D only. It is also possible to obtain a phase separation structure in which the polymer is a matrix.

  The size of the repeating unit of the phase separation structure formed by the block copolymer increases as the molecular weight of the block copolymer increases. The weight average molecular weight of the block copolymer is preferably from 3,000 to 500,000, preferably from 5,000 to 400,000, and more preferably from 6,000 to 300,000.

  The C sphere D matrix and the D sphere C matrix represent resin particles in which a block copolymer having a high Tg segment and a low Tg segment forms a sea-island structure, or a composition containing the same. This sea-island structure is the same as the sea-island structure formed by the high Tg resin and the low Tg resin described above.

  The block copolymer or graft copolymer having a high Tg segment and a low Tg segment can take the form of a resin particle forming a core / shell structure. The core / shell structure is the same as the core / shell structure formed by the high Tg resin and the low Tg resin described above.

  In addition, the method for producing resin particles in which the block copolymer or graft copolymer forms a core / shell structure is, for example, by producing aggregated particles that become a core portion by an emulsion aggregation method, and then forming a single particle on the surface of the aggregated particles. There is a method for producing the resin particles by polymerizing a monomer to form a shell layer.

The synthesis method of the block copolymer or graft polymer is as follows: “4th edition Experimental Chemistry Course 28 Polymer Synthesis (Maruzen, 1992)”, “Macromonomer Chemistry and Industry (IPC, 1990)”, “High Molecular Compatibilization and Evaluation Technology (Technical Information Society, 1992) "," New Polymer One Point 12 Polymer Alloy (Kyoritsu, 1988) "," Angew. Macromol. Chem., 143, pp.1-9 (1986) ) "," Journal of the Adhesion Society of Japan, 26, pp. 112-118 (1990) "," Macromolecules, 28, pp. 4893-4898 (1995) "," J. Am. Chem. Soc., 111, pp. 7641-7643 (1989) "," JP-A-6-83077 ", etc., any appropriate synthesis method described in the literature may be used.
As the resin used for the synthesis of the block copolymer or graft copolymer, for example, an addition polymerization type resin and a polycondensation resin are preferable.

[Temperature characteristics of resin]
“Crystallinity” of the resin means that in differential scanning calorimetry, it has a clear endothermic peak, not a stepwise change in endothermic amount. Specifically, it is measured at a heating rate of 10 (° C./min). It means that the half-value width of the endothermic peak is 10 ° C. or less. The “amorphous” of the resin means that the half width exceeds 10 ° C., shows a stepwise endothermic change, or does not show a clear endothermic peak.

  The glass transition temperature of the resin is determined from a DSC curve obtained by differential scanning calorimetry (DSC), and more specifically, described in the method for determining the glass transition temperature of JIS K7121-1987 “Method for Measuring the Transition Temperature of Plastics”. It is determined by “extrapolated glass transition start temperature”. Also, the melting temperature of the resin is determined by the “melting peak temperature” described in the method for determining the melting temperature of JIS K7121-1987 “Method for measuring the transition temperature of plastics” from the DSC curve obtained by differential scanning calorimetry (DSC). Ask.

As an example, the measurement of the glass transition temperature of a resin composition containing a high Tg resin and a low Tg resin will be described for each aspect of the resin composition.
When the resin composition is a mixture containing both a high Tg resin and a low Tg resin, the glass transition temperatures of the high Tg resin and the low Tg resin before mixing are measured.
When the resin composition includes resin particles in which a high Tg resin and a low Tg resin form a sea-island structure, the high-Tg resin and the low-Tg resin before producing the resin particles forming the sea-island structure The glass transition temperature of each is measured.

When the resin composition contains resin particles in which a high Tg resin and a low Tg resin form a core / shell structure, and the resin particles are produced by an emulsion aggregation method, before the resin particles are produced The glass transition temperatures of the high Tg resin and the low Tg resin are respectively measured.
The measuring method of the melting temperature of the resin composition containing the high melting point resin and the low melting point resin is also the glass transition temperature of the resin composition containing the high Tg resin and the low Tg resin except that the glass transition temperature is changed to the melting temperature. This is the same as the measuring method. Moreover, the measuring method of the glass transition temperature and melting temperature of the resin composition of other resin combinations, such as a resin composition containing a high Tg resin and a low melting point resin, is the same as the measuring method described above.

When the resin composition contains a block copolymer or graft copolymer having a high Tg segment and a low Tg segment, DSC measurement of the block copolymer or graft copolymer in the resin composition is carried out to obtain From the obtained DSC curve, the glass transition temperature derived from the high Tg segment and the glass transition temperature derived from the low Tg segment in the molecule of the block copolymer or graft copolymer are determined.
The same applies to the method for measuring the glass transition temperature or the melting temperature of the resin composition containing the block copolymer or graft copolymer of another embodiment.

-Resin-
The resin will be described.
Examples of the resin include addition polymerization type resins and polycondensation resins.

The addition polymerization type resin is a polymer of a monomer having an ethylenically unsaturated double bond.
Examples of the monomer constituting the addition polymerization type resin (monomer having an ethylenically unsaturated double bond) include styrenes such as styrene, parachlorostyrene, and α-methylstyrene; methyl acrylate, acrylic acid Ethyl, propyl acrylate, butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, etc. (Meth) acrylic acid esters; (meth) acrylonitriles such as acrylonitrile and methacrylonitrile; ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether S; vinyl methyl ketone, vinyl ethyl ketone, vinyl ketones such as vinyl isopropenyl ketone; and isoprene, butene, olefins such as butadiene, etc., can be mentioned β- carboxyethyl acrylate. Among these monomers, a homopolymer obtained by polymerizing one kind of monomer, a copolymer obtained by copolymerizing two or more kinds of monomers, and a mixture thereof may be used.

  The addition polymerization type resin may contain an acidic polar group, a basic polar group, or an alcoholic hydroxyl group as necessary. Examples of the acidic polar group include a carboxy group, a sulfonic acid group, and an acid anhydride.

  Examples of the monomer for adding an acidic polar group to the addition polymerization type resin include an α, β-ethylenically unsaturated compound having a carboxy group or a sulfonic acid group. Of these monomers, acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, cinnamic acid, sulfonated styrene, allylsulfosuccinic acid and the like are preferable.

Examples of the basic polar group include an amino group, an amide group, a hydrazide group, and the like.
Examples of the monomer for adding the basic polar group to the addition polymerization resin include a monomer having a nitrogen atom (hereinafter also referred to as “nitrogen-containing monomer”). Of these nitrogen-containing monomers, (meth) acrylic acid amide compounds, (meth) acrylic acid hydrazide compounds, or (meth) acrylic acid aminoalkyl compounds are preferred.
Here, the above-mentioned notation such as “(meth) acrylic acid” is an abbreviated notation indicating that both structures of methacrylic acid and acrylic acid can be taken. The following notation is the same.

  Examples of (meth) acrylic acid amide compounds include acrylic acid amide, methacrylic acid amide, acrylic acid methylamide, methacrylic acid methylamide, acrylic acid dimethylamide, acrylic acid diethylamide, acrylic acid phenylamide, and acrylic acid benzylamide. Can do.

  Examples of the (meth) acrylic acid hydrazide compound include acrylic acid hydrazide, methacrylic acid hydrazide, acrylic acid methyl hydrazide, methacrylic acid methyl hydrazide, acrylic acid dimethyl hydrazide, and acrylic acid phenyl hydrazide.

  The (meth) acrylic acid aminoalkyl compound may be a (meth) acrylic acid monoalkylaminoalkyl compound or a (meth) acrylic acid dialkylaminoalkyl compound. Examples of the (meth) acrylic acid aminoalkyl compound include 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2- (diethylamino) ethyl (meth) acrylate, and the like.

  As a monomer for forming an alcoholic hydroxyl group, for example, hydroxy (meth) acrylates are preferable. Specifically, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) ) Acrylate and the like.

A chain transfer agent may be used for the polymerization of the addition polymerization type resin.
Although there is no restriction | limiting in particular as a chain transfer agent, For example, the compound which has a thiol component can be mentioned. Examples of the compound having a thiol component include mercaptans. Among the mercaptans, alkyl mercaptans such as hexyl mercaptan, heptyl mercaptan, octyl mercaptan, nonyl mercaptan, decyl mercaptan, dodecyl mercaptan are preferable.

A crosslinking agent can be added to the addition polymerization type resin to form a crosslinked resin. As a crosslinking agent, the polyfunctional monomer which has a 2 or more ethylenically unsaturated group in a molecule | numerator can be mentioned, for example.
Examples of the polyfunctional monomer include aromatic polyvinyl compounds such as divinylbenzene and divinylnaphthalene; divinyl phthalate, divinyl isophthalate, divinyl terephthalate, divinyl homophthalate, divinyl trimesate / trivinyl, and naphthalene dicarboxylic acid. Polyvinyl esters of aromatic polyvalent carboxylic acids such as divinyl acid and diphenyl biphenyl carboxylate; Divinyl esters of nitrogen-containing aromatic compounds such as divinyl pyridine dicarboxylate; Vinyl pyromutate, vinyl furan carboxylate, pyrrole-2- Vinyl esters of unsaturated heterocyclic compounds such as vinyl carboxylate and vinyl thiophenecarboxylate; butanediol methacrylate, hexanediol acrylate, octanediol methacrylate, decanediol acrylate (Meth) acrylic acid esters of linear polyhydric alcohols such as dodecanediol methacrylate; branches such as neopentylglycol dimethacrylate and 2-hydroxy-1,3-diacryloxypropane; ) Acrylic acid esters; Polyethylene glycol di (meth) acrylate, Polypropylene polyethylene glycol di (meth) acrylates; Divinyl succinate, divinyl fumarate, vinyl / divinyl maleate, divinyl diglycolate, vinyl / divinyl itaconate, acetone Divinyl dicarboxylate, divinyl glutarate, divinyl 3,3′-thiodipropionate, trans-aconite divinyl / trivinyl, divinyl adipate, divinyl pimelate, divinyl suberate, dibi azelate Le, sebacate, divinyl dodecanedioate divinyl, mention may be made of the polyvinyl esters of polycarboxylic acids such as oxalic acid divinyl like. These crosslinking agents may be used alone or in combination of two or more.

Among the above crosslinking agents, (meth) acrylic acid esters of linear polyhydric alcohols such as butanediol methacrylate, hexanediol acrylate, octanediol methacrylate, decanediol acrylate, and dodecanediol methacrylate; neopentyl glycol dimethacrylate, 2-hydroxy Branches such as -1,3-diacryloxypropane, (meth) acrylic acid esters of substituted polyhydric alcohols; polyethylene glycol di (meth) acrylate, polypropylene polyethylene glycol di (meth) acrylate, etc. are preferably used. .
The content of the crosslinking agent is preferably 0.05% by mass or more and 5% by mass or less, more preferably 0.1% by mass or more and 1.0% by mass or less, based on the total amount of monomers constituting the addition polymerization resin.

  The addition polymerization type resin may be produced by radical polymerization using a radical polymerization initiator. There is no restriction | limiting in particular as an initiator for radical polymerization, A well-known radical polymerization initiator can be mentioned.

  The amount of the radical polymerization initiator used is preferably 0.01% by mass or more and 15% by mass or less, and more preferably 0.1% by mass or more and 10% by mass or less, based on the total amount of monomers constituting the addition polymerization resin.

The weight average molecular weight of the addition polymerization type resin is preferably from 1,500 to 60,000, and more preferably from 3,000 to 40,000.
The weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured by gel permeation chromatography (GPC). The molecular weight measurement by GPC is performed with a THF solvent using a Tosoh GPC / HLC-8120GPC as a measuring device and a Tosoh column / TSKgel SuperHM-M (15 cm). The weight average molecular weight and the number average molecular weight are calculated using a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample from this measurement result.

An example of the polycondensation resin is a polyester resin. This polyester resin may be crystalline or amorphous.
Examples of the monomer constituting the polyester resin include polyvalent carboxylic acids containing two or more carboxyl groups in one molecule, polyhydric alcohols containing two or more hydroxyl groups in one molecule, and hydroxycarboxylic acids. be able to.

  Among the polycarboxylic acids used to obtain the crystalline polyester resin, examples of the dicarboxylic acid include oxalic acid, glutaric acid, succinic acid, maleic acid, adipic acid, β-methyladipic acid, azelaic acid, and sebacin. Acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, citraconic acid, diglycolic acid, cyclohexane-3,5-diene-1,2-carboxylic acid, malic acid, citric acid, hexa Hydroterephthalic acid, malonic acid, pimelic acid, tartaric acid, mucous acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, m-pheny Range glycolic acid, p-phenylene diglycolic acid, o Phenylene diglycolic acid, diphenylacetic acid, diphenyl-p, p′-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracene dicarboxylic acid, 1 , 4-cyclohexanedicarboxylic acid and the like. These dicarboxylic acids may be used alone or in combination of two or more.

  Examples of the polyvalent carboxylic acid other than dicarboxylic acid include trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, and pyrenetetracarboxylic acid.

  Moreover, you may use what derived the carboxy group of these carboxylic acid into the acid anhydride, mixed acid anhydride, acid chloride, or ester. Of these polycarboxylic acids other than dicarboxylic acids, one kind may be used alone, or two or more kinds may be used in combination. These polyvalent carboxylic acids may be used alone or in combination of two or more.

  Examples of the polyhydric alcohol used to obtain the crystalline polyester resin include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, , 4-butenediol, neopentyl glycol, 1,5-pentane glycol, 1,6-hexane glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, poly Examples thereof include tetramethylene glycol, bisphenol A, bisphenol Z, hydrogenated bisphenol A, cyclohexanedimethanol, and alkylene oxide adducts thereof. Among these polyhydric alcohols, one kind may be used alone, or two or more kinds may be used in combination.

A desired crystalline polyester resin can be obtained by polycondensation of the polyvalent carboxylic acid and the polyhydric alcohol in combination.
Examples of crystalline polyester resins include polyester resins obtained by polycondensation of 1,9-nonanediol and 1,10-decanedicarboxylic acid, polyester resins obtained by polycondensation of cyclohexanediol and adipic acid, Polyester resin obtained by polycondensation of 1,6-hexanediol and sebacic acid, polyester resin obtained by polycondensation of ethylene glycol and succinic acid, polyester obtained by polycondensation of ethylene glycol and sebacic acid Examples thereof include a polyester resin obtained by polycondensation of a resin, 1,4-butanediol and succinic acid.

  Moreover, said polyhydric carboxylic acid and polyhydric alcohol may be used individually by 1 type, respectively, respectively, one may be used individually and the other may be used 2 or more types, or each may be used 2 or more types. When using hydroxycarboxylic acid as a monomer, it may be used individually by 1 type, may use 2 or more types together, and may use polyhydric carboxylic acid and a polyhydric alcohol together.

  As the polyvalent carboxylic acid used to obtain the amorphous polyester resin, for example, among the polyvalent carboxylic acids, examples of the dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, Chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, m-phenylenediglycolic acid, p-phenylenediglycolic acid, o-phenylenediglycolic acid, diphenylacetic acid, diphenyl-p, p'-dicarboxylic Examples thereof include acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracene dicarboxylic acid, and cyclohexanedicarboxylic acid.

  Examples of the polyvalent carboxylic acid other than the dicarboxylic acid include trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, and pyrenetetracarboxylic acid. Moreover, you may use what derived the carboxy group of these carboxylic acid into the acid anhydride, the acid chloride, or ester. These polyvalent carboxylic acids may be used alone or in combination of two or more.

  Among these, it is preferable to use terephthalic acid, its lower ester, diphenylacetic acid, 1,4-cyclohexanedicarboxylic acid, and the like. The lower ester refers to an ester of an aliphatic alcohol having 1 to 8 carbon atoms.

  Examples of the polyhydric alcohol used for obtaining the amorphous polyester resin include the above polyhydric alcohols. Of these polyhydric alcohols, polytetramethylene glycol, bisphenol A, bisphenol Z, hydrogenated bisphenol A, cyclohexanedimethanol, and alkylene oxide adducts thereof are particularly preferably used. These polyhydric alcohols may be used alone or in combination of two or more.

In addition, an amorphous resin or a crystalline resin can be easily obtained by combining the above polycondensable monomers.
The polyvalent carboxylic acid and the polyhydric alcohol are used in order to produce one type of polycondensation resin, each of which may be used alone, or one of them may be used alone and two or more may be used. More than one species may be used. Moreover, when using hydroxycarboxylic acid for producing 1 type of polycondensation resin, 1 type may be used individually, 2 or more types may be used, and polyhydric carboxylic acid and polyhydric alcohol may be used together. .

  The weight average molecular weight of the polycondensation resin is preferably from 1,500 to 60,000, more preferably from 3,000 to 40,000. When the weight average molecular weight is 1,500 or more, cracks in the recording layer and the like and peeling from the base material layer tend to occur. Further, it may be partially branched or cross-linked by selecting the carboxylic acid valence or alcohol valence of the monomer.

-Protrusion-providing particles-
The protrusion imparting particles are particles having a volume average particle diameter of 1 μm or more and 50 μm or less. When the volume average particle diameter of the protrusion-providing particles is in the above range, protrusions are provided on the surface of the recording layer. That is, the desired unevenness (surface roughness) is given to the surface of the recording layer. Thereby, double feeding of the recording medium is suppressed even in a high temperature and high humidity environment.
The volume average particle size of the protrusion imparting particles is preferably 1 μm or more and 40 μm or less, more preferably 3 μm or more and 30 μm or less, and further preferably 5 μm or more and 20 μm or less from the viewpoint of suppressing the double feeding of the recording medium. In particular, the volume average particle diameter of the protrusion imparting particles is preferably larger than the thickness of the recording layer.
If the volume average particle diameter of the protrusion-providing particles is in the above range, low-pressure fixing of the recording layer is difficult to be inhibited.

  The volume average particle diameter of the protrusion imparting particles is a value measured by the following method. After forming the recording layer with the resin composition, the recording layer is cut to prepare a measurement sample. The measurement sample is observed with a SEM (Scanning Electron Microscope) apparatus, and the longest diameter and the shortest diameter are measured for each primary particle of 100 projection-providing particles by image analysis, and the equivalent sphere diameter is measured from the intermediate value. The 50% diameter (D50v) in the volume-based cumulative frequency of the obtained equivalent sphere diameter is defined as the average particle diameter (that is, volume average particle diameter) of the protrusion imparting particles.

The particle size distribution of the protrusion imparting particles is preferably narrow from the viewpoint of realizing the double feeding of the recording medium with a small amount.
The shape of the protrusion-providing particles may be any of spherical, elliptical, polyhedral, plate-like, needle-like, columnar, irregular shape, etc., but from the viewpoint of suppressing the double feeding of the recording medium and reducing the influence of the viscosity of the resin composition. Spherical shape is preferred.

  Examples of the protrusion imparting particles include resin particles, inorganic particles, and organic-inorganic composite particles.

Examples of the resin particles include styrenes (for example, styrene, parachlorostyrene, α-methylstyrene), (meth) acrylic acid esters (for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-acrylate). -Butyl, lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, etc.), ethylenically unsaturated nitriles (for example, acrylonitrile, methacrylate) Nitriles), vinyl ethers (eg, vinyl methyl ether, vinyl isobutyl ether), vinyl ketones (vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl ketone, etc.), olefins (eg, ethylene, propylene, etc.) Emissions, a homopolymer of a monomer such as butadiene) and the like, or particles of these monomers with vinyl resins composed of two or more combined copolymers. Specific examples of vinyl resin particles include styrene resin, (meth) acrylic resin, and styrene-acrylic copolymer particles.
Examples of the resin particles include melamine resin, guanamine resin, silicone resin, fluorine resin, epoxy resin, polyester resin, polyurethane resin, polyamide resin, cellulose resin, polyether resin, non-vinyl resin such as modified rosin, and the above-mentioned Also included are particles such as a mixture with a vinyl resin, or a graft polymer obtained by polymerizing a vinyl monomer in the presence of these.

The resin particles may be non-crosslinked resin particles or crosslinked resin particles. In particular, the resin particles are preferably resin particles having a glass transition temperature of 50 ° C. or higher (preferably 60 ° C. or higher, more preferably 70 ° C. or higher) from the viewpoint of suppressing double feeding.
The glass transition temperature is determined from a DSC curve obtained by differential scanning calorimetry (DSC), and more specifically, described in the method for determining the glass transition temperature in JIS K-1987 “Method for Measuring Transition Temperature of Plastics”. It is determined by “extrapolated glass transition start temperature”.

Examples of the inorganic particles include inorganic oxide particles. Examples of the inorganic oxide particles include silica (for example, fumed silica and sol-gel silica), titania (titanium oxide), alumina (aluminum oxide), zinc oxide, tin oxide, and iron oxide.
Examples of the inorganic particles include calcium carbonate, barium sulfate, boron nitride and the like in addition to the inorganic oxide particles.

  Examples of the organic / inorganic composite particles include the inorganic particles coated with the resin of the resin particles. Specifically, as the organic-inorganic composite particles, for example, particles grafted on the surface of silica, titania, alumina, etc., dissolve the resin in the solvent, and further disperse the inorganic particles as described above, then suspend in water, Examples thereof include capsule particles in which the solvent is removed by heating, reduced pressure, etc., and inorganic particles are used as cores.

Among these, as the protrusion imparting particles, for example, polystyrene particles, poly (meth) acrylate particles (for example, polymethyl methacrylate particles), styrene- (meth) acrylate copolymer particles, silicone resin particles, and the like Preferred are resin particles such as crosslinked resin particles; inorganic particles such as silica particles, titania particles and alumina particles; inorganic particles (eg silica particles) coated with a resin (eg melamine resin and guanamine resin).
In addition, protrusion provision particle | grains may be used individually by 1 type, and may be used together 2 or more types.

  The content of the protrusion-imparting particles is 1% by mass or more with respect to the total solid content of the resin composition (that is, with respect to the entire recording layer) in terms of suppression of double feeding of the recording medium and low pressure fixability of the recording layer. 20 mass% or less is preferable, and 3 mass% or more and 15 mass% or less are more preferable. In particular, when the content of the protrusion-providing particles is 20% by mass or more, the influence on the pressure dependency of the viscosity of the adhesive layer is suppressed, and low-pressure fixing is hardly inhibited. When it is 1% by mass or less, it becomes difficult to obtain the effect of suppressing double feeding.

-Additives-
Examples of other additives include a surfactant, a catalyst, and a solvent.

[Method for producing resin composition]
As an example of the method for producing the resin composition according to the present embodiment, a method in which a resin particle dispersion is prepared by synthesizing a resin in an aqueous solvent by an emulsion polymerization method using a known surfactant. After preparing the resin particle dispersion, different resin particle dispersions may be mixed to form a resin particle dispersion in which different types of resin particles are dispersed.

  Below, the detail of the manufacturing method of the resin composition of the aspect containing high Tg resin and low Tg resin is demonstrated as an example. The aspect including a high melting point resin and a low melting point resin, the aspect including a high Tg resin and a low melting point resin, and the aspect including a low Tg resin and a high melting point resin are also used except that the type of the resin is changed. And a low Tg resin.

-Manufacturing method of mixture containing both high Tg resin and low Tg resin-
When the resin composition is a dispersion, a method of mixing a resin particle dispersion in which particles of high Tg resin are dispersed and a resin particle dispersion in which particles of low Tg resin are dispersed; And a powder having a high Tg resin and a powder having a low Tg resin; if the resin composition is a solid, a solid having a high Tg resin and a low Tg resin. And the like.

-Manufacturing method of resin particles forming sea-island structure-
Resin particles in which a high Tg resin and a low Tg resin form a sea-island structure include, for example, a resin particle dispersion in which particles of a high Tg resin are dispersed and a resin particle dispersion in which particles of a low Tg resin are dispersed Can be formed as an aggregated fusion body by an ordinary emulsion aggregation method.

  In such a case, the resin particles of the high Tg resin and the low Tg resin each have a median diameter of 100 nm or less, preferably 10 nm or more and 90 nm or less, and more preferably 40 nm or more and 80 nm or less, as a resin particle dispersion of the material. When the median diameter of each resin particle is 100 nm or less, the major axis of the island phase contained in the aggregated fusion product is 150 nm or less, and the fixability of the toner image is improved. When the median diameter of each resin particle is 10 nm or more, mixing and dissolution hardly proceed at the time of aggregation and fusion, and it is easy to form a sea-island structure and hardly plasticize at room temperature. Examples of the method of adjusting the median diameter of the resin particles include a method of adjusting the amount of the surfactant used when emulsifying and dispersing the resin of the material.

  In addition, the median diameter of the resin particles can be measured by a known method, and for example, it can be measured with a laser diffraction particle size distribution measuring device (LA-920, manufactured by Horiba, Ltd.).

-Method for producing resin particles having a core / shell structure-
Resin particles having a core / shell structure can be produced, for example, by an emulsion aggregation method. In this case, for example, the second resin particle dispersion is mixed with the above-described steps (resin particle dispersion preparation step, aggregated particle formation step, fusion / unification step) and the dispersion in which the aggregated particles are dispersed, and the aggregated particles A step of aggregating the resin particles so as to further adhere to the surface thereof to form second agglomerated particles, a step of fusing and coalescing the second agglomerated particles to form resin particles having a core / shell structure, Then, resin particles having a core / shell structure are manufactured.

<Recording medium>
The recording medium according to the present embodiment has a base material and a recording layer formed on the base material using a resin composition. Since the recording medium according to the present embodiment has a recording layer formed using the resin composition according to the present embodiment, the toner image can be fixed at a low pressure.

Examples of the base material include paper.
Examples of the paper include high-quality paper, coated paper, craft paper, glassine paper, and recycled paper.

The recording layer is a layer for fixing the toner image.
The thickness of the recording layer is preferably 1 μm to 50 μm, preferably 2 μm to 30 μm, and more preferably 3 μm to 25 μm.

  The recording layer preferably has a phase separation structure that easily exhibits plastic behavior when pressure is applied to the recording layer. Examples of the phase separation structure include a sea-island structure, a core / shell structure aggregation structure, a structure including at least one of a block copolymer and a graft copolymer.

  The recording layer preferably contains at least two kinds of resins or two kinds of segments and has a phase separation structure. More preferably, the recording layer has a phase separation structure including a high Tg resin and a low Tg resin, and a phase separation structure including a resin having a high Tg segment and a low Tg segment. Examples of the phase separation structure include an aggregated fusion of resin particles in which a high Tg resin and a low Tg resin form a sea-island structure, and a resin particle in which a high Tg resin and a low Tg resin form a core / shell structure. Examples include an aggregated fusion, a structure including a block copolymer or a graft copolymer having a high Tg segment and a low Tg segment.

  Hereinafter, as an example of an aspect of the recording layer, an aspect having a phase separation structure including a high Tg resin and a low Tg resin will be described. The aspect including a high melting point resin and a low melting point resin, the aspect including a high Tg resin and a low melting point resin, and the aspect including a low Tg resin and a high melting point resin are also used except that the type of the resin is changed. And a low Tg resin.

  The aggregated fusion of resin particles in which a high Tg resin and a low Tg resin form a sea-island structure forms a phase separation structure in which an island phase exists in the sea phase. In the aggregated fusion, the high Tg resin may be a sea phase and the low Tg resin may be an island phase, the high Tg resin may be an island phase, and the low Tg resin may be a sea phase. The sea phase and the low Tg resin are preferably island phases.

  The sea-island structure of the aggregated fusion is confirmed by the following method. After embedding the recording layer of the recording medium according to this embodiment in an epoxy resin, a section is prepared with a diamond knife or the like, the prepared section is stained with osmium tetroxide in a desiccator, and the stained section is transmitted. Observe with a scanning electron microscope to confirm the structure of the recording layer. Here, the sea phase and the island phase of the sea-island structure are distinguished by shading caused by the degree of resin staining with osmium tetroxide.

  The major axis of the island phase is preferably 150 nm or less. When the high Tg resin is the sea phase and the low Tg resin is the island phase, the low Tg resin phase that is the island phase is preferably finely distributed. In such a case, the diameter of the island phase is preferably 150 nm or less, preferably 5 nm or more. 150 nm or less is more preferable, 50 nm or more and 140 nm or less is more preferable, and 100 nm or more and 130 nm or less is particularly preferable. When the diameter of the island phase is 150 nm or less, the pressure plastic behavior tends to be sufficient, and the toner image is easily fixed at the time of pressure fixing. When the island phase diameter is 5 nm or more, the high Tg resin and the low Tg resin are not mixed and dissolved, and it is easy to form a sea-island structure, and the cake is formed because it is plasticized even at room temperature without pressure. (Blocking) is less likely to occur.

  The major axis of the island phase can be calculated by the following method. After embedding the recording layer in an epoxy resin, a section is prepared with a diamond knife or the like, and the obtained section is observed with a transmission electron microscope. The major axis of the island phase can be calculated by arbitrarily selecting 100 island phases observed in the section and calculating the average major axis using a Luzex image analyzer.

The ratio of the mass of the resin that forms the island phase to the mass of the resin that forms the sea phase is preferably 0.25 or more.
In order to develop an appropriate pressure plastic behavior, for example, when the high Tg resin is the sea phase and the low Tg resin is the island phase, the mass ratio of the low Tg resin is 0. 0 relative to the mass of the high Tg resin. 3 or more are preferable, 0.4 or more are more preferable, and 0.5 or more are more preferable.
The mass ratio of the low Tg resin is preferably less than 1.5 with respect to the mass of the high Tg resin. When it is less than 1.5, plasticization at normal temperature hardly occurs.

  The aggregated fusion of resin particles in which a high Tg resin and a low Tg resin form a core / shell structure is an aggregation of resin particles having a core (core particle) and a coating layer (shell layer) covering the core. It is a fusion. The preferred embodiments of the core and the coating layer are the same as the resin particles in the recording layer forming resin composition.

  The core / shell structure is confirmed by the following method. After embedding the recording layer in an epoxy resin, a section of the resin composition is prepared with a diamond knife or the like, and the obtained section is observed with a transmission electron microscope to confirm the structure of the recording layer.

  The preferred embodiment of the block copolymer or graft copolymer in the structure containing a block copolymer or graft copolymer having a high Tg segment and a low Tg segment is the same as the polymer in the recording layer forming resin composition. It is.

  As a method for producing a recording medium according to the present embodiment, for example, when the resin composition is a dispersion, a resin particle dispersion (resin composition according to the present embodiment) in which at least a resin is dispersed is prepared and prepared. A method in which the resin particle dispersion is applied to a substrate and dried to form; if the resin composition is a powder, the melt of the powder is layered on a peelable substrate, and the formed layer is And a method of laminating on a substrate. Here, the substrate is not particularly limited as long as the formed recording layer is supported and the recording layer is peeled off, and a known substrate can be used.

  Application of the resin particle dispersion is performed by, for example, on-machine or off-machine using a blade coater, roll coater, reverse roll coater, air knife coater, rod coater, cast coater, bar coater, curtain coater die slot coater, gravure coater, etc. Done. In addition to natural drying, a method of artificially accelerating the drying may be employed for the drying. For example, an infrared dryer, a drum dryer, an air cap dryer, an air foil dryer, an air conditioner dryer, or the like can be used.

<Recorded image>
The recorded image according to the present embodiment includes a recording medium, a toner image formed on the recording medium using an electrostatic charge image developing toner and fixed without being embedded in the whole, and at least a part of the toner image. The image information concealing layer which covers and can be peeled in order. The recording medium according to the present embodiment is applied to the recording medium of the image recorded matter according to the present embodiment. The image information hiding layer is a layer that covers the toner image of the recording layer of the recording medium so that the image information cannot be grasped from the outside and can be peeled off as necessary.

  “Fixed without being entirely embedded” means a state in which the toner image is fixed without being completely embedded in the recording layer. The toner image may be fixed by being adhered to the surface of the recording layer, or may be fixed by being partially embedded in the recording layer. Hereinafter, further description will be given with reference to the drawings.

FIG. 1 is a cross-sectional view showing an example of an image recorded matter according to the present embodiment.
An image recording 6 shown in FIG. 1 includes a recording medium 3, a toner image 4, and an image information hiding layer 5. The recording medium 3 includes a base material 2 and a recording layer 1 formed on the base material 2. The toner image 4 is formed on the recording layer 1 of the recording medium 3 using an electrostatic charge image developing toner (hereinafter also referred to as “toner”), and a part of the toner image 4 is not embedded in the recording layer 1. Embedded and fixed. The image information hiding layer 5 covers the toner image (image information) 4. The content of the image information can be confirmed by peeling off the image information hiding layer 5 as necessary. The toner image is preferably an isolated image or line drawing in which toner does not easily overlap.

  The recorded image according to this embodiment is excellent in releasability of the image information hiding layer because the toner image is fixed without being entirely embedded. Here, the peelability is a property representing the ease of peeling of the image information hiding layer and the sharpness of the toner image remaining after peeling of the image information hiding layer.

  The image information concealment layer is not particularly limited as long as the image information to be covered is concealed to such an extent that the image information to be covered cannot be grasped, and has a hardness that does not embed the entire toner image in the recording layer, such as paper, plastic film, metal foil, etc. Is mentioned. These may be laminated or coated with a light-shielding substance.

Examples of the paper include high-quality paper, coated paper, craft paper, glassine paper, and recycled paper.
Examples of the plastic film include a polyester film, a polypropylene film, and a polyvinyl chloride film.
Examples of the metal foil include aluminum foil, copper foil, silver foil, gold foil, stainless steel foil, titanium foil, and metal deposition films thereof.

<Image forming method>
The image forming method according to the present embodiment includes a charging step for charging the surface of an image carrier, an electrostatic image forming step for forming an electrostatic image on the charged surface of the image carrier, and a toner for developing an electrostatic image. A developing step of developing the electrostatic image formed on the surface of the image carrier as a toner image with an electrostatic image developer containing the toner image; and the toner image formed on the surface of the image carrier with the recording layer of the recording medium A transfer step of transferring to the surface of the recording medium; and a fixing step of fixing the toner image transferred to the surface of the recording layer of the recording medium to the recording layer of the recording medium by pressure without embedding the entire toner image; Have

The image forming method according to the present embodiment is an image forming method in which an unfixed toner image is formed on the surface of a recording layer of a recording medium, and a toner fixed image is obtained by applying pressure to the toner image. As a medium, the recording medium according to the present embodiment is used.
Since the image forming method according to the present embodiment uses the recording medium according to the present embodiment, an image forming method capable of fixing a toner image with a low pressure is provided.

  For the charging process, the electrostatic charge image forming process, the developing process, and the transferring process, each process of a known electrophotographic (electrostatic charge developing) image forming method can be used.

The fixing step is a step of fixing the toner image transferred to the surface of the recording layer of the recording medium without embedding the entire toner image in the recording layer of the recording medium by pressure.
“Fixing without embedding the whole” means fixing the toner image transferred onto the surface of the recording layer without being completely embedded in the recording layer. The toner image may be fixed by adhering to the surface of the recording layer, or may be fixed by being partially embedded in the recording layer.

  The pressure applied to the recording medium is preferably 0.2 MPa or more and 2.0 MPa or less, and more preferably 0.3 MPa or more and 1.0 MPa or less. When the pressure applied to the recording medium is 0.2 MPa or more and 2.0 MPa or less, a normal heat fixing device can be used, and the mass and size of the image forming apparatus are not affected.

  FIG. 2 is a cross-sectional view illustrating an example of a recording medium in which a toner image is transferred to the surface of the recording layer of the recording medium. A toner image 4 is placed on the surface of the recording layer 1 of the recording medium 3 according to the present embodiment, and shows a state after the transfer step in the image forming method. 2, the toner image 4 transferred to the surface of the recording layer 1 of the recording medium 3 is recorded on the recording medium 3 by the pressure. The entire toner image 4 is fixed in the layer 1 without being embedded. FIG. 3 shows the recording medium that has undergone the fixing process.

The image forming method according to the present embodiment further includes a covering step of covering at least a part of the toner image fixed on the recording layer of the recording medium with a peelable image information hiding layer, and the image information hiding layer, Adhering to the recording layer of the recording medium by pressure.
The image information hiding layer hides at least a part of the toner image.
When the image forming method according to the present embodiment includes the covering step and the adhering step, it is possible to provide an image forming method capable of producing an image recorded matter having excellent peelability.

  In the image forming method according to the present embodiment, the fixing step and the bonding step may be performed simultaneously. That is, in a state where the surface of the recording layer of the recording medium to which the toner image is transferred is covered with a peelable image information hiding layer, pressure is applied to the image information hiding layer, and the toner image is applied to the recording layer of the recording medium. The image information concealing layer can be adhered to the recording layer of the recording medium while fixing without embedding the entire structure.

  FIG. 4 is a cross-sectional view showing an example of a recording medium in which a toner image is transferred to the surface of the recording layer of the recording medium and the toner image and the recording layer are covered with an image information concealing layer. A toner image 4 is placed on the surface of the recording layer 1 of the recording medium 3 according to the present embodiment, and the toner image 4 and the recording layer 1 are covered with an image information concealment layer 5. The state before the fixing process and the adhesion process of the image forming method further including the process is shown. When pressure is applied to the image information hiding layer 5, the toner image 4 is not embedded in its entirety but fixed to the recording layer 1, while the image information hiding layer 5 adheres to the recording layer 1. The image recorded matter that has undergone the fixing step and the bonding step takes the state shown in FIG.

  Hereinafter, the present embodiment will be specifically described by way of examples. However, the present embodiment is not limited to these examples. In the following description, “part” and “%” all mean “part by mass” and “mass%” unless otherwise specified.

-Preparation of resin particle dispersion-
<Preparation of resin particle dispersion (A1)>
-Styrene: 300 parts-n-butyl acrylate: 100 parts-Acrylic acid: 8 parts-Dodecanethiol: 3 parts

  A solution in which the above compound was mixed and dissolved was prepared. Nonionic surfactant Nonipol 400 (manufactured by Sanyo Chemical Industries, Ltd.): 3 parts, anionic surfactant Neogen SC (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 5 parts dissolved in ion-exchanged water: 250 parts The above-mentioned dissolved product was dispersed and emulsified in a flask to prepare a monomer emulsion.

  Furthermore, 400 parts of nonipol and 5 parts of neogen SC were dissolved in 300 parts of ion-exchanged water, and nitrogen substitution was performed while slowly mixing for 10 minutes to prepare a surfactant aqueous solution. Thereafter, the aqueous surfactant solution was heated to 75 ° C., and 50% of the monomer emulsion was dropped into the aqueous surfactant solution to prepare a reaction solution.

  Thereafter, 50 parts of ion-exchanged water in which 4 parts of ammonium persulfate was dissolved was added to the reaction solution, and the remaining 50% of the monomer emulsion was added dropwise over 1 hour. Thereafter, the contents in the flask were stirred and kept at 75 ° C. in an oil bath, and emulsion polymerization was continued for 4 hours.

  As a result, an anionic resin particle dispersion (A1) having a center diameter of 200 nm, a glass transition temperature of 54 ° C., a weight average molecular weight Mw of 47,000, and a number average molecular weight of Mn of 12,500 was obtained.

<Preparation of resin particle dispersion (A2)>
Emulsion polymerization was performed under the same conditions as in the preparation of the resin particle dispersion (A1) except that styrene: 100 parts and n-butyl acrylate: 300 parts. As a result, an anionic resin particle dispersion (A2) in which resin particles having a center diameter of 200 nm, a glass transition temperature of 6 ° C., a weight average molecular weight Mw of 39,000, and a number average molecular weight of Mn of 10,500 were dispersed was obtained.

<Preparation of resin particle dispersion (A3)>
Emulsion polymerization was performed under the same conditions as in the preparation of the resin particle dispersion (A1) except that styrene: 320 parts and n-butyl acrylate: 80 parts. As a result, an anionic resin particle dispersion (A3) was obtained in which resin particles having a center diameter of 220 nm, a glass transition temperature of 57 ° C., a weight average molecular weight Mw of 42,000, and a number average molecular weight of Mn of 13,000 were dispersed.

<Preparation of resin particle dispersion (A4)>
Emulsion polymerization was performed under the same conditions as in the preparation of the resin particle dispersion (A1) except that styrene: 30 parts and n-butyl acrylate: 370 parts. As a result, an anionic resin particle dispersion (A4) in which resin particles having a center diameter of 200 nm, a glass transition temperature of −30 ° C., a weight average molecular weight Mw of 32,000 and a number average molecular weight of Mn of 13,000 was dispersed was obtained.

<Preparation of resin particle dispersion (A5)>
Emulsion polymerization was performed under the same conditions as in the preparation of the resin particle dispersion (A1) except that styrene was 200 parts and n-butyl acrylate was 200 parts. As a result, an anionic resin particle dispersion (A5) was obtained in which resin particles having a center diameter of 200 nm, a glass transition temperature of 30 ° C., a weight average molecular weight Mw of 37,000, and a number average molecular weight of Mn of 12,000 were dispersed.

<Preparation of resin particle dispersion (A6)>
Emulsion polymerization was performed under the same conditions as in the preparation of the resin particle dispersion (A1) except that styrene was 350 parts and n-butyl acrylate was 50 parts. As a result, an anionic resin particle dispersion (A6) in which resin particles having a center diameter of 210 nm, a glass transition temperature of 80 ° C., a weight average molecular weight Mw of 36,000, and a number average molecular weight of Mn of 11,500 were dispersed was obtained.

<Preparation of resin particle dispersion (A7)>
Emulsion polymerization was performed under the same conditions as in the preparation of the resin particle dispersion (A1) except that styrene: 50 parts and n-butyl acrylate: 350 parts. As a result, an anionic resin particle dispersion (A7) in which resin particles having a center diameter of 180 nm, a glass transition temperature of −35 ° C., a weight average molecular weight Mw of 32,000 and a number average molecular weight of Mn of 9,000 was dispersed was obtained.

<Preparation of resin particle dispersion (A8)>
Emulsion polymerization was carried out under the same conditions as in the preparation of the resin particle dispersion (A1) except that styrene: 380 parts and n-butyl acrylate: 20 parts. As a result, an anionic resin particle dispersion (A8) was obtained in which resin particles having a center diameter of 200 nm, a glass transition temperature of 90 ° C., a weight average molecular weight Mw of 40,000, and a number average molecular weight of Mn of 13,500 were dispersed.

<Preparation of resin particle dispersion (B1)>
In a round glass flask, 300 parts of ion-exchanged water and 1.5 parts of TTAB (tetradecyltrimethylammonium bromide, Sigma-Aldrich) were added to prepare an aqueous TTAB solution.

  The prepared TABB aqueous solution was purged with nitrogen for 20 minutes and heated to 65 ° C. with stirring. 40 parts of n-butyl acrylate monomer was added to the TABB aqueous solution and further stirred for 20 minutes. Subsequently, initiator V-50 (2,2′-azobis (2-methylpropionamidine) dihydrochloride, manufactured by Wako Pure Chemical Industries, Ltd.): 0.5 part dissolved in ion-exchanged water: 10 parts The liquid was put into a flask.

  The flask was kept at 65 ° C. for 3 hours. Styrene: 50 parts, n-butyl acrylate: 20 parts, acrylic acid: 2.5 parts and dodecanethiol: 0.8 parts, TTAB: 0.5 parts in ion-exchanged water: 100 parts dissolved in TTAB aqueous solution, Emulsified to prepare an emulsion. The prepared emulsion was continuously charged into the flask using a metering pump over 2 hours. The temperature in the flask was raised to 70 ° C. and held for another 2 hours to complete the polymerization.

  As a result, resin particles having a core (glass transition temperature−50 ° C.) / Shell (glass transition temperature + 50 ° C.) structure having a weight average molecular weight Mw of 22,000, a number average molecular weight Mn of 8,000, a center diameter of 170 nm, and a solid content of 25%. A dispersed resin particle dispersion (B1) was obtained.

<Preparation of resin particle dispersion (C1)>
・ 1,4-Cyclohexanedicarboxylic acid: 175 parts ・ Bisphenol A 1 ethylene oxide adduct (2 mol adduct in terms of both ends): 310 parts ・ Dodecylbenzenesulfonic acid: 0.5 parts And polycondensation was carried out at 100 ° C. for 4 hours under a nitrogen atmosphere to obtain a transparent amorphous resinous compound. The weight average molecular weight obtained by GPC was 5,000, and the glass transition temperature (onset) was 50 ° C.

-Caprolactone: 90 parts-Dodecylbenzenesulfonic acid: 0.2 parts The above compounds were mixed, put into a reaction vessel equipped with a stirrer, and subjected to polycondensation at 90 ° C for 5 hours under a nitrogen atmosphere. A crystalline polyester oligomer was obtained. The weight average molecular weight obtained by GPC was 6,000, the glass transition temperature (onset) was −60 ° C., and the melting temperature was 60 ° C.

  The resulting amorphous resinous compound: 50 parts and the crystalline polyester oligomer: 50 parts were mixed at 100 ° C. and heated in a reaction vessel equipped with a stirrer for 2 hours, thereby producing a block copolymer. A resin was obtained. The glass transition temperature (onset) obtained by DSC as a block copolymer was 45 ° C. Moreover, the weight average molecular weight obtained by GPC was 11,500, and the number average molecular weight was 4,000.

  Soft resin sodium dodecylbenzenesulfonate: 0.5 part is added to 100 parts of this resin as a surfactant, and ion-exchanged water: 300 parts are further added, and heated at 80 ° C. in a round glass flask with a homogenizer ( It was mixed and dispersed with IKA, Ultra Turrax T50). Thereafter, the pH of the system was further adjusted to 5.0 with a 0.5 mol / L sodium hydroxide aqueous solution, and then heated to 90 ° C. while continuing to stir with a homogenizer, and the resin particles had a center diameter of 180 nm and a solid content of 20 % Of a block copolymer polyester resin particle was dispersed to obtain a resin particle dispersion (C1).

<Preparation of resin particle dispersion (C2)>
In the preparation of the resin particle dispersion (C1), the amorphous resinous compound: 50 parts and the crystalline polyester oligomer: 50 parts were changed to the amorphous resinous compound: 30 parts and the crystalline polyester oligomer: 70 parts. Resin was prepared in the same manner as C1, and a resin particle dispersion (C2) having a resin particle central diameter of 180 nm was obtained. The glass transition temperature (onset) obtained by DSC was 35 ° C. The weight average molecular weight obtained by GPC was 11,000, and the number average molecular weight was 3,500.

[Example 1]
<Preparation of aqueous dispersion (1)>
The resin particle dispersion (A1) and the resin particle dispersion (A2) are mixed at a volume ratio of 30:70 (resin particle dispersion (A1): resin particle dispersion (A2)) to obtain a resin composition having a solid content of 42% by mass. An aqueous dispersion of the product was obtained. In this water dispersion, crosslinked polymethyl methacrylate particles (SSX-115, manufactured by Sekisui Plastics Co., Ltd., volume average particle size 15 μm, protrusion-providing particles in an amount of 2.1% by mass with respect to the total solid content. ) And stirred with a three-one motor to obtain an aqueous dispersion (1).

The obtained aqueous dispersion (1) was evaporated to dryness to produce a pellet-shaped sample. Prepared samples the flow tester (Shimadzu Corporation, Shimadzu Flow Tester CFT-500) was set in, the measuring conditions described above, to measure the viscosity of the resin composition to obtain T ₁ and T _10. A temperature difference ΔT (T ₁ −T ₁₀ ) was calculated from the obtained T ₁ and T ₁₀ .

<Preparation of recording medium (1)>
Then, on the label paper (V860) manufactured by Fuji Xerox Co., Ltd. as a base material, the aqueous dispersion (1) is applied and air-dried using a bar coater so that the film thickness after drying becomes 10 μm. Thus, a recording layer was formed. Thereby, a recording medium (1) was obtained.
When the recording medium (1) was cut and the cross section was observed with a scanning electron microscope, it was observed that a large number of protrusions were formed on the surface of the recording layer by the protrusion-providing particles.

[Example 2]
<Preparation of aqueous dispersion (2)>
The resin particle dispersion (A3) and the resin particle dispersion (A4) are mixed at a volume ratio of 30:70 (resin particle dispersion (A3): resin particle dispersion (A4)) to obtain a resin composition having a solid content of 42% by mass. An aqueous dispersion of the product was obtained. To this aqueous dispersion, silicone resin particles (Tospearl 1110, Momentive Performance Materials Co., Ltd., volume average particle diameter 11 μm, protrusion imparting particles) are added in an amount of 4.2 mass% based on the total solid content. The mixture was stirred with a three-one motor to obtain an aqueous dispersion (2).

<Preparation of recording medium (2)>
Then, on the label paper (V860) manufactured by Fuji Xerox Co., Ltd. as the base material, the aqueous dispersion (2) is applied and air-dried using a bar coater so that the film thickness after drying becomes 8 μm. Thus, a recording layer was formed. Thereby, a recording medium (2) was obtained.
When the recording medium (2) was cut and the cross section was observed with a scanning electron microscope, it was observed that a large number of protrusions were formed on the surface of the recording layer by the protrusion-providing particles.

[Example 3]
<Preparation of aqueous dispersion (3)>
The resin particle dispersion (B1) was prepared as an aqueous dispersion of a resin composition having a solid content of 25% by mass. In this aqueous dispersion, crosslinked polymethyl methacrylate particles (SSX-115, manufactured by Sekisui Plastics Co., Ltd., volume average particle size 15 μm, protrusion-providing particles in an amount of 1.2% by mass with respect to the total solid content. ) And stirred with a three-one motor to obtain an aqueous dispersion (3).

<Preparation of recording medium (3)>
Then, on the label paper (V860) manufactured by Fuji Xerox Co., Ltd. as the base material, the aqueous dispersion (3) is applied and air-dried using a bar coater so that the film thickness after drying becomes 10 μm. Thus, a recording layer was formed. Thereby, a recording medium (3) was obtained.
When the recording medium (3) was cut and the cross section was observed with a scanning electron microscope, it was observed that many protrusions were formed on the surface of the recording layer by the protrusion-providing particles.

[Example 4]
<Preparation of aqueous dispersion (4)>
The resin particle dispersion (C1) was prepared as an aqueous dispersion of a resin composition having a solid content of 20% by mass. To this aqueous dispersion, melamine silica composite particles (Optobeads, Nissan Chemical Industries, Ltd., volume average particle diameter 8 μm, protrusion imparting particles) are added in an amount of 2.0% by mass with respect to the total solid content. The mixture was stirred with a motor to obtain an aqueous dispersion (4).

<Preparation of recording medium (4)>
Then, on the label paper (V860) manufactured by Fuji Xerox Co., Ltd. as the base material, the aqueous dispersion (4) is applied and air-dried using a bar coater so that the film thickness after drying becomes 5 μm. Thus, a recording layer was formed. As a result, a recording medium (4) was obtained.
When the recording medium (4) was cut and the cross section was observed with a scanning electron microscope, it was observed that many protrusions were formed on the surface of the recording layer by the protrusion-providing particles.

[Example 5]
<Preparation of aqueous dispersion (5)>
The resin particle dispersion (A6) and the resin particle dispersion (A7) are mixed at a volume ratio of 30:70 (resin particle dispersion (A6): resin particle dispersion (A7)) to obtain a resin composition having a solid content of 42% by mass. An aqueous dispersion (5) of the product was obtained. In this water dispersion, crosslinked polymethyl methacrylate particles (SSX-115, manufactured by Sekisui Plastics Co., Ltd., volume average particle size 15 μm, protrusion-providing particles in an amount of 2.1% by mass with respect to the total solid content. ) And stirred with a three-one motor to obtain an aqueous dispersion (5).

<Preparation of recording medium (5)>
And the recording medium (5) was obtained like Example 1 using the water dispersion (5).
When the recording medium (5) was cut and the cross section was observed with a scanning electron microscope, it was observed that a large number of protrusions were formed on the surface of the recording layer by the protrusion-providing particles.

[Example 6]
<Preparation of aqueous dispersion (6)>
The resin particle dispersion (A3) and the resin particle dispersion (A5) are mixed at a volume ratio of 30:70 (resin particle dispersion (A3): resin particle dispersion (A5)) to obtain a resin composition having a solid content of 42% by mass. An aqueous dispersion of the product was obtained. In this water dispersion, crosslinked polymethyl methacrylate particles (SSX-115, manufactured by Sekisui Plastics Co., Ltd., volume average particle size 15 μm, protrusion-providing particles in an amount of 2.1% by mass with respect to the total solid content. ) And stirred with a three-one motor to obtain an aqueous dispersion (6).

<Preparation of recording medium (6)>
And the recording medium (6) was obtained like Example 1 using the water dispersion (6).
When the recording medium (6) was cut and the cross section was observed with a scanning electron microscope, it was observed that a large number of protrusions were formed on the surface of the recording layer by the protrusion-providing particles.

[Example 7]
<Preparation of aqueous dispersion (7)>
The resin particle dispersion (A5) and the resin particle dispersion (A4) are mixed at a volume ratio of 30:70 (resin particle dispersion (A5): resin particle dispersion (A4)) to obtain a resin composition having a solid content of 42% by mass. An aqueous dispersion of the product was obtained. In this water dispersion, crosslinked polymethyl methacrylate particles (SSX-115, manufactured by Sekisui Plastics Co., Ltd., volume average particle size 15 μm, protrusion-providing particles in an amount of 2.1% by mass with respect to the total solid content. ) And stirred with a three-one motor to obtain an aqueous dispersion (7).

<Preparation of recording medium (7)>
And the recording medium (7) was obtained like Example 1 using the water dispersion (7).
When the recording medium (7) was cut and the cross section was observed with a scanning electron microscope, it was observed that a large number of protrusions were formed on the surface of the recording layer by the protrusion-providing particles.

[Example 8]
<Preparation of aqueous dispersion (8)>
The resin particle dispersion (C2) was prepared as an aqueous dispersion of a resin composition having a solid content of 20% by mass. In this water dispersion, cross-linked polymethyl methacrylate particles (SSX-115, manufactured by Sekisui Plastics Co., Ltd., volume average particle size 15 μm, protrusion-providing particles in an amount of 1.0 mass% with respect to the total solid content. ) And stirred with a three-one motor to obtain an aqueous dispersion (8).

<Preparation of recording medium (8)>
And the recording medium (8) was obtained like Example 1 using the water dispersion (8).
When the recording medium (8) was cut and the cross section was observed with a scanning electron microscope, it was observed that a large number of protrusions were formed on the surface of the recording layer by the protrusion-providing particles.

[Comparative Example 1]
<Preparation of water dispersion (R1)>
A resin particle dispersion (A4) was prepared as an aqueous dispersion (R1) of a resin composition having a solid content of 42% by mass. In this water dispersion, crosslinked polymethyl methacrylate particles (SSX-115, manufactured by Sekisui Plastics Co., Ltd., volume average particle size 15 μm, protrusion-providing particles in an amount of 2.1% by mass with respect to the total solid content. ) And stirred with a three-one motor to obtain an aqueous dispersion (R1).

<Preparation of recording medium (R1)>
Then, a recording medium (R1) was obtained in the same manner as in Example 1 using the aqueous dispersion (R1).
When the recording medium (R1) was cut and the cross section was observed with a scanning electron microscope, it was observed that many protrusions were formed on the surface of the recording layer by the protrusion-providing particles.

[Comparative Example 2]
<Preparation of water dispersion (R2)>
The resin particle dispersion (A3) and the resin particle dispersion (A5) are mixed at a volume ratio of 50:50 (resin particle dispersion (A3): resin particle dispersion (A5)) to obtain a resin composition having a solid content of 42% by mass. An aqueous dispersion of the product was obtained. In this water dispersion, crosslinked polymethyl methacrylate particles (SSX-115, manufactured by Sekisui Plastics Co., Ltd., volume average particle size 15 μm, protrusion-providing particles in an amount of 2.1% by mass with respect to the total solid content. ) And stirred with a three-one motor to obtain an aqueous dispersion (R2).

<Preparation of recording medium (R2)>
Then, a recording medium (R2) was obtained in the same manner as in Example 1 using the aqueous dispersion (R2).
When the recording medium (R2) was cut and the cross section was observed with a scanning electron microscope, it was observed that a large number of protrusions were formed on the surface of the recording layer by the protrusion-providing particles.

[Comparative Example 3]
<Preparation of water dispersion (R3)>
The resin particle dispersion (A8) and the resin particle dispersion (A7) are mixed at a volume ratio of 30:70 (resin particle dispersion (A8): resin particle dispersion (A7)) to obtain a resin composition having a solid content of 42% by mass. An aqueous dispersion of the product was obtained. In this water dispersion, crosslinked polymethyl methacrylate particles (SSX-115, manufactured by Sekisui Plastics Co., Ltd., volume average particle size 15 μm, protrusion-providing particles in an amount of 2.1% by mass with respect to the total solid content. ) And stirred with a three-one motor to obtain an aqueous dispersion (R3).

<Preparation of recording medium (R3)>
Then, using the aqueous dispersion (R3), a recording medium (R3) was obtained in the same manner as in Example 1.
When the recording medium (R3) was cut and the cross section was observed with a scanning electron microscope, it was observed that a large number of protrusions were formed on the surface of the recording layer by the protrusion-providing particles.

[Comparative Example 4]
<Preparation of water dispersion (R4)>
The resin particle dispersion (A1) and the resin particle dispersion (A2) are mixed at a volume ratio of 30:70 (resin particle dispersion (A1): resin particle dispersion (A2)), and crosslinked polymethyl methacrylate particles are added. The aqueous dispersion (R4) of the resin composition having a solid content of 42% by mass was obtained.

<Preparation of recording medium (R4)>
Then, a recording medium (R4) was obtained in the same manner as in Example 1 using the aqueous dispersion (R4).
When the recording medium (R5) was cut and the cross section was observed with a scanning electron microscope, it was observed that the surface of the recording layer had no protrusions and was flat.

[Example 9]
<Preparation of aqueous dispersion (9)>
The resin particle dispersion (A1) and the resin particle dispersion (A2) are mixed at a volume ratio of 30:70 (resin particle dispersion (A1): resin particle dispersion (A2)) to obtain a resin composition having a solid content of 42% by mass. An aqueous dispersion of the product was obtained. In this water dispersion, crosslinked polymethyl methacrylate particles (SSX-115, manufactured by Sekisui Plastics Co., Ltd., volume average particle size 15 μm, protrusion-providing particles in an amount of 2.1% by mass with respect to the total solid content. ) And stirred with a three-one motor to obtain an aqueous dispersion (9).

<Preparation of recording medium (9)>
Then, on the label paper (V860) manufactured by Fuji Xerox Co., Ltd. as the base material, the aqueous dispersion (9) is applied and air-dried using a bar coater so that the film thickness after drying becomes 20 μm. Thus, a recording layer was formed. As a result, a recording medium (9) was obtained.
When the recording medium (9) was cut and the cross section was observed with a scanning electron microscope, it was observed that some protrusions were formed on the surface of the recording layer.

Here, with respect to the aqueous dispersions (2) to (9) and the aqueous dispersions (R1) to (R4), similarly to the aqueous dispersion (1) of Example 1, the temperature difference ΔT (T ₁ −T ₁₀ ) was calculated. And the following evaluation was performed about Examples 1-9 and Comparative Examples 1-4.

[Evaluation]
<Evaluation of fixability and continuous running>
A character image is fixed by applying pressure to the recording medium obtained in each example by using an electrophotographic image forming apparatus using toner, and a character image is obtained by fixing at room temperature (in-machine temperature of the image forming apparatus is 50 ° C.). Collected. The image forming apparatus used is a modified version of DocuPrint 4050 (printing speed A4 44 sheets / min) manufactured by Fuji Xerox Co., Ltd. Character images are fixed in a high-temperature, high-humidity environment (temperature 28 ° C., humidity 80 RH%) with 500 recording media stacked in the apparatus overnight and seasoned overnight. Was performed under conditions adjusted to 0.5 MPa.

The surface of the collected character image was strongly rubbed with Kimwipe (registered trademark) (manufactured by Nippon Paper Crecia Co., Ltd.). Fixability was evaluated by visually observing the strongly rubbed character image and the Kimwipe used.
The evaluation criteria are as follows. A fixing grade of G3 or higher was regarded as an acceptable level for actual use.
-Fixing grade-
G5: No image loss and no toner transfer to the Kimwipe side.
G4: Although there is a slight image defect, there is no effect on actual use. There is a slight transition to the Kimwipe side.
G3: There is an image defect portion, and there is a shift to the Kimwipe side.
G2: Even if there is an image defect, it can be read. Large amount of migration to the Kimwipe side.
G1: Image disappeared, unreadable, almost all moved to Kimwipe side.

On the other hand, under the same conditions as in the evaluation of the fixability, 500 character images were continuously output on A4 paper. This continuous output was evaluated according to the following criteria.
-Evaluation criteria for continuous running-
G +: 500 sheets were output without any double feeding of the recording medium and no paper jam. G: Up to 300 sheets of printing were output without double feeding of the recording medium and no paper jam. N: With 100 sheets output, double feeding of recording media occurred even once or paper jam occurred

<Evaluation of peelability>
A recording medium produced in the same manner as in the evaluation of fixability was prepared. A character image was transferred to this recording medium using Fuji Xerox MONO 200b. Using Fuji Xerox MONO 200b, a solid toner image was thermally fixed on both sides of Fuji Xerox C2 paper to produce a black paper for coating. The covering black paper was superimposed on the image surface of the recording medium onto which the character image was transferred. The recording medium on which the black paper for covering is overlapped is passed through the fixing device of the image forming apparatus used in the evaluation of fixing properties, and the black paper for covering is adhered to the surface of the character image while fixing the character image by pressure. An image recorded matter was prepared by fixing (the internal temperature of the image forming apparatus was 50 ° C.). The fixing of the character image and the adhesion of the covering black paper were carried out under the conditions that the fixing machine was not heated and the maximum pressure was adjusted to 0.5 MPa.

About the produced image recorded matter, the covering black paper is peeled off from the image recorded matter, and the peelability is determined by the peeling force and the clearness (visual confirmation) of the character image concealed by the covering black paper. evaluated.
The evaluation criteria are as follows. Grade G3 or higher was regarded as an acceptable level for actual use.
Grade G5: It can be peeled off with an appropriate peeling force by hand, and no defect is observed in both the image and the recording medium.
G4: It can be peeled off with an appropriate peeling force by hand, and although there is slight peeling on the recording medium, there is no effect on the image.
G3: The film can be peeled off with an appropriate peeling force by hand, but the recording medium or image is slightly peeled or chipped.
G2: Peeling force by hand is slightly large, and the recording medium and image are peeled off or missing.
G1: The peel strength is large by hand, and the recording medium and the image are markedly peeled or missing.

<Structure of resin composition>
It was confirmed by the above method whether the recording layer of the recording medium had a core / shell structure or a sea-island structure.

Tables 1 and 2 list the evaluation results together with the characteristics of the resin composition. In Table 1, “(whole)” indicates physical properties of the whole polymer, not physical properties of each part in the polymer. In Table 2, “---” indicates that evaluation could not be performed. In Table 2, “ΔT” represents a difference (T ₁ −T ₁₀ ) between T ₁ and T ₁₀ . “ΔTg” represents a difference in glass transition temperature.

In Comparative Example 1, the recording media were stuck together in the image forming apparatus, and it was not possible to produce a recording medium for evaluation and an image recorded matter.
From the results shown in Table 2, it can be seen that in this example, good results were obtained in each evaluation of fixability and peelability. In addition, in this example, good results were also obtained for continuous running performance, and it can be seen that double feeding of the recording medium is suppressed even in a high temperature and high humidity environment.

DESCRIPTION OF SYMBOLS 1 Recording layer 2 Base material 3 Recording medium 4 Toner image 5 Image information concealment layer 6 Image recorded matter

Claims (8)

Wherein the resin, and the volume average particle size of the 50μm smaller particles than 1 [mu] m, meet the following equation (1),
The resin includes at least two kinds of resins having different glass transition temperatures,
Of the two types of resins, the temperature having the higher glass transition temperature is 40 ° C. or more and less than 60 ° C., and the temperature having the lower glass transition temperature is −100 ° C. or more and less than 10 ° C.,
A resin composition for forming a recording layer of a recording medium.
Equation _{(1) 20 ℃ ≦ T 1} -T 10 ≦ 120 ℃
In the formula (1), T ₁ represents a temperature at which the viscosity becomes 10 ⁴ Pa · s at an applied pressure of 1 MPa, which is measured using a flow tester after preparing a solid sample of the resin from the resin composition. . T ₁₀ represents a temperature at which the viscosity becomes 10 ⁴ Pa · s at an applied pressure of 10 MPa, which was measured by using a flow tester by preparing a solid sample of the resin from the resin composition. 2. The resin composition for forming a recording layer of a recording medium according to claim 1 , wherein the two kinds of resins have glass transition temperatures different by 30 ° C. or more. Wherein at least one of the two resins, the recording layer forming resin composition of the recording medium according to claim 1 or claim 2 having a glass transition temperature of 40 ° C. or higher. A substrate;
A recording layer formed on the substrate using the resin composition for forming a recording layer of a recording medium according to any one of claims 1 to 3 ,
A recording medium. The recording medium according to claim 4 , wherein a volume average particle diameter of the particles is larger than a thickness of the recording layer. A recording medium according to claim 4 or claim 5 ,
A toner image formed using an electrostatic charge image developing toner on the recording layer of the recording medium and fixed without being embedded in its entirety;
A peelable image information hiding layer that covers at least a portion of the toner image;
Recorded images in order. A charging step for charging the surface of the image carrier;
An electrostatic charge image forming step of forming an electrostatic charge image on the surface of the charged image carrier;
A developing step of developing an electrostatic image formed on the surface of the image carrier as a toner image with an electrostatic image developer containing an electrostatic image developing toner;
A transfer step of transferring to the surface of the recording layer of the recording medium according to the toner image formed on the surface of the image carrier to claim 4 or claim 5,
A fixing step of fixing the toner image transferred to the surface of the recording layer of the recording medium to the recording layer of the recording medium by pressure without embedding the entire toner image;
An image forming method comprising: Further, a covering step of covering at least a part of the toner image fixed on the recording layer of the recording medium with a peelable image information hiding layer;
An adhesion step of adhering the image information hiding layer to the recording layer of the recording medium by pressure;
The image forming method according to claim 7 .