CN112239581A - Pressure-responsive particle and method for producing printed matter - Google Patents
Pressure-responsive particle and method for producing printed matter Download PDFInfo
- Publication number
- CN112239581A CN112239581A CN202010695575.5A CN202010695575A CN112239581A CN 112239581 A CN112239581 A CN 112239581A CN 202010695575 A CN202010695575 A CN 202010695575A CN 112239581 A CN112239581 A CN 112239581A
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- CN
- China
- Prior art keywords
- pressure
- responsive
- particles
- meth
- acrylate
- Prior art date
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/14—Copolymers of styrene with unsaturated esters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B31—MAKING ARTICLES OF PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER; WORKING PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER
- B31D—MAKING ARTICLES OF PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER, NOT PROVIDED FOR IN SUBCLASSES B31B OR B31C
- B31D1/00—Multiple-step processes for making flat articles ; Making flat articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B31—MAKING ARTICLES OF PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER; WORKING PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER
- B31F—MECHANICAL WORKING OR DEFORMATION OF PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER
- B31F1/00—Mechanical deformation without removing material, e.g. in combination with laminating
- B31F1/0003—Shaping by bending, folding, twisting, straightening, flattening or rim-rolling; Shaping by bending, folding or rim-rolling combined with joining; Apparatus therefor
- B31F1/0045—Bending or folding combined with joining
- B31F1/0048—Bending plates, sheets or webs at right angles to the axis of the article being formed and joining the edges
- B31F1/0051—Bending plates, sheets or webs at right angles to the axis of the article being formed and joining the edges for making articles of definite lentgh
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B37/1284—Application of adhesive
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
- B42C—BOOKBINDING
- B42C9/00—Applying glue or adhesive peculiar to bookbinding
- B42C9/0081—Applying glue or adhesive peculiar to bookbinding applying adhesive to individual sheets for binding them together
- B42C9/0087—Applying glue or adhesive peculiar to bookbinding applying adhesive to individual sheets for binding them together sheet shingling devices
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- Developing Agents For Electrophotography (AREA)
Abstract
The present invention relates to a pressure-responsive particle and a method for producing a printed matter. The pressure-responsive particles contain a styrene resin and a (meth) acrylate resin, the (meth) acrylate resin contains 2 kinds of (meth) acrylates as polymerization components, the mass ratio of the (meth) acrylates in the entire polymerization components is 90 mass% or more, the pressure-responsive particles have 2 glass transition points, and the difference between the lowest glass transition temperature and the highest glass transition temperature is 30 ℃ or more.
Description
Technical Field
The present invention relates to a pressure-responsive particle and a method for producing a printed matter.
Background
Patent document 1 describes an aqueous dispersion type pressure-sensitive adhesive composition containing two kinds of acrylic polymers in an aqueous solvent.
Patent document 2 describes a bonding material satisfying the expression "20 ℃ C. or less T (1MPa) -T (10 MPa)" (T (1MPa) indicates that the viscosity reaches 10 under an applied pressure of 1MPa4pa · s, T (10MPa) means that the viscosity reaches 10 under an applied pressure of 10MPa4Temperature at pa · s).
Patent document 3 describes a pressure fixing toner having a core portion and a shell layer, the core portion including a styrene resin and a (meth) acrylate resin having a glass transition temperature lower by 30 ℃ or more than that of the styrene resin, and having a sea-island structure composed of a sea portion including the styrene resin and island portions including the (meth) acrylate resin, the island portions having a major diameter of 200nm to 500 nm; the shell layer covers the core portion and contains a resin having a glass transition temperature of 50 ℃ or higher.
Patent document 4 describes an aqueous dispersion type pressure-sensitive adhesive composition containing an acrylic polymer (a) as a polymer of a monomer raw material (a) and an acrylic polymer (B) as a polymer of a monomer raw material (B), wherein the acrylic polymer (B) has a glass transition temperature of 0 ℃ or higher, and the acrylic polymer (B) has a weight average molecular weight of more than 0.3 × 104And is 5X 104Hereinafter, the weight average molecular weight of the acrylic polymer (A) is 40X 104The difference between the glass transition temperature of the acrylic polymer (B) and the glass transition temperature of the acrylic polymer (A) is 70 ℃ or more, and the monomer raw material (B) contains a carboxyl group-containing monomer in a proportion of 3 to 20 wt%.
Patent document 5 describes a pressure-contact postcard sheet in which the adhesive layer contains an acrylic acid-alkyl methacrylate copolymer.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2012-188512
Patent document 2: japanese laid-open patent publication No. 2018-002889
Patent document 3: japanese patent laid-open publication No. 2018-163198
Patent document 4: japanese patent No. 6468727
Patent document 5: japanese patent laid-open No. 2007-229993
Disclosure of Invention
Technical problem to be solved by the invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide a pressure-responsive particle comprising a styrene resin and a (meth) acrylate resin, which is easily phase-changed by pressure and has excellent adhesiveness, as compared to a pressure-responsive particle in which the (meth) acrylate resin is a homopolymer of a (meth) acrylate.
Means for solving the problems
Specific means for solving the above technical problems include the following means.
<1> a pressure-responsive particle, wherein,
the pressure-responsive particles contain a styrene-based resin and a (meth) acrylate resin,
the (meth) acrylate resin contains 2 kinds of (meth) acrylates as polymerization components, and the mass ratio of the (meth) acrylate to the total polymerization components is 90 mass% or more, and
the pressure-responsive particles have 2 glass transition points, and the difference between the lowest glass transition temperature and the highest glass transition temperature is 30 ℃ or more.
<2> the pressure-responsive particles as stated in <1>, wherein the mass ratio of styrene in the entire polymerization components of the styrene-based resin is in the range of 60 to 95 mass%.
<3> <1> wherein the mass ratio of the 2 kinds of (meth) acrylic esters contained as a polymerization component in the (meth) acrylic ester resin is in the range of 80:20 to 20: 80.
<4> the pressure-responsive particles as described in <1>, wherein the difference in the number of carbon atoms of the alkyl groups of the 2 kinds of (meth) acrylates contained as the polymerization component in the (meth) acrylate resin is in the range of 1 to 4.
<5> the pressure-responsive particle as stated in <1>, wherein the styrene-based resin further contains a (meth) acrylate as a polymerization component.
<6> the pressure-responsive particles as stated in <5>, wherein the (meth) acrylic acid ester contained as a polymerization component in the styrene-based resin is selected from n-butyl acrylate and 2-ethylhexyl acrylate.
<7> the pressure-responsive particle as stated in <5>, wherein the styrene-based resin and the (meth) acrylate resin contain the same (meth) acrylate as a polymerization component.
<8> the pressure-responsive particles as described in <1>, wherein the above-mentioned (meth) acrylate resin contains 2-ethylhexyl acrylate and n-butyl acrylate as polymerization components.
<9> the pressure-responsive particle as stated in <1>, wherein the content of the styrene resin is larger than the content of the (meth) acrylate resin.
<10> the pressure-responsive particle as stated in <1>, which contains:
a sea phase comprising the above-mentioned styrenic resin, and
an island phase comprising the above (meth) acrylate resin dispersed in the above sea phase.
<11> the pressure-responsive particle as stated in <10>, wherein the average diameter of said island phase is in the range of 200nm to 500 nm.
<12> the pressure-responsive particle as stated in <1>, which comprises a core portion comprising the styrene resin and the (meth) acrylate resin, and a shell layer covering the core portion.
<13> the pressure-responsive particle as stated in <12>, wherein the shell layer contains the styrene resin.
<14> the pressure-responsive particle as stated in <1>, which exhibits a viscosity of 10000Pa · s at a pressure of 4MPa at a temperature of 90 ℃ or less.
<15> the pressure-responsive particle as described in any one of <1> to <14>, which contains a silica particle or a titanium oxide particle having an average primary particle diameter of 1nm or more and 300nm or less as an external additive.
<16> the pressure-responsive particles as stated in <15>, wherein the titanium oxide particles have an average primary particle diameter of 10nm or more and 100nm or less.
<17> the pressure-responsive particles as stated in <15>, wherein an amount of the silica particles added externally is in a range of 1 to 3 parts by mass with respect to 100 parts by mass of the pressure-responsive mother particles contained in the pressure-responsive particles.
<18> the pressure-responsive particle as stated in <15>, wherein a content of the titanium oxide particle is in a range of 0.5 parts by mass to 5 parts by mass with respect to 100 parts by mass of the pressure-responsive mother particle contained in the pressure-responsive particle.
<19> a method for producing a printed matter, comprising the steps of:
an arrangement step of arranging the pressure-responsive particles on a recording medium using the pressure-responsive particles according to any one of <1> to <14 >; and
and a pressure bonding step of folding and pressure bonding the recording medium or overlapping the recording medium with another recording medium and pressure bonding the recording medium.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the aspect of <1>, there can be provided the pressure-responsive particle comprising a styrene-based resin and a (meth) acrylate-based resin, which is more likely to undergo a phase change due to pressure and has excellent adhesiveness than a pressure-responsive particle in which the (meth) acrylate-based resin is a homopolymer of a (meth) acrylate.
According to the aspect of <2>, there can be provided the pressure-responsive particles which are more likely to undergo phase transition by pressure than in the case where the mass ratio of styrene in the entire polymerization components of the styrene-based resin is more than 95 mass%.
According to the aspect of <3>, there can be provided the pressure-responsive particles which are more likely to undergo phase change by pressure and are excellent in adhesiveness, as compared with the case where the mass ratio of the 2 (meth) acrylates having the largest mass ratio among the at least 2 (meth) acrylates contained as the polymerization components in the (meth) acrylate-based resin is out of the range of 80:20 to 20: 80.
According to the aspect of <4>, there can be provided the pressure-responsive particles of <4> which are more likely to undergo a phase change by pressure and are excellent in adhesion, as compared with the case where the difference in the number of carbon atoms of the alkyl groups of the 2 kinds of alkyl (meth) acrylates is 5 or more.
According to the aspect <5>, <6> or <7>, there can be provided a pressure-responsive particle which is susceptible to a phase change by pressure as compared with a pressure-responsive particle comprising polystyrene instead of a styrenic resin.
According to the aspect of <8>, there can be provided the pressure-responsive particle of <8> which is superior in adhesiveness to a pressure-responsive particle comprising a styrene-based resin and a (meth) acrylate-based resin, wherein the (meth) acrylate-based resin is a homopolymer of 2-ethylhexyl acrylate.
According to the aspect of <9>, the pressure-responsive particles can maintain adhesiveness as compared with the case where the content of the styrene-based resin is smaller than the content of the (meth) acrylate-based resin.
According to the aspect of <10>, there can be provided a pressure-responsive particle which is more likely to undergo a phase change by pressure and has excellent adhesiveness than a case where the sea-island structure is not provided.
According to the aspect of <11>, there can be provided the pressure-responsive particles which are susceptible to phase transition by pressure as compared with the case where the average diameter of the island phase is larger than 500 nm.
According to the aspect of <12>, there can be provided a pressure-responsive particle in which a phase change is more likely to occur due to pressure than in the case of a core/shell structure in which only a styrene-based resin or only a (meth) acrylate-based resin is contained in a core portion.
According to the aspect of <13>, there can be provided a pressure-responsive particle which is more likely to undergo a phase change by pressure than a case where a shell layer does not contain a styrene-based resin but contains other resins.
According to the aspect <14>, there can be provided a pressure-responsive particle which is easily subjected to a phase change by pressure as compared with the case where the temperature showing a viscosity of 10000Pa · s at a pressure of 4MPa is more than 90 ℃.
According to the aspect of <15>, there is provided a pressure-responsive particle having more excellent adhesiveness than the case where the pressure-responsive particle of <1> contains an external additive having an average particle diameter of more than 300nm or does not contain titanium oxide particles.
According to the aspect <16>, there is provided a pressure-responsive particle having more excellent adhesiveness than the case where the average particle diameter of the titanium oxide particle is larger than 100 nm.
According to the aspect of <17>, there is provided a pressure-responsive particle having more excellent interlayer releasability than the case where the amount of silica particles added is less than 1% by mass or more than 3% by mass based on the total mass of the pressure-responsive mother particles.
According to the aspect of <18>, there is provided a pressure-responsive particle having more excellent adhesiveness than when the content of the titanium oxide particle is less than 0.5 parts by mass or more than 5 parts by mass with respect to 100 parts by mass of the pressure-responsive mother particle.
According to the aspect of <19>, there can be provided a method for producing a printed matter, in which pressure-responsive particles are used, the pressure-responsive particles used in the method being more likely to undergo a phase change due to pressure and having superior adhesion, as compared with pressure-responsive particles containing a styrene-based resin and a (meth) acrylate-based resin, the (meth) acrylate-based resin being a homopolymer of a (meth) acrylate.
Drawings
Fig. 1 is a schematic diagram showing an example of a printed matter manufacturing apparatus according to the present embodiment.
Fig. 2 is a schematic diagram showing another example of the printed matter manufacturing apparatus according to the present embodiment.
Fig. 3 is a schematic diagram showing still another example of the printed matter manufacturing apparatus according to the present embodiment.
Detailed Description
Embodiments of the present invention will be described below. The description and examples are intended to illustrate embodiments and are not intended to limit the scope of the embodiments.
The numerical ranges expressed by the term "to" in the present invention mean ranges including the numerical values described before and after the term "to" as the minimum value and the maximum value, respectively.
In the numerical ranges recited in the present invention, the upper limit or the lower limit recited in one numerical range may be replaced with the upper limit or the lower limit recited in the other numerical range. In addition, in the numerical ranges recited in the present invention, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the embodiments.
The term "step" in the present invention includes not only an independent step but also a step that can achieve the intended purpose of the step even when it cannot be clearly distinguished from other steps.
In the case of describing the embodiment of the present invention with reference to the drawings, the configuration of the embodiment is not limited to the configuration shown in the drawings. The sizes of the components in the drawings are schematic, and the relative relationship between the sizes of the components is not limited to this.
Each component in the present invention may contain two or more corresponding substances. In the case where the amount of each component in the composition in the present invention is referred to, in the case where two or more substances corresponding to each component are present in the composition, the total amount of the two or more substances present in the composition is referred to unless otherwise specified.
The particles corresponding to the respective components in the present invention may contain two or more kinds. When two or more kinds of particles corresponding to each component are present in the composition, the particle diameter of each component refers to a value for a mixture of the two or more kinds of particles present in the composition unless otherwise specified.
The term "(meth) acrylic acid" in the present invention means that it may be either of "acrylic acid" and "methacrylic acid".
In the present invention, the "toner for electrostatic image development" is also simply referred to as "toner", and the "electrostatic image developer" is also simply referred to as "developer".
In the present invention, a printed matter formed by folding a recording medium and joining opposing surfaces or a printed matter formed by overlapping 2 or more types of recording media and joining opposing surfaces is referred to as a "pressure-printed matter".
< pressure-responsive particles >
The pressure-responsive particle of the present embodiment includes:
styrenic resins comprising styrene and other vinyl monomers in the polymerization components; and
a (meth) acrylate resin containing at least 2 kinds of (meth) acrylates in a polymerization component, wherein the mass ratio of the (meth) acrylates to the total polymerization component is 90 mass% or more,
the pressure-responsive particles have at least 2 glass transition temperatures, and the difference between the lowest glass transition temperature and the highest glass transition temperature is 30 ℃ or more.
The pressure-responsive particles of the present embodiment undergo a phase change due to pressure by exhibiting thermal characteristics of "having at least 2 glass transition temperatures, and having a difference between the lowest glass transition temperature and the highest glass transition temperature of 30 ℃ or more". In the present invention, the pressure-responsive particles that undergo a phase change by pressure are pressure-responsive particles that satisfy the following formula 1.
Formula 1. T1-T2 at 10 ℃ -
In the formula 1, T1 is a temperature showing a viscosity of 10000 pas at a pressure of 1MPa, and T2 is a temperature showing a viscosity of 10000 pas at a pressure of 10 MPa. The method for obtaining the temperature T1 and the temperature T2 is described below.
The pressure-responsive particles of the present embodiment are easily changed in phase by pressure and are excellent in adhesiveness by including "a styrene-based resin containing styrene and other vinyl monomers in polymerization components" and a "(meth) acrylate-based resin containing at least 2 kinds of (meth) acrylates in the polymerization components, the mass ratio of the (meth) acrylates in the entire polymerization components being 90 mass% or more". The mechanism is presumed as follows.
In general, since the styrene-based resin and the (meth) acrylate-based resin have low compatibility with each other, it is considered that both resins are contained in the pressure-responsive mother particle in a phase-separated state. When the pressure-responsive mother particles are pressurized, the (meth) acrylate-based resin having a relatively low glass transition temperature first flows, and this flow affects the styrene-based resin, so that both resins flow. Further, it is considered that when the two resins in the pressure-responsive mother particle are fluidized by pressurization and then cured by depressurization to form a resin layer, a phase separation state is formed again because of low compatibility.
In the (meth) acrylate-based resin containing at least 2 kinds of (meth) acrylates in the polymerization component, since the kind of the ester group bonded to the main chain is at least two, the degree of arrangement of molecules in a solid state is low as compared with a homopolymer of (meth) acrylate, and thus the resin is likely to flow under pressure. It is also presumed that when the mass ratio of the (meth) acrylic ester in the entire polymerization components is 90 mass% or more, the degree of molecular alignment in the solid state is further lowered due to the presence of at least two kinds of ester groups at a high density, and thus the flow under pressure is more likely to occur. Therefore, it is presumed that the pressure-responsive particles of the present embodiment are more likely to flow by pressure, i.e., to change phase by pressure, than the pressure-responsive particles in which the (meth) acrylate-based resin is a homopolymer of (meth) acrylate.
Further, it is presumed that, in the (meth) acrylate-based resin containing at least 2 kinds of (meth) acrylates in the polymerization component and having a mass ratio of the (meth) acrylates to the total polymerization component of 90 mass% or more, the phase separation from the styrene-based resin is a minute phase separation because the degree of molecular arrangement is also low when the curing is performed again. It is presumed that the more minute the phase separation state between the styrene resin and the (meth) acrylate resin, the higher the state uniformity of the joint surface with respect to the object to be joined, and the excellent adhesiveness. Therefore, it is presumed that the pressure-responsive particles of the present embodiment are more excellent in adhesiveness than the pressure-responsive particles in which the (meth) acrylate-based resin is a homopolymer of (meth) acrylate.
The components, structures, and characteristics of the pressure-responsive particles of the present embodiment are described in detail below. In the following description, unless otherwise specified, "styrene-based resin" means "styrene-based resin containing styrene and other vinyl monomers in the polymerization component", and "(meth) acrylate-based resin" means "(meth) acrylate-based resin containing at least 2 kinds of (meth) acrylate esters in the polymerization component, wherein the mass ratio of the (meth) acrylate esters to the total polymerization component is 90 mass% or more".
The pressure-responsive particles of the present embodiment contain at least a pressure-responsive mother particle and, if necessary, an external additive.
[ pressure-responsive mother particle ]
The pressure-responsive mother particle contains at least a styrene-based resin and a (meth) acrylate-based resin. The pressure-responsive master particles may also contain colorants, release agents, other additives.
In the pressure-responsive master batch, it is preferable that the styrene resin content is larger than the (meth) acrylate resin content in view of maintaining the adhesiveness. The content of the styrene resin is preferably 55 to 80 mass%, more preferably 60 to 75 mass%, and still more preferably 65 to 70 mass% with respect to the total content of the styrene resin and the (meth) acrylate resin.
Styrene resin-
The pressure-responsive mother particle constituting the pressure-responsive particle of the present embodiment contains a styrene-based resin containing styrene and other vinyl monomers in polymerization components.
The mass ratio of styrene in the total polymerization components of the styrene-based resin is preferably 60 mass% or more, more preferably 70 mass% or more, and even more preferably 75 mass% or more, from the viewpoint of suppressing fluidization of the pressure-responsive particles in a non-pressurized state; from the viewpoint of forming the pressure-responsive particles that are likely to undergo a phase change by pressure, the ratio is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less.
Examples of the other vinyl monomer other than styrene constituting the styrene-based resin include styrene-based monomers other than styrene and acrylic monomers.
Examples of the styrenic monomer other than styrene include: vinyl naphthalene; alkyl-substituted styrenes such as α -methylstyrene, o-methylstyrene, m-methylstyrene, p-ethylstyrene, 2, 4-dimethylstyrene, p-n-butylstyrene, p-t-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, and p-n-dodecylstyrene; aryl-substituted styrenes such as p-phenylstyrene; alkoxy-substituted styrenes such as p-methoxystyrene; halogen-substituted styrenes such as p-chlorostyrene, 3, 4-dichlorostyrene, p-fluorostyrene, 2, 5-difluorostyrene, and the like; nitro-substituted styrenes such as m-nitrostyrene, o-nitrostyrene, and p-nitrostyrene; and so on. The styrene monomer may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
As the acrylic monomer, at least one acrylic monomer selected from the group consisting of (meth) acrylic acid and (meth) acrylic acid esters is preferable. Examples of the (meth) acrylate include alkyl (meth) acrylate, carboxyl-substituted alkyl (meth) acrylate, hydroxyl-substituted alkyl (meth) acrylate, alkoxy-substituted alkyl (meth) acrylate, and di (meth) acrylate. The acrylic monomer may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate, and isobornyl (meth) acrylate.
Examples of the carboxy-substituted alkyl (meth) acrylate include 2-carboxyethyl (meth) acrylate and the like.
Examples of the hydroxy-substituted alkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
Examples of the alkoxy-substituted alkyl (meth) acrylate include 2-methoxyethyl (meth) acrylate and the like.
Examples of the di (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, pentanediol di (meth) acrylate, hexanediol di (meth) acrylate, nonanediol di (meth) acrylate, and decanediol di (meth) acrylate.
Examples of the (meth) acrylate include 2- (diethylamino) ethyl (meth) acrylate, benzyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, and the like.
Examples of the other vinyl monomers constituting the styrene-based resin include, in addition to styrene-based monomers and acrylic monomers: (meth) acrylonitrile; vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl ketone, vinyl ethyl ketone, and vinyl isopropenyl ketone; olefins such as isoprene, butylene, and butadiene.
In the styrene-based resin, from the viewpoint of forming pressure-responsive particles that are likely to undergo a phase change due to pressure, the polymerization component preferably contains a (meth) acrylate, more preferably contains an alkyl (meth) acrylate, still more preferably contains an alkyl (meth) acrylate having an alkyl group with a carbon number of 2 to 10, still more preferably contains an alkyl (meth) acrylate having an alkyl group with a carbon number of 4 to 8, and particularly preferably contains at least one of n-butyl acrylate and 2-ethylhexyl acrylate. The styrene-based resin and the (meth) acrylate-based resin preferably contain the same kind of (meth) acrylate as a polymerization component, from the viewpoint of forming the pressure-responsive particles which are likely to undergo a phase change due to pressure.
The mass ratio of the (meth) acrylate in the total polymerization components of the styrene-based resin is preferably 40 mass% or less, more preferably 30 mass% or less, and still more preferably 25 mass% or less, from the viewpoint of suppressing fluidization of the pressure-responsive particles in an unpressurized state, and is preferably 5 mass% or more, more preferably 10 mass% or more, and still more preferably 15 mass% or more, from the viewpoint of forming the pressure-responsive particles that are likely to undergo a phase change due to pressure. The (meth) acrylic acid ester herein is preferably an alkyl (meth) acrylate, more preferably an alkyl (meth) acrylate in which the alkyl group has 2 to 10 carbon atoms, and still more preferably an alkyl (meth) acrylate in which the alkyl group has 4 to 8 carbon atoms.
The styrene-based resin particularly preferably contains at least one of n-butyl acrylate and 2-ethylhexyl acrylate as a polymerization component, and the mass ratio of the total amount of n-butyl acrylate and 2-ethylhexyl acrylate in the total polymerization component of the styrene-based resin is preferably 40 mass% or less, more preferably 30 mass% or less, and even more preferably 25 mass% or less, from the viewpoint of suppressing fluidization of the pressure-responsive particles in an unpressurized state, and is preferably 5 mass% or more, more preferably 10 mass% or more, and even more preferably 15 mass% or more, from the viewpoint of forming the pressure-responsive particles which are likely to undergo a phase change due to pressure.
The weight average molecular weight of the styrene resin is preferably 3000 or more, more preferably 4000 or more, and further preferably 5000 or more from the viewpoint of suppressing fluidization of the pressure-responsive particles in an unpressurized state, and is preferably 60000 or less, more preferably 55000 or less, and further preferably 50000 or less from the viewpoint of forming pressure-responsive particles that are likely to undergo a phase change due to pressure.
In the present invention, the weight average molecular weight of the resin is measured by Gel Permeation Chromatography (GPC). In the molecular weight measurement by GPC, HLC-8120GPC manufactured by Toso, TSKgel SuperHM-M (15cm) manufactured by Toso, was used as a GPC apparatus, and tetrahydrofuran was used as a solvent. The weight average molecular weight of the resin was calculated using a molecular weight calibration curve prepared using a monodisperse polystyrene standard sample.
The glass transition temperature of the styrene resin is preferably 30 ℃ or higher, more preferably 40 ℃ or higher, and still more preferably 50 ℃ or higher, from the viewpoint of suppressing fluidization of the pressure-responsive particles in an unpressurized state, and is preferably 110 ℃ or lower, more preferably 100 ℃ or lower, and still more preferably 90 ℃ or lower, from the viewpoint of forming pressure-responsive particles that are likely to undergo a phase change by pressure.
In the present invention, the glass transition temperature of the resin is determined from a Differential Scanning Calorimetry curve (DSC curve) obtained by Differential Scanning Calorimetry (DSC). More specifically, according to JIS K7121: 1987 "method for measuring transition temperature of Plastic", the "extrapolated glass transition onset temperature" described in the method for measuring glass transition temperature.
The glass transition temperature of the resin can be controlled by the kind of the polymerization component and the polymerization ratio. The glass transition temperature has the following tendency: the higher the density of soft units such as methylene, ethylene, and ethylene oxide contained in the main chain is, the more the glass transition temperature tends to decrease; the higher the density of rigid units such as aromatic rings and cyclohexane rings contained in the main chain, the higher the glass transition temperature tends to be. In addition, the higher the density of the aliphatic group of the side chain, the more the glass transition temperature tends to decrease.
The mass ratio of the styrene resin in the present embodiment to the whole pressure-responsive mother particles is preferably 55 mass% or more, more preferably 60 mass% or more, and even more preferably 65 mass% or more in terms of suppressing fluidization of the pressure-responsive particles in an unpressurized state, and is preferably 80 mass% or less, more preferably 75 mass% or less, and even more preferably 70 mass% or less in terms of forming the pressure-responsive particles that are likely to undergo a phase change due to pressure.
- (meth) acrylate-based resin-
The pressure-responsive mother particle constituting the pressure-responsive particle of the present embodiment contains a (meth) acrylate-based resin containing at least 2 kinds of (meth) acrylates in a polymerization component, and the mass ratio of the (meth) acrylates in the entire polymerization component is 90 mass% or more.
The mass ratio of the (meth) acrylate to the entire polymerization component of the (meth) acrylate-based resin is 90 mass% or more, preferably 95 mass% or more, more preferably 98 mass% or more, and even more preferably 100 mass%.
Examples of the (meth) acrylate include alkyl (meth) acrylate, carboxyl-substituted alkyl (meth) acrylate, hydroxyl-substituted alkyl (meth) acrylate, alkoxy-substituted alkyl (meth) acrylate, and di (meth) acrylate.
Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate, and isobornyl (meth) acrylate. Examples of the carboxy-substituted alkyl (meth) acrylate include 2-carboxyethyl (meth) acrylate and the like. Examples of the hydroxy-substituted alkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
Examples of the alkoxy-substituted alkyl (meth) acrylate include 2-methoxyethyl (meth) acrylate and the like.
Examples of the di (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, pentanediol di (meth) acrylate, hexanediol di (meth) acrylate, nonanediol di (meth) acrylate, and decanediol di (meth) acrylate.
Examples of the (meth) acrylate include 2- (diethylamino) ethyl (meth) acrylate, benzyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, and the like.
The (meth) acrylic acid ester may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
As the (meth) acrylic ester, from the viewpoint of forming pressure-responsive particles which are easily changed in phase by pressure and are excellent in adhesiveness, alkyl (meth) acrylates are preferable, alkyl (meth) acrylates in which the number of carbon atoms of the alkyl group is 2 to 10 are more preferable, alkyl (meth) acrylates in which the number of carbon atoms of the alkyl group is 4 to 8 are further more preferable, and n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferable. The styrene-based resin and the (meth) acrylate-based resin preferably contain the same kind of (meth) acrylate as a polymerization component, from the viewpoint of forming the pressure-responsive particles which are likely to undergo a phase change due to pressure.
The mass ratio of the alkyl (meth) acrylate in the entire polymerization component of the (meth) acrylate-based resin is preferably 90 mass% or more, more preferably 95 mass% or more, further preferably 98 mass% or more, and further preferably 100 mass% from the viewpoint of forming pressure-responsive particles that are easily phase-changed by pressure and have excellent adhesiveness. The alkyl (meth) acrylate herein is preferably an alkyl (meth) acrylate in which the alkyl group has 2 to 10 carbon atoms, and more preferably an alkyl (meth) acrylate in which the alkyl group has 4 to 8 carbon atoms.
The mass ratio of the 2 (meth) acrylates having the largest mass ratio among the at least 2 (meth) acrylates contained as the polymerization components in the (meth) acrylate resin is preferably 80:20 to 20:80, more preferably 70: 30 to 30: 70, and even more preferably 60: 40 to 40: 60, from the viewpoint of forming pressure-responsive particles which are easily phase-changed by pressure and have excellent adhesiveness.
The 2 species having the largest mass ratio among the at least 2 species of (meth) acrylates contained as the polymerization component in the (meth) acrylate-based resin are preferably alkyl (meth) acrylates. The alkyl (meth) acrylate herein is preferably an alkyl (meth) acrylate in which the alkyl group has 2 to 10 carbon atoms, and more preferably an alkyl (meth) acrylate in which the alkyl group has 4 to 8 carbon atoms.
When 2 (meth) acrylic esters, which are the most abundant among at least 2 (meth) acrylic esters contained as a polymerization component in the (meth) acrylate-based resin, are alkyl (meth) acrylates, the difference in the number of carbon atoms of the alkyl groups of the 2 (meth) acrylic esters is preferably 1 to 4, more preferably 2 to 4, and still more preferably 3 or 4, from the viewpoint of forming pressure-responsive particles that are easily transformed by pressure and have excellent adhesion.
In the (meth) acrylate-based resin, from the viewpoint of forming pressure-responsive particles which are easily subjected to phase change by pressure and are excellent in adhesion, it is preferable that n-butyl acrylate and 2-ethylhexyl acrylate be contained as polymerization components, and it is particularly preferable that 2 of at least 2 (meth) acrylates contained as polymerization components in the (meth) acrylate-based resin be n-butyl acrylate and 2-ethylhexyl acrylate in the largest mass ratio. The mass ratio of the total amount of n-butyl acrylate and 2-ethylhexyl acrylate to the total amount of the polymerization components of the (meth) acrylate resin is preferably 90 mass% or more, more preferably 95 mass% or more, still more preferably 98 mass% or more, and still more preferably 100 mass%.
The (meth) acrylate resin may contain a vinyl monomer other than the (meth) acrylate in the polymerization component. Examples of vinyl monomers other than (meth) acrylic acid esters include: (meth) acrylic acid; styrene; styrenic monomers other than styrene; (meth) acrylonitrile; vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone, and vinyl isopropenyl ketone; olefins such as isoprene, butylene, and butadiene. These vinyl monomers may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
When the (meth) acrylate-based resin contains a vinyl monomer other than a (meth) acrylate in the polymerization component, the vinyl monomer other than a (meth) acrylate is preferably at least one of acrylic acid and methacrylic acid, and more preferably acrylic acid.
The weight average molecular weight of the (meth) acrylate-based resin is preferably 5 ten thousand or more, more preferably 10 ten thousand or more, and even more preferably 12 ten thousand or more in terms of suppressing fluidization of the pressure-responsive particles in an unpressurized state, and is preferably 25 ten thousand or less, more preferably 22 ten thousand or less, and even more preferably 20 ten thousand or less in terms of forming the pressure-responsive particles that are likely to undergo a phase change due to pressure.
The glass transition temperature of the (meth) acrylate-based resin is preferably 10 ℃ or lower, more preferably 0 ℃ or lower, and still more preferably-10 ℃ or lower, from the viewpoint of forming pressure-responsive particles that are likely to undergo a phase change by pressure, and is preferably-90 ℃ or higher, more preferably-80 ℃ or higher, and still more preferably-70 ℃ or higher, from the viewpoint of suppressing fluidization of the pressure-responsive particles in an unpressurized state.
The mass ratio of the (meth) acrylate-based resin in the present embodiment to the entire pressure-responsive mother particle is preferably 20 mass% or more, more preferably 25 mass% or more, and even more preferably 30 mass% or more in terms of forming the pressure-responsive particles that are likely to undergo a phase change due to pressure, and is preferably 45 mass% or less, more preferably 40 mass% or less, and even more preferably 35 mass% or less in terms of suppressing fluidization of the pressure-responsive particles in an unpressurized state.
The total amount of the styrene-based resin and the (meth) acrylate-based resin contained in the pressure-responsive mother particle in the present embodiment is preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, further preferably 95% by mass or more, and further preferably 100% by mass, based on the entire pressure-responsive mother particle.
Other resins
The pressure-responsive master particles may contain, for example, polystyrene; epoxy resin, polyester resin, polyurethane resin, polyamide resin, cellulose resin, polyether resin, modified rosin; and so on. These resins may be used singly or in combination of two or more.
Various additives
The pressure-responsive mother particle may contain, as required, a colorant (e.g., pigment or dye), a releasing agent (e.g., hydrocarbon wax, natural wax such as carnauba wax, rice bran wax or candelilla wax, synthetic or mineral/petroleum wax such as montan wax, ester wax such as fatty acid ester or montanic acid ester), a charge control agent, and the like.
When the pressure-responsive particles of the present embodiment are made into transparent pressure-responsive particles, the amount of the coloring agent in the pressure-responsive mother particles is preferably 1.0 mass% or less with respect to the whole pressure-responsive mother particles, and from the viewpoint of improving the transparency of the pressure-responsive particles, the smaller the amount of the coloring agent, the more preferable.
Structure of pressure-responsive mother particles
The internal structure of the pressure-responsive mother particle is preferably an island-in-sea structure, and the pressure-responsive mother particle preferably has: a sea phase comprising a styrenic resin; and an island-in-sea structure comprising island phases of a (meth) acrylate resin dispersed in the sea phase. The specific manner of the styrenic resin contained in the sea phase is as described above. Specific modes of the (meth) acrylate-based resin contained in the island phase are as described above. Island phases containing no (meth) acrylate resin may be dispersed in the sea phase.
When the pressure-responsive mother particle has a sea-island structure, the average diameter of the island phase is preferably 200nm to 500 nm. When the average diameter of the island phase is 500nm or less, the pressure-responsive mother particle is likely to undergo phase transition by pressure, and when the average diameter of the island phase is 200nm or more, the mechanical strength required for the pressure-responsive mother particle (for example, strength that is unlikely to deform when stirred in a developer) is excellent. From this viewpoint, the average diameter of the island phase is more preferably 220nm to 450nm, and still more preferably 250nm to 400 nm.
As a method of controlling the average diameter of the island phases of the sea-island structure within the above range, for example, there can be mentioned: in the method for producing the pressure-responsive master batch described later, the amount of the (meth) acrylate resin is increased or decreased relative to the amount of the styrene resin, and the time for maintaining the resin particles at a high temperature is increased or decreased in the step of fusing/uniting (fusing/uniting) the aggregated resin particles.
The sea-island structure was confirmed and the average diameter of the island phase was measured by the following method.
The pressure-responsive particles are embedded in epoxy resin, a section is prepared with a diamond knife or the like, and the prepared section is stained with osmium tetroxide or ruthenium tetroxide in a desiccator. The stained sections were observed by a Scanning Electron Microscope (SEM). The sea phase and the island phase of the sea-island structure are distinguished by the shade due to the degree of dyeing of the resin with osmium tetroxide or ruthenium tetroxide, and the presence or absence of the sea-island structure is confirmed by this method. 100 island phases were randomly selected from the SEM image, the major axis of each island phase was measured, and the average of the 100 major axes was defined as the average diameter.
The pressure-responsive mother particle may be a pressure-responsive mother particle having a single-layer structure, or may be a pressure-responsive mother particle having a core/shell structure including a core and a shell layer covering the core. The pressure-responsive mother particle is preferably of a core/shell structure in terms of suppressing fluidization of the pressure-responsive particle in an unpressurized state.
When the pressure-responsive mother particle has a core/shell structure, the core portion preferably contains a styrene-based resin and a (meth) acrylate-based resin, since the phase change is likely to occur due to pressure. In addition, from the viewpoint of suppressing fluidization of the pressure-responsive particles in an unpressurized state, it is preferable that the shell layer contains a styrene-based resin. The styrene-based resin is described in detail above. Specific embodiments of the (meth) acrylate-based resin are as described above.
In the case where the pressure-responsive mother particle has a core/shell structure, the core preferably has: a sea phase comprising a styrenic resin and an island phase comprising a (meth) acrylate-based resin dispersed in the sea phase. The average diameter of the island phase is preferably in the above range. In addition to the above configuration of the core portion, it is preferable that the shell layer contains a styrene resin. In this case, the sea phase in the core portion and the shell layer form a continuous structure, and the pressure-responsive mother particle is likely to undergo a phase change by pressure. Specific modes of the styrene-based resin contained in the sea phase of the core portion and the shell layer are as described above. Specific embodiments of the (meth) acrylate-based resin contained in the island phase of the core portion are as described above.
Examples of the resin contained in the shell layer include: polystyrene; non-vinyl resins such as epoxy resins, polyester resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, and modified rosins; and so on. These resins may be used singly or in combination of two or more.
The average thickness of the shell layer is preferably 120nm or more, more preferably 130nm or more, and further preferably 140nm or more from the viewpoint of suppressing deformation of the pressure-responsive mother particle, and is preferably 550nm or less, more preferably 500nm or less, and further preferably 400nm or less from the viewpoint of facilitating phase transition of the pressure-responsive mother particle by pressure.
The average thickness of the shell layer was measured by the following method.
The pressure-responsive particles are embedded in epoxy resin, a section is prepared with a diamond knife or the like, and the prepared section is stained with osmium tetroxide or ruthenium tetroxide in a desiccator. The stained section was observed by a Scanning Electron Microscope (SEM). From the SEM images, 10 sections of the pressure-responsive mother particles were randomly selected, the thickness of the shell layer at 20 was measured for each 1 pressure-responsive mother particle and the average value was calculated, and the average value of 10 pressure-responsive mother particles was taken as the average thickness.
The volume average particle diameter (D50v) of the pressure-responsive mother particles is preferably 4 μm or more, more preferably 5 μm or more, and still more preferably 6 μm or more in terms of ease of handling of the pressure-responsive mother particles, and the D50v is preferably 12 μm or less, more preferably 10 μm or less, and still more preferably 9 μm or less in terms of ease of phase transition of the pressure-responsive mother particles as a whole due to pressure.
The volume average particle diameter (D50v) of the pressure-responsive mother particles was measured using a Coulter Multisizer II (manufactured by Beckman Coulter Co.) and a pore having a pore diameter of 100 μm. The pressure-responsive mother particles of 0.5mg to 50mg were added to 2mL of a5 mass% aqueous solution of sodium alkylbenzenesulfonate and dispersed, and then mixed with 100mL to 150mL of an electrolytic solution (ISOTON-II, manufactured by Beckman Coulter corporation) and subjected to a dispersion treatment with an ultrasonic disperser for 1 minute, and the resulting dispersion was used as a sample. The particle diameters of 50000 particles having particle diameters of 2 to 60 μm in the sample were measured. The particle diameter at the cumulative 50% point in the volume-based particle size distribution from the smaller diameter side was defined as the volume average particle diameter (D50 v).
In the pressure-responsive particles of the present embodiment, it is preferable that titanium oxide particles are further contained as an external additive in addition to the pressure-responsive parent particles having the above-described properties. It is presumed that the above-mentioned interaction between the pressure-responsive mother particles and the titanium oxide particles functions by containing the titanium oxide particles, and contributes to the improvement of the adhesiveness. In particular, it is considered that the titanium oxide particles exert a more effective interaction with the resin species contained in the pressure-responsive mother particles, and pressure-responsive particles having excellent adhesion are obtained.
The pressure responsive particles of the present embodiment can provide pressure responsive particles having excellent adhesion by including titanium oxide particles as an external additive. In the pressure-responsive particles of the present embodiment, the titanium oxide particles are preferably adhered to the surface of the pressure-responsive mother particles.
The crystal structure of the titanium oxide particles is not particularly limited, and examples thereof include a rutile type, an anatase type, and a brookite type. From the viewpoint of improving adhesiveness, the average primary particle diameter of the titanium oxide particles is preferably 1nm to 180nm, more preferably 1nm to 100nm, and still more preferably 10nm to 90 nm.
The titanium oxide particles contained in the external additive of the pressure-responsive particles of the present embodiment are preferably titanium oxide particles surface-treated with a surface treatment agent, from the viewpoint of improving dispersibility in the pressure-responsive particles. As the surface treatment agent, a silicon-containing organic compound is preferable. Examples of the silicon-containing organic compound include an alkoxysilane compound, a silazane compound, and a silicon oil.
Examples of the alkoxysilane compound used for the surface treatment of the titanium oxide particles include: tetramethoxysilane, tetraethoxysilane; methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, hexyltrimethoxysilane, n-octyltrimethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, vinyltriethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, butyltriethoxysilane, hexyltriethoxysilane, decyltriethoxysilane, dodecyltriethoxysilane, phenyltrimethoxysilane, o-methylphenyltrimethoxysilane, p-methylphenyltrimethoxysilane, phenyltriethoxysilane, benzyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane; trimethylmethoxysilane and trimethylethoxysilane.
Examples of the silazane compound used for the surface treatment of the titanium oxide particles include dimethyldisilazane, trimethyldisilazane, tetramethyldisilazane, pentamethyldisilazane, and hexamethyldisilazane.
Examples of the silicone oil used for the surface treatment of the titanium oxide particles include silicone oils such as dimethylpolysiloxane, diphenylpolysiloxane, and phenylmethylpolysiloxane; modified silicone oils (also referred to as "reactive silicone oils") such as amino-modified silicones, epoxy-modified silicones, carboxyl-modified silicones, methanol-modified silicones, fluorine-modified silicones, methacryl-modified silicones, mercapto-modified silicones, and phenol-modified silicones; and so on.
The surface treatment method using the surface treatment agent may be any method as long as it is a known method, and may be either a dry method or a wet method.
The amount of the surface treatment agent (also referred to as "treatment amount") is, for example, preferably 0.5 to 20 mass%, more preferably 3 to 15 mass%, based on the mass of the titanium oxide particles other than the surface treatment agent. The content of the titanium oxide particles contained in the external additive of the pressure-responsive particles of the present embodiment is preferably 0.5 to 5 parts by mass, more preferably 0.5 to 3 parts by mass, and further preferably 1 to 2.5 parts by mass, relative to 100 parts by mass of the pressure-responsive mother particles, from the viewpoint of improving adhesiveness.
The pressure-responsive particles of the present embodiment preferably contain, as an external additive, silica particles having an average primary particle diameter of 50nm to 300nm (hereinafter, silica particles having an average primary particle diameter in the above range are also referred to as "large-diameter silica particles"). When the pressure-responsive particles include large-diameter silica particles, both the adhesiveness and the releasability between the pressure-responsive particle layers can be satisfied in a pressure-bonded printed product obtained by pressure-bonding using the pressure-responsive particles.
It is considered that when pressure-responsive particles having large-diameter silica particles with an average primary particle diameter of 50nm or more as an external additive are used to pressure bond a printed matter, the releasability between the pressure-responsive particle layers can be improved by the large-diameter silica particles dispersed in the pressure-responsive particle layers. Further, it is considered that when pressure-responsive particles having large-diameter silica particles with an average primary particle diameter of 300nm or less are used as an external additive to pressure bond a printed matter, the adhesion between the pressure-responsive particle layers is easily maintained by the large-diameter silica particles dispersed in the pressure-responsive particle layers.
The average primary particle diameter of the large-diameter silica particles is 50nm to 300nm, preferably 55nm to 280nm, and more preferably 60nm to 200 nm.
The method for making the average primary particle diameter of the large-diameter silica particles within the above range is not particularly limited, and for example, in the case where the large-diameter silica particles are sol-gel silica particles, there can be mentioned: and a method of controlling the amount of the alkoxysilane added dropwise with respect to the amount of the alkali catalyst solution.
The large-diameter silica particles are made of silicon dioxide (SiO)2The particles as the main component may be crystalline or amorphous. The large-diameter silica particles may be particles produced using a silicon compound such as water glass or alkoxysilane as a raw material, or may be particles obtained by pulverizing quartz. Specifically, examples of the large-diameter silica particles include: sol gel silica particles; aqueous colloidal silica particles; alcoholic silica particles; fumed silica particles obtained by a vapor phase method or the like; fused silica particles; and so on. Among the above, the large-diameter silica particles preferably contain sol-gel silica particles from the viewpoint of further improving the releasability between the pressure-responsive particle layers.
The sol-gel silica particles are obtained, for example, in the following manner. Tetraalkoxysilane (TMOS or the like) is added dropwise to a base catalyst solution containing an alcohol compound and aqueous ammonia, and the tetraalkoxysilane is hydrolyzed and condensed to obtain a suspension containing sol-gel silica particles. Subsequently, the solvent was removed from the suspension to obtain granules. Subsequently, the granules were dried, thereby obtaining sol-gel silica particles.
From the viewpoint of dispersibility, the average circularity of the large-diameter silica particles is preferably 0.85 to 0.99, more preferably 0.86 to 0.98, and still more preferably 0.90 to 0.97. From the viewpoint of production, the average circularity of the large-diameter silica particles is preferably 0.99 or less. When the average circularity of the large-diameter silica particles is 0.85 or more, the large-diameter silica particles tend to be suppressed from being buried in the surface of the pressure-responsive mother particles.
The method for making the average circularity of the large diameter silica particles within the above range is not particularly limited, and for example, when the large diameter silica particles are sol-gel silica particles, there can be mentioned: and a method of controlling the amount of the alkoxysilane added dropwise with respect to the amount of the alkali catalyst solution.
The average circularity of the large diameter silica particles is calculated by the following method. The surface of the pressure-responsive mother particle was observed at 40,000 times using a Scanning Electron Microscope (SEM), and an image was obtained for at least 100 large-diameter silica particles on the outer edge of the pressure-responsive mother particle. The obtained images of the large-diameter silica particles were analyzed by using image processing analysis software winrofo (manufactured by mitsubishi corporation), and the circularity of each large-diameter silica particle was determined from the following formula. In the following formula, a represents a projected area and PM represents a circumferential length. The arithmetic mean of the circularities of the large diameter silica particles thus obtained was defined as the mean circularity of the large diameter silica particles.
Roundness (equivalent circle diameter/circumference) [2 × (a pi) 1/2]/PM
The large-diameter silica particles may be hydrophobic large-diameter silica particles subjected to hydrophobic surface treatment. The hydrophobizing agent is not particularly limited, and a silicon-containing organic compound is preferable. Examples of the silicon-containing organic compound include the above-mentioned alkoxysilane compound, silazane compound, and silicone oil. These may be used alone or in combination of two or more.
Among these, 1, 1, 1, 3, 3, 3-Hexamethyldisilazane (HMDS) is preferable as the hydrophobizing agent for the sol-gel silica particles.
The amount of the hydrophobizing agent is, for example, preferably 10 mass% to 100 mass%, more preferably 40 mass% to 80 mass% with respect to 100 parts by mass of the silica particles, from the viewpoint of effectively hydrophobizing the surfaces of the silica particles.
When the large-diameter silica particles are hydrophobic large-diameter silica particles subjected to a hydrophobic surface treatment, the average primary particle diameter of the large-diameter silica particles is the average primary particle diameter of the hydrophobic sol gel silica particles subjected to the hydrophobic surface treatment.
The amount of the large-diameter silica particles added to the total mass of the pressure-responsive master particles is preferably 0.1 mass% to 10 mass%, more preferably 0.5 mass% to 5 mass%, and still more preferably 1 mass% to 3 mass%. When the amount of the large-diameter silica particles added is 0.1 mass% or more, the releasability between the pressure-responsive particle layers tends to be further improved. On the other hand, when the amount of the large-diameter silica particles added is 10 mass% or less, the decrease in the adhesiveness between the pressure-responsive particle layers tends to be further suppressed.
The average primary particle diameter of the external additive is measured by the following method. Here, the particle diameter refers to the diameter of a circle having the same area as the primary particle image (so-called equivalent circle diameter). Specifically, the pressure-responsive particle layer is formed of pressure-responsive particles to which an external additive including titanium oxide particles or large-diameter silica particles is externally added, and the pressure-responsive particle layer is observed with an SEM (Scanning Electron Microscope) device at an arbitrary magnification to take an Electron Microscope image. In the obtained electron microscope image, the equivalent circle diameter is obtained by image analysis for an arbitrary external additive particle. This operation is performed for 100 arbitrary external additive particles. The average primary particle diameter of the external additive particles is determined as the particle diameter at 50% cumulative point from the small diameter side (50% diameter, D50v) in the number-based distribution of the primary particle diameters of the external additive particles.
[ other external additives ]
Examples of the external additive other than titanium oxide and large-diameter silica particles (hereinafter also simply referred to as "other external additive") include inorganic particles. Examples of the inorganic particles include silica particles having an average primary particle diameter of less than 50nm, and Al2O3、CuO、ZnO、SnO2、CeO2、Fe2O3、MgO、BaO、CaO、K2O、Na2O、ZrO2、CaO·SiO2、K2O·(TiO2)n、Al2O3·2SiO2、CaCO3、MgCO3、BaSO4、MgSO4And the like.
The surface of the inorganic particles as the external additive is desirably subjected to a hydrophobic treatment. The hydrophobization treatment is performed by, for example, immersing the inorganic particles in a hydrophobization agent or the like. The hydrophobizing agent is not particularly limited, and examples thereof include a silane coupling agent, silicone oil, titanate coupling agent, and aluminum coupling agent. These treating agents may be used singly or in combination of two or more. The amount of the hydrophobizing agent is, for example, 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the inorganic particles.
Examples of the external additive include resin particles (resin particles of polystyrene, polymethyl methacrylate, melamine resin, and the like), a detergent active agent (for example, a metal salt of a higher fatty acid typified by zinc stearate, and particles of a fluorine-based high molecular weight material).
The amount of the other external additive added is preferably 0.01 to 5 mass%, more preferably 0.01 to 2.0 mass%, with respect to the pressure-responsive mother particle.
[ characteristics of pressure-responsive particles ]
When the pressure-responsive particles of the present embodiment have at least 2 glass transition temperatures, one of the glass transition temperatures is presumed to be the glass transition temperature of the styrene-based resin, and the other is presumed to be the glass transition temperature of the (meth) acrylate-based resin.
The pressure-responsive particles of the present embodiment may have 3 or more glass transition temperatures, but the number of glass transition temperatures is preferably 2. As the number of glass transition temperatures of 2, there are the following: the resin contained in the pressure-responsive particles is in the form of only a styrene-based resin and a (meth) acrylate-based resin; a form in which the content of the other resin than the styrene-based resin and the (meth) acrylate-based resin is small (for example, a form in which the content of the other resin is 5 mass% or less with respect to the entire pressure-responsive particles).
The pressure-responsive particles of the present embodiment have at least 2 glass transition temperatures, and the difference between the lowest glass transition temperature and the highest glass transition temperature is 30 ℃ or more. The difference between the lowest glass transition temperature and the highest glass transition temperature is more preferably 40 ℃ or more, still more preferably 50 ℃ or more, and still more preferably 60 ℃ or more, from the viewpoint that the pressure-responsive particles are likely to undergo phase transition by pressure. The upper limit of the difference between the lowest glass transition temperature and the highest glass transition temperature is, for example, 140 ℃ or lower, 130 ℃ or lower, or 120 ℃ or lower.
The lowest glass transition temperature exhibited by the pressure-responsive particles of the present embodiment is preferably 10 ℃ or less, more preferably 0 ℃ or less, and even more preferably-10 ℃ or less, from the viewpoint that the pressure-responsive particles are likely to undergo a phase change by pressure, and is preferably-90 ℃ or more, more preferably-80 ℃ or more, and even more preferably-70 ℃ or more, from the viewpoint that fluidization of the pressure-responsive particles in an unpressurized state is suppressed.
The pressure-responsive particles of the present embodiment preferably exhibit a maximum glass transition temperature of 30 ℃ or higher, more preferably 40 ℃ or higher, and still more preferably 50 ℃ or higher, from the viewpoint of suppressing fluidization of the pressure-responsive particles in an unpressurized state, and the maximum glass transition temperature is preferably 70 ℃ or lower, more preferably 65 ℃ or lower, and still more preferably 60 ℃ or lower, from the viewpoint of facilitating phase transition of the pressure-responsive particles by pressure.
In the present invention, the glass transition temperature of the pressure-responsive particles is determined from a Differential Scanning Calorimetry curve (DSC curve) obtained by Differential Scanning Calorimetry (DSC). More specifically, according to JIS K7121: 1987 "method for measuring transition temperature of Plastic", the "extrapolated glass transition onset temperature" described in the method for measuring glass transition temperature.
The pressure-responsive particles of the present embodiment are pressure-responsive particles that undergo a phase change due to pressure, and satisfy the following formula 1.
Formula 1. T1-T2 at 10 ℃ -
In formula 1, T1 is a temperature showing a viscosity of 10000 pas at a pressure of 1MPa, and T2 is a temperature showing a viscosity of 10000 pas at a pressure of 10 MPa.
The temperature difference (T1-T2) is preferably 10 ℃ or more, preferably 15 ℃ or more, more preferably 20 ℃ or more from the viewpoint that the pressure-responsive particles are likely to undergo a phase change by pressure, and is preferably 120 ℃ or less, more preferably 100 ℃ or less, and still more preferably 80 ℃ or less from the viewpoint that fluidization of the pressure-responsive particles in an unpressurized state is suppressed.
The value of the temperature T1 is preferably 140 ℃ or less, more preferably 130 ℃ or less, further preferably 120 ℃ or less, and further preferably 115 ℃ or less. The lower limit of the temperature T1 is preferably 80 ℃ or higher, more preferably 85 ℃ or higher.
The value of the temperature T2 is preferably 40 ℃ or higher, more preferably 50 ℃ or higher, and still more preferably 60 ℃ or higher. The upper limit of the temperature T2 is preferably 85 ℃ or lower.
An index indicating that the pressure-responsive particles are likely to undergo a phase transition by pressure is a temperature difference (T1 to T3) between a temperature T1 at a pressure of 1MPa exhibiting a viscosity of 10000Pa · s and a temperature T3 at a pressure of 4MPa exhibiting a viscosity of 10000Pa · s, and the temperature difference (T1 to T3) is preferably 5 ℃ or more. The temperature difference (T1-T3) of the pressure-responsive particles of the present embodiment is preferably 5 ℃ or more, more preferably 10 ℃ or more, from the viewpoint that the phase change is easily caused by pressure.
The temperature difference (T1-T3) is usually 25 ℃ or less.
The temperature T3 at which the pressure-responsive particles of the present embodiment exhibit a viscosity of 10000Pa · s under a pressure of 4MPa is preferably 90 ℃ or less, more preferably 85 ℃ or less, and still more preferably 80 ℃ or less, from the viewpoint of making the temperature difference (T1-T3) 5 ℃ or more. The lower limit of the temperature T3 is preferably 60 ℃ or higher.
The temperature T1, the temperature T2, and the temperature T3 were determined as follows.
The pressure-responsive particles were compressed to prepare a granular sample. The granular sample was placed in a flow tester (CFT-500, manufactured by Shimadzu corporation), the applied pressure was fixed at 1MPa, and the viscosity with respect to the temperature was measured at 1 MPa. From the obtained viscosity graph, it was confirmed that the viscosity reached 10 under the applied pressure of 1MPa4Temperature T1 at pa s. The temperature T2 was determined in the same manner as the determination method of the temperature T1, except that the applied pressure was changed from 1MPa to 10 MPa. The temperature T3 was determined in the same manner as the temperature T1, except that the applied pressure was changed from 1MPa to 4 MPa. A temperature difference (T1-T2) was calculated from the temperature T1 and the temperature T2. A temperature difference (T1-T3) was calculated from the temperature T1 and the temperature T3.
[ method for producing pressure-responsive particles ]
The pressure-responsive particles of the present embodiment are obtained by externally adding an external additive to a pressure-responsive mother particle after the production of the pressure-responsive mother particle.
The pressure-responsive mother particles can be produced by any of a dry process (e.g., kneading and pulverizing process) and a wet process (e.g., aggregation-coalescence process, suspension polymerization process, dissolution-suspension process, etc.). The production method is not particularly limited, and a known production method is used. Among these, the pressure-responsive mother particles can be obtained by an agglutination-combination method (agglutination-integration method).
In the case of producing a pressure-responsive mother particle by the aggregation-coalescence method, the pressure-responsive mother particle is produced, for example, by the following steps:
a step of preparing a styrene-based resin particle dispersion in which styrene-based resin particles containing a styrene-based resin are dispersed (styrene-based resin particle dispersion preparation step);
a step of forming composite resin particles containing a styrene resin and a (meth) acrylate resin by polymerization for producing the (meth) acrylate resin in a styrene resin particle dispersion liquid (composite resin particle forming step);
a step of aggregating the composite resin particles in a composite resin particle dispersion liquid in which the composite resin particles are dispersed to form aggregated particles (aggregated particle forming step); and
and a step of heating the aggregated particle dispersion liquid in which the aggregated particles are dispersed to fuse/merge the aggregated particles to form pressure-responsive mother particles (fusion/merge (fusion/unification) step).
The details of each step will be described below.
In the following description, a method of obtaining a pressure-responsive mother particle containing no colorant and no release agent will be described. Colorants, release agents, and other additives may be used as needed. In the case where the pressure-responsive mother particle contains the colorant and the release agent, the fusion/combination step is performed after mixing the composite resin particle dispersion liquid, the colorant particle dispersion liquid, and the release agent particle dispersion liquid. The colorant particle dispersion liquid and the release agent particle dispersion liquid can be produced, for example, by mixing the materials and then performing a dispersion treatment using a known dispersion machine.
Preparation of styrene resin particle Dispersion
The styrene resin particle dispersion is, for example, a dispersion in which styrene resin particles are dispersed in a dispersion medium by a surfactant.
Examples of the dispersion medium include aqueous media such as water and alcohols. These may be used alone in 1 kind, or in combination of 2 or more kinds.
Examples of the surfactant include: anionic surfactants such as sulfate, sulfonate, phosphate and soap surfactants; cationic surfactants such as amine salt type and quaternary ammonium salt type; nonionic surfactants such as polyethylene glycol-based, alkylphenol-ethylene oxide adduct-based, and polyol-based surfactants; and so on. The nonionic surfactant may be used in combination with an anionic surfactant or a cationic surfactant. Among these, anionic surfactants are preferable. The surfactant may be used alone or in combination of two or more.
Examples of a method for dispersing styrene resin particles in a dispersion medium include a method in which a styrene resin is mixed with a dispersion medium and the mixture is stirred and dispersed using a rotary shear homogenizer, a ball mill with a medium, a sand mill, a bead mill, or the like.
Another method for dispersing styrene resin particles in a dispersion medium is an emulsion polymerization method. Specifically, a polymerization component of a styrene resin is mixed with a chain transfer agent or a polymerization initiator, and then an aqueous medium containing a surfactant is further mixed and stirred to prepare an emulsion, and polymerization for producing the styrene resin is performed in the emulsion. In this case, as the chain transfer agent, dodecanethiol is preferably used.
The volume average particle diameter of the styrene resin particles dispersed in the styrene resin particle dispersion is preferably 100nm to 250nm, more preferably 120nm to 220nm, and still more preferably 150nm to 200 nm.
The volume average particle diameter of the resin particles contained in the resin particle dispersion is measured by a laser diffraction particle size distribution measuring apparatus (for example, LA-700 manufactured by horiba ltd.), and the particle diameter at which 50% of the particle diameter is accumulated in a volume-based particle size distribution from the smaller diameter side is defined as the volume average particle diameter (D50 v).
The content of the styrene resin particles contained in the styrene resin particle dispersion liquid is preferably 30 mass% to 60 mass%, more preferably 40 mass% to 50 mass%.
-composite resin particle formation step-
The composite resin particles containing a styrene resin and a (meth) acrylate resin are formed by mixing a styrene resin particle dispersion and a polymerization component of the (meth) acrylate resin, and performing polymerization for producing the (meth) acrylate resin in the styrene resin particle dispersion.
The composite resin particles are preferably resin particles containing a styrene-based resin and a (meth) acrylate-based resin in a microphase separated state. The resin particles can be produced, for example, by the following method.
A polymerization component of a (meth) acrylate-based resin (a monomer group containing at least 2 types of (meth) acrylates) is added to a styrene-based resin particle dispersion, and an aqueous medium is added as needed. Then, while slowly stirring the dispersion, the temperature of the dispersion is heated to a temperature equal to or higher than the glass transition temperature of the styrene-based resin (for example, a temperature 10 ℃ to 30 ℃ higher than the glass transition temperature of the styrene-based resin). Then, an aqueous medium containing a polymerization initiator is slowly dropped while maintaining the temperature, and further, stirring is continued for a long time in a range of 1 hour to 15 hours. In this case, ammonium persulfate is preferably used as the polymerization initiator.
Although the detailed mechanism is not necessarily clear, it is presumed that, in the case of the above method, the monomer and the polymerization initiator are impregnated into the styrene-based resin particles, and the (meth) acrylate is polymerized inside the styrene-based resin particles. It is presumed that composite resin particles in which a (meth) acrylate resin is contained in styrene resin particles and the styrene resin and the (meth) acrylate resin in the particles are microphase-separated can be obtained.
During or after the production of the composite resin particles, a polymerization component of a styrene resin (i.e., styrene and other vinyl monomers) may be added to the dispersion in which the composite resin particles are dispersed, and the polymerization reaction may be continued. From this, it is presumed that composite resin particles in which a styrene resin and a (meth) acrylate resin are microphase-separated in the interior of the particles and the styrene resin is adhered to the surfaces of the particles can be obtained. In the pressure-responsive particles produced using the composite resin particles in which the styrene resin is adhered to the particle surfaces, generation of coarse powder is relatively small.
The other vinyl monomer as a polymerization component of the styrene resin adhering to the surface of the composite resin particle preferably includes a monomer of the same kind as at least one of monomers constituting the styrene resin or the (meth) acrylate resin contained in the composite resin particle, and specifically preferably includes at least one of n-butyl acrylate and 2-ethylhexyl acrylate.
The volume average particle diameter of the composite resin particles dispersed in the composite resin particle dispersion liquid is preferably 140nm to 300nm, more preferably 150nm to 280nm, and still more preferably 160nm to 250 nm.
The content of the composite resin particles contained in the composite resin particle dispersion liquid is preferably 20 mass% to 50 mass%, more preferably 30 mass% to 40 mass%.
-an aggregated particle formation step-
The composite resin particles are aggregated in the composite resin particle dispersion liquid to form aggregated particles having a diameter close to the diameter of the target pressure-responsive mother particle.
Specifically, for example, a coagulant is added to a composite resin particle dispersion, the pH of the composite resin particle dispersion is adjusted to be acidic (for example, pH2 or more and 5 or less), a dispersion stabilizer is added as needed, and then the resulting mixture is heated to a temperature close to the glass transition temperature of a styrene resin (specifically, for example, glass transition temperature of the styrene resin is-30 ℃ or more and glass transition temperature of the styrene resin is-10 ℃ or less) to coagulate the composite resin particles, thereby forming coagulated particles.
In the aggregated particle forming step, the pH of the composite resin particle dispersion may be adjusted to be acidic (for example, pH2 or more and 5 or less) by adding the aggregating agent at room temperature (for example, 25 ℃) while stirring the composite resin particle dispersion with a rotary shear homogenizer, and heating may be performed after adding the dispersion stabilizer if necessary.
Examples of the aggregating agent include a surfactant having a polarity opposite to that of the surfactant contained in the composite resin particle dispersion liquid, an inorganic metal salt, and a metal complex having a valence of 2 or more. When a metal complex is used as the coagulant, the amount of the surfactant used is reduced, and the charging characteristics are improved.
An additive that forms a complex or a similar bond with the metal ion of the coagulant may be used together with the coagulant as needed. As the additive, a chelating agent is suitably used.
Examples of the inorganic metal salt include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate; inorganic metal salt polymers such as polyaluminum chloride, polyaluminum hydroxide and calcium polysulfide; and so on.
As the chelating agent, a water-soluble chelating agent can be used. Examples of the chelating agent include hydroxycarboxylic acids such as tartaric acid, citric acid, and gluconic acid; aminocarboxylic acids such as iminodiacetic acid (IDA), nitrilotriacetic acid (NTA), and ethylenediaminetetraacetic acid (EDTA); and so on.
The addition amount of the chelating agent is preferably 0.01 part by mass or more and 5.0 parts by mass or less, and more preferably 0.1 part by mass or more and less than 3.0 parts by mass with respect to 100 parts by mass of the resin particles.
Fusion/merging step
Next, the agglomerated particle dispersion liquid in which the agglomerated particles are dispersed is heated to, for example, a glass transition temperature of a styrene resin or higher (for example, a temperature 10 to 30 ℃ higher than the glass transition temperature of the styrene resin) to fuse/merge the agglomerated particles, thereby forming the pressure-responsive mother particles.
The pressure-responsive mother particle obtained through the above steps generally has an island-in-sea structure having: a sea phase containing a styrene-based resin and an island phase containing a (meth) acrylate-based resin dispersed in the sea phase. It is presumed that when the styrene-based resin and the (meth) acrylate-based resin in the composite resin particles are in a microphase separated state, the styrene-based resin aggregates with each other to form a sea phase and the (meth) acrylate-based resin aggregates with each other to form an island phase in the fusion/coalescence step.
The average diameter of the island phases of the sea-island structure can be controlled by, for example, increasing or decreasing the amount of the styrene-based resin particle dispersion or the amount of at least 2 (meth) acrylic esters used in the composite resin particle formation step, or increasing or decreasing the time for which the particles are maintained at a high temperature in the fusion/coalescence step.
The pressure-responsive mother particle of the core/shell structure is produced, for example, by the following steps:
a step of forming 2 nd agglomerate particles by further mixing the agglomerate particle dispersion with the styrene resin particle dispersion and agglomerating the agglomerate particles so that styrene resin particles adhere to the surfaces of the agglomerate particles; and
and a step of heating the 2 nd agglutinated particle dispersion liquid in which the 2 nd agglutinated particles are dispersed to fuse and combine the 2 nd agglutinated particles to form the pressure-responsive mother particles of the core/shell structure.
The pressure-responsive mother particle of the core/shell structure obtained through the above steps has a shell layer comprising a styrenic resin. Instead of the styrene-based resin particle dispersion, a resin particle dispersion in which other types of resin particles are dispersed may be used to form a shell layer containing other types of resins.
After the completion of the fusion/combination step, the pressure-responsive mother particles formed in the solution are subjected to a known washing step, a solid-liquid separation step, and a drying step to obtain pressure-responsive mother particles in a dried state. In the cleaning step, displacement cleaning with ion-exchanged water can be sufficiently performed from the viewpoint of chargeability. In the solid-liquid separation step, suction filtration, pressure filtration, or the like may be performed in terms of productivity. The drying step may be freeze drying, pneumatic drying, fluidized drying, vibratory fluidized drying, or the like, from the viewpoint of productivity.
Then, for example, an external additive is added to the obtained pressure-responsive mother particles in a dry state and mixed, thereby producing the pressure-responsive particles of the present embodiment. The mixing can be performed by, for example, a V-type mixer, a Henschel mixer, a Loedige mixer, or the like. Further, if necessary, coarse particles of the pressure-responsive particles may be removed by using a vibration sieve, a wind sieve, or the like.
< Box (cartridge) >
The cartridge of the present embodiment is a cartridge that stores the pressure-responsive particles of the present embodiment and is attached to and detached from a printed matter manufacturing apparatus. After the cartridge is attached to the apparatus for producing printed matter, the cartridge is connected to a mechanism for disposing the pressure-responsive particles on the recording medium, which is provided in the apparatus for producing printed matter, by a supply pipe.
The pressure responsive particles are supplied from the cartridge to the arrangement mechanism, and the cartridge is replaced when the number of the pressure responsive particles stored in the cartridge is reduced.
< apparatus for producing printed matter, method for producing printed matter, and printed matter >
The printed matter manufacturing apparatus of the present embodiment includes: an arrangement mechanism that stores the pressure-responsive particles of the present embodiment and arranges the pressure-responsive particles on a recording medium; and a pressure bonding mechanism for folding and pressure bonding the recording medium or overlapping the recording medium and another recording medium and pressure bonding the recording medium.
The arrangement mechanism may be provided with, for example, a device for applying the pressure-responsive particles to the recording medium, or may further be provided with a fixing device for fixing the pressure-responsive particles applied to the recording medium.
The pressure bonding mechanism includes, for example, a folding device that folds the recording medium on which the pressure-responsive particles are arranged, a superimposing device that superimposes the recording medium on which the pressure-responsive particles are arranged and another recording medium, and a pressurizing device that pressurizes the superimposed recording medium.
The pressure device provided in the pressure bonding mechanism applies pressure to the recording medium on which the pressure-responsive particles are arranged. This fluidizes the pressure-responsive particles on the recording medium, thereby exhibiting adhesiveness.
The method for manufacturing a printed matter of the present embodiment is performed by the apparatus for manufacturing a printed matter of the present embodiment. The method for producing a printed matter of the present embodiment uses the pressure-responsive particles of the present embodiment, and includes the steps of: a disposing step of disposing the pressure-responsive particles on a recording medium; and a pressure bonding step of folding and pressure bonding the recording medium or overlapping the recording medium with another recording medium and pressure bonding the recording medium.
The disposing step may include, for example, a step of imparting the pressure-responsive particles onto the recording medium, and may further include a step of fixing the pressure-responsive particles imparted onto the recording medium.
The pressure bonding step includes, for example, a folding step of folding the recording medium, a stacking step of stacking the recording medium on another recording medium, and a pressing step of pressing the stacked recording media.
The pressure-responsive particles may be disposed on the entire surface of the recording medium or may be disposed on a part of the recording medium. The pressure-responsive particles are disposed in 1 layer or a plurality of layers on the recording medium. The layer of the pressure-responsive particles may be a layer continuous in the planar direction of the recording medium, or may be a layer discontinuous in the planar direction of the recording medium. The layer of the pressure-responsive particles may be a layer in which the pressure-responsive particles are arranged in a state of retaining particles, or a layer in which adjacent pressure-responsive particles are fused and arranged.
Regarding the amount of the pressure-responsive particles (preferably transparent pressure-responsive particles) on the recording medium, the amount is, for example, 0.5g/m in the region where the particles are arranged2Above 50g/m21g/m below2Above 40g/m21.5g/m below2Above 30g/m2The following. The layer thickness of the pressure-responsive particles (preferably transparent pressure-responsive particles) on the recording medium is, for example, 0.2 μm to 25 μm, 0.4 μm to 20 μm, and 0.6 μm to 15 μm.
Examples of the recording medium suitable for the printed matter manufacturing apparatus according to the present embodiment include coated paper, cloth, nonwoven fabric, resin film, resin sheet, and the like, which are discharged or coated with a resin or the like on the surface of the paper. The recording medium may have images on one side or both sides.
An example of the printed matter manufacturing apparatus according to the present embodiment will be described below, but the present embodiment is not limited thereto.
Fig. 1 is a schematic configuration diagram showing an example of the printed matter manufacturing apparatus according to the present embodiment. The apparatus for manufacturing a printed product shown in fig. 1 includes a placement mechanism 100 and a pressure bonding mechanism 200 disposed downstream of the placement mechanism 100. The arrow indicates the transport direction of the recording medium.
The disposing mechanism 100 is a device that disposes the pressure-responsive particles on the recording medium P using the pressure-responsive particles of the present embodiment. An image is formed in advance on one side or both sides of the recording medium P.
The arrangement mechanism 100 includes an application device 110 and a fixing device 120 arranged downstream of the application device 110.
The imparting device 110 imparts the pressure-responsive particles M onto the recording medium P. Examples of the application method used by the application device 110 include a spray method, a bar coating method, a die coating method, a doctor blade coating method, a roll coating method, a reverse roll coating method, a gravure printing method, a screen printing method, an ink jet method, a lamination method, and an electrophotographic method. The pressure-responsive particles M may be dispersed in a dispersion medium according to an application method to prepare a liquid composition, and the liquid composition may be applied to the application device 110.
The recording medium P to which the pressure-responsive particles M are imparted by the imparting device 110 is conveyed to the fixing device 120.
The fixing device 120 is, for example: a heating device having a heating source for heating the pressure-responsive particles M on the recording medium P passing therethrough to fix the pressure-responsive particles M on the recording medium P; a pressurizing device including a pair of pressurizing members (roller/roller, belt/roller) for pressurizing the recording medium P passing therethrough to fix the pressure-responsive particles M to the recording medium P; a pressure heating device including a pair of pressure members (roller/roller, belt/roller) having a heat source therein, for pressurizing and heating the recording medium P passing therethrough to fix the pressure-responsive particles M to the recording medium P; and so on.
When the fixing device 120 includes a heat source, the surface temperature of the recording medium P when heated by the fixing device 120 is preferably 10 ℃ to 80 ℃, more preferably 20 ℃ to 60 ℃, and still more preferably 30 ℃ to 50 ℃.
In the case where the fixing device 120 has a pressing member, the pressure applied to the recording medium P by the pressing member may be lower than the pressure applied to the recording medium P2 by the pressing device 230.
The recording medium P passes through the arrangement mechanism 100, thereby forming a recording medium P1 on which the pressure-responsive particles M are imparted on an image. The recording medium P1 is conveyed toward the pressure bonding mechanism 200.
In the printed matter manufacturing apparatus of the present embodiment, the arrangement mechanism 100 and the pressure bonding mechanism 200 may be in a close manner or in a spaced manner. In the case where the arranging mechanism 100 is spaced apart from the crimping mechanism 200, the arranging mechanism 100 and the crimping mechanism 200 may be connected by, for example, a conveying mechanism (e.g., a belt conveyor) that conveys the recording medium P1.
The pressure bonding mechanism 200 includes a folding device 220 and a pressing device 230, and is a mechanism for folding and pressure bonding the recording medium P1.
The folding device 220 folds the recording medium P1 passed through the device, thereby producing a folded recording medium P2. The folding form of the recording medium P2 may be, for example, a half-folded form, a triple-folded form, or a quadruple-folded form, and the recording medium P2 may be only partially folded. The recording medium P2 is in a state in which the pressure-responsive particles M are disposed on at least a portion of at least one of the two opposing surfaces.
The folding device 220 may have a pair of pressing members (e.g., roller/roll, belt/roll) that apply pressure to the recording medium P2. The pressure applied to the recording medium P2 by the pressing member of the folding device 220 may be lower than the pressure applied to the recording medium P2 by the pressing device 230.
The pressure-bonding mechanism 200 may include a superimposing device for superimposing the recording medium P1 on another recording medium, instead of the folding device 220. The form in which the recording medium P1 is stacked on another recording medium is, for example, a form in which 1 sheet of another recording medium is stacked on the recording medium P1, a form in which 1 sheet of another recording medium is stacked on each of a plurality of positions on the recording medium P1, or the like. The other recording medium may be a recording medium on which an image is formed in advance on one or both sides, a recording medium on which no image is formed, or a pressure-sensitive printed product prepared in advance.
The recording medium P2 that has left the folding device 220 (or the overlapping device) is conveyed toward the pressing device 230.
The pressing device 230 includes a pair of pressing members (i.e., pressing rollers 231 and 232). The pressure roller 231 and the pressure roller 232 are pressed against each other while being in contact with each other on their outer peripheral surfaces, and apply pressure to the recording medium P2 passing therethrough. The pair of pressing members provided in the pressing device 230 is not limited to the combination of the pressing roller and the pressing roller, and may be a combination of the pressing roller and the pressing belt, or a combination of the pressing belt and the pressing belt.
When pressure is applied to the recording medium P2 passing through the pressurizing device 230, the pressure-responsive particles M on the recording medium P2 fluidize by the pressure and exhibit adhesiveness.
The pressurizing device 230 may or may not have a heat source (e.g., a halogen heater) for heating the recording medium P2 inside. When the pressurizing device 230 does not have a heat source inside, it is not excluded that the temperature inside the pressurizing device 230 becomes equal to or higher than the ambient temperature due to heat dissipation of a motor or the like provided in the pressurizing device 230.
The recording medium P2 passes through the pressurizing device 230, and the folded surfaces are bonded to each other by the fluidized pressure-responsive particles M, thereby producing a pressure-bonded printed product P3. In the press-contact printed product P3, the 2 opposed surfaces are partially or entirely bonded to each other.
The completed press-bonded printed product P3 is discharged from the pressing device 230.
The first mode of the pressure-contact printed matter P3 is a pressure-contact printed matter in which the folded recording medium is bonded with the pressure-responsive particles M on the opposite surfaces. The pressure-contact printed product P3 of the present embodiment is manufactured by a printed product manufacturing apparatus provided with the folding apparatus 220.
The second embodiment of the pressure-contact printed matter P3 is a pressure-contact printed matter in which 2 or more recording media stacked one on another are bonded to each other with the pressure-responsive particles M on the facing surfaces. The pressure-contact printed product P3 of the present embodiment is manufactured by a pressure-contact printed product manufacturing apparatus including a superimposing apparatus.
The apparatus for manufacturing printed products according to the present embodiment is not limited to the apparatus of the type in which the recording medium P2 is continuously conveyed from the folding device 220 (or the superimposing device) to the pressing device 230. The printed matter manufacturing apparatus according to the present embodiment may be an apparatus of the following embodiment: the recording medium P2 left from the folding device 220 (or the stacker) is stored, and the recording medium P2 is conveyed to the pressing device 230 after the storage amount of the recording medium P2 reaches a predetermined amount.
In the printed matter manufacturing apparatus of the present embodiment, the folding device 220 (or the superimposing device) and the pressure-bonding pressing device 230 may be in a close manner or in a spaced manner. In the case where the folding device 220 (or the overlapping device) is spaced apart from the crimping and pressurizing device 230, the folding device 220 (or the overlapping device) is connected to the crimping and pressurizing device 230, for example, by a conveying mechanism (e.g., a belt conveyor) that conveys the recording medium P2.
The apparatus for manufacturing a printed matter of the present embodiment may include a cutting mechanism for cutting the recording medium into a predetermined size. The cutting mechanism is, for example, the following cutting mechanisms: a cutting mechanism disposed between the disposing mechanism 100 and the pressure bonding mechanism 200, for cutting out a region where the pressure responsive particles M are not disposed, which is a part of the recording medium P1; a cutting mechanism disposed between the folding device 220 and the pressing device 230, for cutting out a region where the pressure-responsive particles M are not disposed, which is a part of the recording medium P2; a cutting mechanism disposed downstream of the press-bonding mechanism 200, for cutting out a region which is a part of the press-bonded printed product P3 and to which the pressure-responsive particles M are not bonded; and so on.
The printed matter manufacturing apparatus of the present embodiment is not limited to the single-sheet type apparatus. The printed matter manufacturing apparatus of the present embodiment may be an apparatus of the following form: the long-sized recording medium is subjected to a placement step and a pressure-bonding step to form a long-sized pressure-bonded printed product, and then the long-sized pressure-bonded printed product is cut into a predetermined size.
The apparatus for producing a printed matter of the present embodiment may further include a color image forming unit for forming a color image on a recording medium using a coloring material. Examples of the color image forming means include a means for forming a color ink image on a recording medium by an ink jet method using a color ink as a coloring material, a means for forming a color image on a recording medium by an electrophotographic method using a color electrostatic image developer, and the like.
The manufacturing apparatus having the above configuration performs the following manufacturing method: the method for producing a printed matter of the present embodiment further includes a color image forming step of forming a color image on a recording medium using a coloring material. Specific examples of the colored image forming step include: a step of forming a colored ink image on a recording medium by an ink jet method using a colored ink as a coloring material, a step of forming a colored image on a recording medium by an electrophotographic method using a colored electrostatic image developer, and the like.
< sheet for producing printed matter, method for producing sheet for producing printed matter >
The sheet for producing printed matter of the present embodiment includes a base material and pressure-responsive particles disposed on the base material. The sheet for producing printed matter of the present embodiment is produced using the pressure-responsive particles of the present embodiment. The pressure-responsive particles on the substrate may or may not retain the shape of the particles before being disposed on the substrate.
The sheet for producing printed matter of the present embodiment is suitable for use in, for example: a masking sheet (masking sheet) that is superimposed on and bonded to the recording medium when information recorded on the recording medium is desired to be concealed; a release sheet used for providing an adhesive layer on the recording media when the recording media are overlapped and adhered to each other; and so on.
Examples of the substrate to be applied to the sheet for producing printed matter according to the present embodiment include coated paper, cloth, nonwoven fabric, resin film, resin sheet, and the like, which are discharged or coated with a resin or the like on the surface of the paper. The substrate may be imaged on one or both sides.
In the sheet for producing printed matter of the present embodiment, the pressure-responsive particles may be disposed on the entire surface of the substrate or may be disposed on a part of the substrate. The pressure-responsive particles are disposed in 1 layer or a plurality of layers on the substrate. The layer of the pressure-responsive particles may be a layer continuous in the plane direction of the substrate, or may be a layer discontinuous in the plane direction of the substrate. The layer of the pressure-responsive particles may be a layer in which the pressure-responsive particles are arranged in a state of retaining particles, or a layer in which adjacent pressure-responsive particles are fused and arranged.
As for the amount of the pressure-responsive particles on the substrate, it is, for example, 0.5g/m in the region where the particles are disposed2Above 50g/m21g/m below2Above 40g/m21.5g/m below2Above 30g/m2The following. The layer thickness of the pressure-responsive particles on the substrate is, for example, 0.2 μm to 25 μm, 0.4 μm to 20 μm, and 0.6 μm to 15 μm.
The sheet for producing printed matter of the present embodiment is produced, for example, by a production method including an arrangement step of arranging the pressure-responsive particles on a base material using the pressure-responsive particles of the present embodiment.
The disposing step includes, for example, an imparting step of imparting the pressure-responsive particles onto the substrate, and further may include a fixing step of fixing the pressure-responsive particles imparted onto the substrate.
The applying step is realized by applying methods such as a spray method, a bar coating method, a die coating method, a doctor blade coating method, a roll coating method, a reverse roll coating method, a gravure printing method, a screen printing method, an ink jet method, a lamination method, and an electrophotographic method. The liquid composition may be prepared by dispersing the pressure-responsive particles in a dispersion medium according to the imparting method of the imparting step, and the liquid composition may be applied to the imparting step.
The fixing steps are for example: a heating step of heating the pressure-responsive particles on the substrate by a heating source to fix the pressure-responsive particles on the substrate; a pressing step of pressing the substrate to which the pressure-responsive particles are applied with a pair of pressing members (roller/roll, belt/roll) to fix the pressure-responsive particles to the substrate; a pressure-heating step of pressurizing and heating the substrate to which the pressure-responsive particles are applied by a pair of pressurizing members (roller/roller, belt/roller) having a heat source therein, thereby fixing the pressure-responsive particles to the substrate; and so on.
< production of printed matter by electrophotography >
An embodiment example in which the pressure-responsive particles of the present embodiment are applied to an electrophotographic process will be described. In the electrophotographic process, the pressure-responsive particles can be used as a toner.
< Electrostatic image developer >
The electrostatic image developer of the present embodiment contains at least the pressure-responsive particles of the present embodiment. The electrostatic image developer according to the present embodiment may be a one-component developer containing only the pressure-responsive particles according to the present embodiment, or may be a two-component developer in which the pressure-responsive particles according to the present embodiment are mixed with a carrier.
The carrier is not particularly limited, and known carriers can be used. Examples of the carrier include: a coated carrier in which a surface of a core material made of magnetic powder is coated with a resin; dispersing a magnetic powder dispersion carrier mixed with magnetic powder in matrix resin; a resin-impregnated carrier in which porous magnetic powder is impregnated with a resin; and so on. The magnetic powder-dispersed carrier and the resin-impregnated carrier may have a core material of particles constituting the carrier and a surface thereof coated with a resin.
Examples of the magnetic powder include: magnetic metals such as iron, nickel, and cobalt; magnetic oxides such as ferrite and magnetite; and so on.
Examples of the resin and the matrix resin for coating include polyethylene, polypropylene, polystyrene, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl ether, polyvinyl ketone, a vinyl chloride-vinyl acetate copolymer, a styrene-acrylate copolymer, a pure silicone resin containing an organosiloxane bond or a modified product thereof, a fluororesin, a polyester, a polycarbonate, a phenol resin, an epoxy resin, and the like. The coating resin and the matrix resin may contain other additives such as conductive particles. Examples of the conductive particles include: metals such as gold, silver, and copper, carbon black, titanium oxide, zinc oxide, tin oxide, barium sulfate, aluminum borate, and potassium titanate.
When the surface of the core material is coated with a resin, there are included: a method of coating with a coating layer forming solution in which a coating resin and various additives (used as needed) are dissolved in an appropriate solvent. The solvent is not particularly limited, and may be selected in consideration of the kind of the resin to be used, coating suitability, and the like.
Specific examples of the resin coating method include: an immersion method in which a core material is immersed in a coating layer forming solution; a spraying method for spraying a coating layer forming solution onto the surface of a core material; a fluidized bed method of spraying a coating layer forming solution in a state in which a core material is suspended by flowing air; a kneading coater method in which a core material of a carrier and a solution for forming a coating layer are mixed, and then the solvent is removed; and so on.
The mixing ratio (mass ratio) of the pressure-responsive particles to the carrier in the two-component developer is preferably 1: 100 to 30: 100, and more preferably 3: 100 to 20: 100.
< apparatus and method for producing printed matter >
The printed matter manufacturing device applying the electronic photography mode comprises: a disposing mechanism that stores a developer containing the pressure-responsive particles of the present embodiment and disposes the pressure-responsive particles on a recording medium by an electrophotographic method; and a pressure bonding mechanism for folding and pressure bonding the recording medium or overlapping the recording medium and another recording medium and pressure bonding the recording medium.
The method for manufacturing a printed matter according to the present embodiment is performed by the printed matter manufacturing apparatus according to the present embodiment.
The method for manufacturing the printed matter by using the electronic photography mode comprises the following steps: a disposing step of disposing the pressure-responsive particles on a recording medium by an electrophotographic method using a developer containing the pressure-responsive particles of the present embodiment; and a pressure bonding step of folding and pressure bonding the recording medium or overlapping the recording medium with another recording medium and pressure bonding the recording medium.
The arrangement mechanism included in the printed matter manufacturing apparatus of the present embodiment includes, for example:
a photoreceptor;
a charging mechanism for charging the surface of the photoreceptor;
an electrostatic image forming unit configured to form an electrostatic image on the surface of the charged photoreceptor;
a developing mechanism that stores the electrostatic image developer of the present embodiment and develops an electrostatic image formed on the surface of the photoreceptor into a pressure-responsive particle-applying portion by the electrostatic image developer; and
and a transfer mechanism for transferring the pressure-responsive particle-applying section formed on the surface of the photoreceptor to the surface of the recording medium.
The arrangement mechanism preferably further includes a fixing mechanism for fixing the pressure-responsive particle applying section transferred to the surface of the recording medium.
The arrangement steps included in the method for manufacturing a printed matter of the present embodiment include, for example, the steps of:
a charging step of charging the surface of the photoreceptor;
an electrostatic image forming step of forming an electrostatic image on the surface of the charged photoreceptor;
a developing step of developing the electrostatic image formed on the surface of the photoreceptor into a pressure-responsive particle-applying portion with the electrostatic image developer of the present embodiment; and
and a transfer step of transferring the pressure-responsive particle-providing portion formed on the surface of the photoreceptor to the surface of a recording medium.
The disposing step preferably further includes a fixing step of fixing the pressure-responsive particle imparting portion transferred to the surface of the recording medium.
The above-mentioned arrangement mechanism is, for example, the following devices: a direct transfer type device for directly transferring the pressure-responsive particle-applying portion formed on the surface of the photoreceptor to a recording medium; an intermediate transfer system device that primarily transfers the pressure-responsive particle-applying portion formed on the surface of the photoreceptor to the surface of the intermediate transfer body, and secondarily transfers the pressure-responsive particle-applying portion transferred to the surface of the intermediate transfer body to the surface of the recording medium; a device provided with a cleaning mechanism for cleaning the surface of the photoreceptor after transfer and before charging of the pressure-responsive particle-applying section; a device including a charge removing mechanism for irradiating a charge removing light to the surface of the photoreceptor after transfer by the pressure-responsive particle applying section and before charging to remove the charge; and so on. In the case where the arrangement mechanism is an intermediate transfer type apparatus, the transfer mechanism includes, for example: an intermediate transfer body that transfers the pressure-responsive particle imparting portion to a surface; a primary transfer mechanism for primarily transferring the pressure-responsive particle imparting section formed on the surface of the photoreceptor to the surface of the intermediate transfer body; and a secondary transfer mechanism that secondarily transfers the pressure-responsive particle imparting portion transferred to the surface of the intermediate transfer body to the surface of the recording medium.
In the arrangement mechanism, a portion including the developing mechanism may be a cartridge structure (so-called process cartridge) detachably attached to the arrangement mechanism. As the process cartridge, for example, a process cartridge storing the electrostatic image developer of the present embodiment and provided with a developing mechanism is suitably used.
The pressure bonding mechanism included in the printed matter manufacturing apparatus of the present embodiment applies pressure to the recording medium on which the pressure-responsive particles of the present embodiment are arranged. As a result, the pressure-responsive particles of the present embodiment flow on the recording medium and exhibit adhesiveness. In order to fluidize the pressure-responsive particles of the present embodiment, the pressure applied to the recording medium by the pressure bonding mechanism is preferably 3MPa to 300MPa, more preferably 10MPa to 200MPa, and further preferably 30MPa to 150 MPa.
The pressure-responsive particles of the present embodiment may be disposed on the entire surface of the recording medium or may be disposed on a part of the recording medium. The pressure-responsive particles of the present embodiment are disposed in 1 layer or more on the recording medium.
The layer of the pressure-responsive particles of the present embodiment may be a layer continuous in the plane direction of the recording medium, or may be a layer discontinuous in the plane direction of the recording medium. The layer of the pressure-responsive particles of the present embodiment may be a layer in which the pressure-responsive mother particles are aligned in a state of holding the particles, or may be a layer in which adjacent pressure-responsive mother particles are fused and aligned with each other.
The amount of the pressure-responsive particles (preferably transparent pressure-responsive particles) in the present embodiment on the recording medium is, for example, 0.5g/m in the arranged region2Above 50g/m21g/m below2Above 40g/m21.5g/m below2Above 30g/m2The following. The layer thickness of the pressure-responsive particles (preferably transparent pressure-responsive particles) of the present embodiment on the recording medium is, for example, 0.2 μm to 25 μm, 0.4 μm to 20 μm, and 0.6 μm to 15 μm.
Examples of the recording medium suitable for the printed matter manufacturing apparatus of the present embodiment include coated paper, cloth, nonwoven fabric, resin film, resin sheet, and the like, which are discharged or the surface of which is coated with a resin or the like. The recording medium may have images on one side or both sides.
An example of the printed matter manufacturing apparatus according to the present embodiment will be described below, but the present embodiment is not limited thereto.
Fig. 2 is a schematic configuration diagram showing an example of the printed matter manufacturing apparatus of the present embodiment. The printed matter manufacturing apparatus shown in fig. 2 includes a placement mechanism 100 and a pressure bonding mechanism 200 disposed downstream of the placement mechanism 100. The arrow indicates the rotation direction of the photoreceptor or the conveyance direction of the recording medium.
The disposing mechanism 100 is a direct transfer type apparatus that disposes the pressure-responsive particles of the present embodiment on the recording medium P by electrophotography using a developer containing the pressure-responsive particles of the present embodiment. In the recording medium P, an image is formed in advance on one side or both sides.
The arrangement mechanism 100 has a photosensitive body 101. Disposed around the photoreceptor 101 are, in order: a charging roller (an example of a charging mechanism) 102 that charges the surface of the photoreceptor 101; an exposure device (an example of an electrostatic imaging mechanism) 103 that exposes the surface of the charged photoreceptor 101 with laser light to form an electrostatic image; a developing device (an example of a developing mechanism) 104 that supplies the pressure-responsive particles to the electrostatic image to develop the electrostatic image; a transfer roller (an example of a transfer mechanism) 105 for transferring the developed pressure-responsive particle-applying portion onto the recording medium P; and a photoreceptor cleaning device (an example of a cleaning mechanism) 106 that removes the pressure-responsive particles remaining on the surface of the photoreceptor 101 after transfer.
The operation of the disposing mechanism 100 for disposing the pressure-responsive particles of the present embodiment on the recording medium P will be described.
First, the surface of the photoreceptor 101 is charged by the charging roller 102. The exposure device 103 irradiates the surface of the charged photoreceptor 101 with a laser beam based on image data sent from a control unit, not shown. Thereby, an electrostatic image of the arrangement pattern of the pressure-responsive particles of the present embodiment is formed on the surface of the photoreceptor 101.
The electrostatic image formed on the photoreceptor 101 rotates to a development position with the operation of the photoreceptor 101. At the development position, the electrostatic image on the photosensitive member 101 is developed and visualized by the developing device 104, and a pressure-responsive particle-applying portion is formed.
A developer containing at least the pressure-responsive particles of the present embodiment and a carrier is stored in the developing device 104. The pressure-responsive particles of the present embodiment are stirred together with the carrier inside the developing device 104, thereby generating frictional electrification, and are held on the developer roller. The surface of the photoreceptor 101 passes through the developing device 104, whereby the pressure-responsive particles are electrostatically attached to the electrostatic image on the surface of the photoreceptor 101, and the electrostatic image is developed by the pressure-responsive particles. The photoreceptor 101 having the pressure-responsive particle imparting portion formed thereon continues to operate, and the pressure-responsive particle imparting portion developed on the photoreceptor 101 is conveyed to a transfer position.
When the pressure-responsive particle-applying portion on the photosensitive body 101 is conveyed to the transfer position, a transfer bias is applied to the transfer roller 105, and an electrostatic force from the photosensitive body 101 toward the transfer roller 105 acts on the pressure-responsive particle-applying portion, so that the pressure-responsive particle-applying portion on the photosensitive body 101 is transferred onto the recording medium P.
The pressure responsive particles remaining on the photoreceptor 101 are removed and recovered by the photoreceptor cleaning device 106. The photoreceptor cleaning device 106 is, for example, a cleaning blade, a cleaning brush, or the like. The photoreceptor cleaning device 106 is preferably a cleaning brush in order to suppress the phenomenon that the pressure-responsive particles of the present embodiment remaining on the surface of the photoreceptor adhere to the surface of the photoreceptor in a film form due to the flow of pressure.
The recording medium P to which the pressure-responsive particle applying section is transferred is conveyed to a fixing device (an example of a fixing mechanism) 107. The fixing device 107 is, for example, a pair of fixing members (roller/roller, belt/roller). The arrangement mechanism 100 may not include the fixing device 107, but preferably includes the fixing device 107 in order to prevent the pressure-responsive particles of the present embodiment from falling off the recording medium P. The pressure applied to the recording medium P by the fixing device 107 may be lower than the pressure applied to the recording medium P2 by the pressurizing device 230, and specifically, is preferably 0.2MPa or more and 1MPa or less.
The fixing device 107 may or may not have a heat source (e.g., a halogen heater) therein for heating the recording medium P. When the fixing device 107 has a heat source inside, the surface temperature of the recording medium P when heated by the heat source is preferably 150 ℃ to 220 ℃, more preferably 155 ℃ to 210 ℃, and still more preferably 160 ℃ to 200 ℃. When the fixing device 107 does not have a heat source inside, it is not excluded that the temperature inside the fixing device 107 becomes equal to or higher than the ambient temperature due to heat dissipation from the motor and the like provided in the arrangement mechanism 100.
The recording medium P passes through the arrangement mechanism 100, thereby forming the recording medium P1 having the pressure-responsive particles of the present embodiment imparted on the image. The recording medium P1 is conveyed to the pressure bonding mechanism 200.
In the printed matter manufacturing apparatus of the present embodiment, the arrangement mechanism 100 and the pressure bonding mechanism 200 may be in a close manner or in a spaced manner. In the case where the arranging mechanism 100 is spaced apart from the pressure bonding mechanism 200, the arranging mechanism 100 and the pressure bonding mechanism 200 are connected by, for example, a conveying mechanism (e.g., a belt conveyor) that conveys the recording medium P1.
The pressure bonding mechanism 200 includes a folding device 220 and a pressing device 230, and is a mechanism for folding and pressure bonding the recording medium P1.
The folding device 220 folds the recording medium P1 passed through the device, thereby producing a folded recording medium P2. The folding method of the recording medium P2 may be, for example, a double-fold method, a triple-fold method, or a quadruple-fold method, and may be a method in which only a part of the recording medium P2 is folded. The recording medium P2 is in a state in which the pressure-responsive particles according to the present embodiment are disposed on at least a portion of at least one of the two opposing surfaces.
The folding device 220 may have a pair of pressing members (e.g., roller/roll, belt/roll) that apply pressure to the recording medium P2. The pressure applied to the recording medium P2 by the pressing member of the folding device 220 may be lower than the pressure applied to the recording medium P2 by the pressing device 230, and specifically, is preferably 1MPa or more and 10MPa or less.
The pressure-bonding mechanism 200 may include a superimposing device for superimposing the recording medium P1 on another recording medium, instead of the folding device 220. Examples of a method of superimposing the recording medium P1 on another recording medium include a method of superimposing one other recording medium on the recording medium P1, and a method of superimposing 1 other recording medium at each of a plurality of positions on the recording medium P1. The other recording medium may be a recording medium on which an image is formed in advance on one or both sides, may be a recording medium on which no image is formed, or may be a pressure-sensitive printed product prepared in advance.
The recording medium P2 that has left the folding device 220 (or the overlapping device) is conveyed toward the pressing device 230.
The pressing device 230 includes a pair of pressing members (i.e., pressing rollers 231 and 232). The pressure roller 231 and the pressure roller 232 are pressed against each other on the outer peripheral surface thereof, and apply pressure to the recording medium P2 passing therethrough. The pair of pressing members provided in the pressing device 230 is not limited to the combination of the pressing roller and the pressing roller, and may be a combination of the pressing roller and the pressing belt, or a combination of the pressing belt and the pressing belt.
When pressure is applied to the recording medium P2 passing through the pressurizing device 230, the pressure-responsive particles of the present embodiment flow on the recording medium P2 due to the pressure, and exhibit adhesiveness. The pressure applied to the recording medium P2 by the pressurizing device 230 is preferably 3MPa to 300MPa, more preferably 10MPa to 200MPa, and still more preferably 30MPa to 150 MPa.
The pressurizing device 230 may or may not have a heat source (e.g., a halogen heater) for heating the recording medium P2 inside. When the pressurizing device 230 has a heat source inside, the surface temperature of the recording medium P2 when heated by the heat source is preferably 30 ℃ to 120 ℃, more preferably 40 ℃ to 100 ℃, and still more preferably 50 ℃ to 90 ℃. When the pressurizing device 230 does not have a heat source inside, it is not excluded that the temperature inside the pressurizing device 230 becomes equal to or higher than the ambient temperature due to heat dissipation of a motor or the like provided in the pressurizing device 230.
The recording medium P2 passes through the pressurizing device 230, and the folded surfaces are bonded by the fluidized pressure-responsive particles of the present embodiment, thereby producing a pressure-contact printed product P3. In the pressure-contact printed product P3, the facing surfaces are partially or entirely bonded to each other.
The completed press-bonded printed product P3 is discharged from the pressing device 230.
The first embodiment of the pressure-contact printed matter P3 is a pressure-contact printed matter in which the folded recording medium is bonded with the pressure-responsive particles of the present embodiment on the opposite surfaces. The pressure-contact printed product P3 of the present embodiment is manufactured by a printed product manufacturing apparatus provided with a folding apparatus 220.
The second embodiment of the pressure-contact printed matter P3 is a pressure-contact printed matter in which 2 or more recording media stacked one on another are bonded to each other at the opposite surfaces thereof by the pressure-responsive particles of the present embodiment. The pressure-contact printed product P3 of the present embodiment is manufactured by a pressure-contact printed product manufacturing apparatus including a superimposing apparatus.
The printed matter manufacturing apparatus of the present embodiment is not limited to an apparatus of a type that continuously conveys the recording medium P2 from the folding apparatus 220 (or the superimposing apparatus) to the pressing apparatus 230. The printed matter manufacturing apparatus of the present embodiment may be an apparatus of the following embodiment: the recording medium P2 left from the folding device 220 (or the stacking device) is stored, and the recording medium P2 is conveyed to the pressing device 230 after the storage amount of the recording medium P2 reaches a predetermined amount.
In the printed matter manufacturing apparatus of the present embodiment, the folding device 220 (or the superimposing device) and the pressure-bonding and pressurizing device 230 may be in a close manner or in a spaced manner. In the case where the folding device 220 (or the overlapping device) is spaced apart from the crimping and pressurizing device 230, the folding device 220 (or the overlapping device) is connected to the crimping and pressurizing device 230, for example, by a conveying mechanism (e.g., a belt conveyor) that conveys the recording medium P2.
The printed matter manufacturing apparatus of the present embodiment may include a cutting mechanism that cuts the recording medium into a predetermined size. The cutting mechanism is, for example, the following mechanism: a trimming mechanism disposed between the disposing mechanism 100 and the pressure bonding mechanism 200, for cutting out a region which is a part of the recording medium P1 and in which the pressure-responsive particles according to the present embodiment are not disposed; a cutting mechanism disposed between the folding device 220 and the pressing device 230, for cutting out a region which is a part of the recording medium P2 and in which the pressure-responsive particles according to the present embodiment are not disposed; a cutting mechanism disposed downstream of the pressure-contact mechanism 200, for cutting out a region which is a part of the pressure-contact printed product P3 and to which the pressure-responsive particles of the present embodiment are not bonded; and so on.
The printed matter manufacturing apparatus of the present embodiment is not limited to the single-sheet type apparatus. The printed matter manufacturing apparatus of the present embodiment may be an apparatus of the following form: the long-sized recording medium is subjected to a placement step and a pressure-bonding step to form a long-sized pressure-bonded printed product, and then the long-sized pressure-bonded printed product is cut into a predetermined size.
The printed matter manufacturing apparatus of the present embodiment may further include a colored image forming mechanism that forms a colored image on a recording medium by an electrophotographic method using a colored electrostatic image developer. The color imaging mechanism includes, for example:
a photoreceptor;
a charging mechanism for charging the surface of the photoreceptor;
an electrostatic image forming unit configured to form an electrostatic image on the surface of the charged photoreceptor;
a developing mechanism for storing a colored electrostatic image developer and developing an electrostatic image formed on the surface of the photoreceptor into a colored toner image by the colored electrostatic image developer;
a transfer mechanism for transferring the colored toner image formed on the surface of the photoreceptor to the surface of a recording medium; and
and a heat fixing mechanism for heat-fixing the colored toner image transferred to the surface of the recording medium.
The method for producing a printed matter of the present embodiment can be carried out by the production apparatus configured as described above, further including a colored image forming step of forming a colored image on a recording medium by an electrophotographic method using a colored electrostatic image developer. The colored imaging step specifically comprises the steps of:
a charging step of charging the surface of the photoreceptor;
an electrostatic image forming step of forming an electrostatic image on the surface of the charged photoreceptor;
a developing step of developing the electrostatic image formed on the surface of the photoreceptor into a colored toner image with a colored electrostatic image developer;
a transfer step of transferring the colored toner image formed on the surface of the photoreceptor to a surface of a recording medium; and
and a heat fixing step of heat-fixing the colored toner image transferred to the surface of the recording medium.
The color image forming means included in the printed matter manufacturing apparatus of the present embodiment is, for example, the following: a direct transfer type device for directly transferring the colored toner image formed on the surface of the photoreceptor to a recording medium; an intermediate transfer type device that primarily transfers the colored toner image formed on the surface of the photoreceptor to the surface of the intermediate transfer body, and secondarily transfers the colored toner image transferred to the surface of the intermediate transfer body to the surface of a recording medium; a device having a cleaning mechanism for cleaning the surface of the photoreceptor after the transfer of the color toner image and before the charging; a device including a charge removing mechanism for irradiating a charge removing light to the surface of the photoreceptor after the transfer of the color toner image and before charging to remove the charge; and so on. In the case where the color image forming mechanism is an intermediate transfer type device, the transfer mechanism includes, for example: an intermediate transfer body that transfers the colored toner image to a surface; a primary transfer mechanism for primary-transferring the colored toner image formed on the surface of the photoreceptor to the surface of the intermediate transfer member; and a secondary transfer mechanism for secondary-transferring the colored toner image transferred to the surface of the intermediate transfer body to the surface of a recording medium.
In the printed matter manufacturing apparatus of the present embodiment, when the arrangement mechanism of the developer including the pressure-responsive particles of the present embodiment and the color image forming mechanism adopt the intermediate transfer method, the arrangement mechanism and the color image forming mechanism may share the intermediate transfer body and the secondary transfer mechanism.
In the printed matter manufacturing apparatus of the present embodiment, the arrangement mechanism of the developer containing the pressure-responsive particles of the present embodiment and the color image forming mechanism may share a heat fixing mechanism.
An example of the printed matter manufacturing apparatus of the present embodiment including the color image forming means is described below, but the present embodiment is not limited thereto. In the following description, main parts shown in the drawings will be described, and the description of the other parts will be omitted.
Fig. 3 is a schematic configuration diagram showing an example of the printed matter manufacturing apparatus of the present embodiment. The printed matter manufacturing apparatus shown in fig. 3 includes: a printing mechanism 300 that performs both the arrangement of the pressure-responsive particles of the present embodiment on a recording medium and color image formation; and a press bonding mechanism 200 disposed downstream of the printing mechanism 300.
The printing mechanism 300 is a 5-drum tandem printing mechanism and an intermediate transfer printing mechanism. The printing mechanism 300 includes: a unit 10T configuring the pressure responsive particles (T) of the present embodiment; and units 10Y, 10M, 10C, and 10K forming images of respective colors of yellow (Y), magenta (M), cyan (C), and black (K). The unit 10T is a disposing mechanism for disposing the pressure-responsive particles of the present embodiment on the recording medium P using a developer containing the pressure-responsive particles of the present embodiment. The units 10Y, 10M, 10C, and 10K are mechanisms for forming a colored image on the recording medium P using a developer containing a colored toner, respectively. The units 10T, 10Y, 10M, 10C, and 10K employ an electrophotographic method.
The units 10T, 10Y, 10M, 10C, and 10K are juxtaposed spaced apart from each other in the horizontal direction. The units 10T, 10Y, 10M, 10C, and 10K may be process cartridges that are detachable from the printing mechanism 300.
Below the units 10T, 10Y, 10M, 10C, and 10K, an intermediate transfer belt (an example of an intermediate transfer body) 20 is extended through each unit. The intermediate transfer belt 20 is wound around a driving roller 22, a supporting roller 23, and a counter roller 24 that are in contact with the inner surface of the intermediate transfer belt 20, and is driven in a direction from the unit 10T to the unit 10K. An intermediate transfer body cleaning device 21 is provided on the image holding surface side of the intermediate transfer belt 20 so as to face the driving roller 22.
The units 10T, 10Y, 10M, 10C, and 10K are provided with developing devices (an example of a developing mechanism) 4T, 4Y, 4M, 4C, and 4K, respectively. The developing devices 4T, 4Y, 4M, 4C, and 4K are supplied with the pressure-responsive particles, yellow toner, magenta toner, cyan toner, and black toner of the present embodiment stored in the cartridges 8T, 8Y, 8M, 8C, and 8K, respectively.
Since the cells 10T, 10Y, 10M, 10C, and 10K have the same configuration and operation, the cell 10T in which the pressure-responsive particles of the present embodiment are disposed on the recording medium will be described as a representative cell.
The unit 10T has a photoreceptor 1T. Disposed around the photoreceptor 1T are, in order: a charging roller (an example of a charging mechanism) 2T that charges the surface of the photoreceptor 1T; an exposure device (an example of an electrostatic image forming means) 3T that exposes the surface of the charged photoreceptor 1T with laser light to form an electrostatic image; a developing device (an example of a developing mechanism) 4T that supplies the pressure-responsive particles to the electrostatic image to develop the electrostatic image; a primary transfer roller (an example of a primary transfer mechanism) 5T that transfers the developed pressure-responsive particle-applying portion onto the intermediate transfer belt 20; and a photoreceptor cleaning device (an example of a cleaning mechanism) 6T that removes the pressure-responsive particles remaining on the surface of the photoreceptor 1T after the primary transfer. The primary transfer roller 5T is disposed inside the intermediate transfer belt 20 and is disposed at a position facing the photoreceptor 1T.
The operation of the unit 10T is exemplified below, and the configuration of the pressure-responsive particles and the operation of the color image formation of the present embodiment on the recording medium P are explained.
First, the surface of the photoreceptor 1T is charged by the charging roller 2T. The exposure device 3T irradiates the surface of the charged photoreceptor 1T with a laser beam based on image data sent from a control unit, not shown. Thereby, an electrostatic image of the arrangement pattern of the pressure-responsive particles of the present embodiment is formed on the surface of the photoreceptor 1T.
The electrostatic image formed on the photoreceptor 1T rotates to the development position as the photoreceptor 1T operates. At the development position, the electrostatic image on the photoreceptor 1T is developed and visualized by the developing device 4T, and a pressure-responsive particle-applying portion is formed.
The developing device 4T stores therein a developer containing at least the pressure-responsive particles of the present embodiment and a carrier. The pressure-responsive particles of the present embodiment are stirred together with the carrier inside the developing device 4T, thereby generating frictional electrification, and are held on the developer roller. The surface of the photoreceptor 1T passes through the developing device 4T, and thereby the pressure-responsive particles are electrostatically attached to the electrostatic image on the surface of the photoreceptor 1T, and the electrostatic image is developed by the pressure-responsive particles. The photoreceptor 1T on which the pressure-responsive particle applying section is formed continues to operate, and the pressure-responsive particle applying section developed on the photoreceptor 1T is conveyed to the primary transfer position.
When the pressure-responsive particle-applying portion on the photoreceptor 1T is conveyed to the primary transfer position, a primary transfer bias is applied to the primary transfer roller 5T, and an electrostatic force from the photoreceptor 1T toward the primary transfer roller 5T acts on the pressure-responsive particle-applying portion, so that the pressure-responsive particle-applying portion on the photoreceptor 1T is transferred onto the intermediate transfer belt 20. The pressure responsive particles remaining on the photoreceptor 1T are removed and recovered by the photoreceptor cleaning device 6T. The photoreceptor cleaning device 6T is, for example, a cleaning blade, a cleaning brush, or the like, and is preferably a cleaning brush.
The same operation as in the unit 10T is also performed in the units 10Y, 10M, 10C, and 10K using the developer containing the colored toner. The intermediate transfer belt 20 of the pressure-responsive particle applying section to which the pressure-responsive particles of the present embodiment are transferred in the unit 10T passes through the units 10Y, 10M, 10C, and 10K in this order, and multiple transfer of toner images of the respective colors onto the intermediate transfer belt 20 is performed.
The intermediate transfer belt 20, which has undergone multiple transfers of the pressure-responsive particle imparting portion and the toner image through the units 10T, 10Y, 10M, 10C, and 10K, reaches a secondary transfer portion composed of the intermediate transfer belt 20, a counter roller 24 in contact with the inner surface of the intermediate transfer belt, and a secondary transfer roller (an example of a secondary transfer mechanism) 26 disposed on the image holding surface side of the intermediate transfer belt 20. On the other hand, the recording medium P is fed by the feeding member to the gap where the secondary transfer roller 26 contacts the intermediate transfer belt 20, and the secondary transfer bias is applied to the counter roller 24. At this time, an electrostatic force from the intermediate transfer belt 20 toward the recording medium P acts on the pressure-responsive particle applying portion and the toner image, and the pressure-responsive particle applying portion and the toner image on the intermediate transfer belt 20 are transferred onto the recording medium P.
The recording medium P on which the pressure-responsive particle applying section and the toner image are transferred is conveyed to a heat fixing device (an example of a heat fixing mechanism) 28. The heat fixing device 28 includes a heat source such as a halogen heater, and heats the recording medium P. The surface temperature of the recording medium P when heated by the heat fixing device 28 is preferably 150 ℃ to 220 ℃, more preferably 155 ℃ to 210 ℃, and still more preferably 160 ℃ to 200 ℃. The colored toner image is thermally fixed on the recording medium P by passing through the thermal fixing device 28.
The heat fixing device 28 is preferably a device that applies pressure while heating, for example, a pair of fixing members (roller/roller, belt/roller) having a heat source therein may be used, in order to suppress the pressure-responsive particles of the present embodiment from falling off from the recording medium P and to improve the fixing property of the colored image on the recording medium P. In the case where the heat fixing device 28 applies pressure, the pressure applied to the recording medium P by the heat fixing device 28 may be lower than the pressure applied to the recording medium P2 by the pressure device 230, and specifically, is preferably 0.2MPa or more and 1MPa or less.
The recording medium P passes through the printing mechanism 300, and the recording medium P1 to which the color image and the pressure-responsive particles of the present embodiment are applied is formed. The recording medium P1 is conveyed toward the pressure bonding mechanism 200.
The configuration of the pressure bonding mechanism 200 in fig. 3 may be the same as that of the pressure bonding mechanism 200 in fig. 2, and a detailed description of the configuration and operation of the pressure bonding mechanism 200 is omitted.
In the printed matter manufacturing apparatus of the present embodiment, the printing mechanism 300 and the pressure bonding mechanism 200 may be in a close manner or in a spaced manner. The printing mechanism 300 is connected to the pressure bonding mechanism 200, for example, by a conveying mechanism (e.g., a belt conveyor) that conveys the recording medium P1, with the printing mechanism 300 spaced from the pressure bonding mechanism 200.
The printed matter manufacturing apparatus of the present embodiment may include a cutting mechanism that cuts the recording medium into a predetermined size. The cutting mechanism is, for example, the following mechanism: a cutting mechanism disposed between the printing mechanism 300 and the pressure bonding mechanism 200, for cutting out a region which is a part of the recording medium P1 and in which the pressure-responsive particles according to the present embodiment are not disposed; a cutting mechanism disposed between the folding device 220 and the pressing device 230, for cutting out a region which is a part of the recording medium P2 and in which the pressure-responsive particles according to the present embodiment are not disposed; a cutting mechanism disposed downstream of the pressure-contact mechanism 200, for cutting out a region which is a part of the pressure-contact printed product P3 and to which the pressure-responsive particles of the present embodiment are not bonded; and so on.
The printed matter manufacturing apparatus of the present embodiment is not limited to the single-sheet type apparatus. The printed matter manufacturing apparatus of the present embodiment may be an apparatus of the following form: the long-strip-shaped recording medium is subjected to a colored imaging step, a configuration step and a pressure welding step to form a long-strip-shaped pressure welding printed matter, and then the long-strip-shaped pressure welding printed matter is cut into a preset size.
< Process Cartridge >
The process cartridge of the present embodiment will be explained.
The process cartridge according to the present embodiment is a process cartridge that is attachable to and detachable from a printed matter manufacturing apparatus, and includes a developing mechanism that stores the electrostatic image developer according to the present embodiment and develops an electrostatic image formed on a surface of a photoreceptor into a pressure-responsive particle applying portion by the electrostatic image developer.
The process cartridge according to the present embodiment may have a configuration including a developing mechanism and, if necessary, at least one selected from a photoreceptor, a charging mechanism, an electrostatic image forming mechanism, a transfer mechanism, and the like.
An example of an embodiment of the process cartridge is a cartridge in which a photoreceptor, a charging roller (an example of a charging mechanism) provided around the photoreceptor, a developing device (an example of a developing mechanism), and a photoreceptor cleaning device (an example of a cleaning mechanism) are integrated with a casing. The housing has an opening for exposure. The housing has a mounting rail, and the process cartridge is mounted to the printed matter manufacturing apparatus via the mounting rail.
[ examples ]
The following examples are intended to describe embodiments of the invention in detail, but the invention is not limited to these examples. In the following description, "part" and "%" are based on weight unless otherwise specified.
< preparation of Dispersion containing styrenic resin particles >
[ preparation of styrene resin particle Dispersion (St1) ]
The above materials were mixed and dissolved to prepare a monomer solution.
8 parts of an anionic surfactant (Dowfax 2A1, manufactured by Dow Chemical Co.) was dissolved in 205 parts of ion-exchanged water, and the monomer solution was added thereto to carry out dispersion and emulsification, thereby obtaining an emulsion.
2.2 parts of an anionic surfactant (Dowfax 2A1, manufactured by Dow Chemical Co., Ltd.) was dissolved in 462 parts of ion-exchanged water, and the solution was put into a polymerization flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen inlet tube, and heated to 73 ℃ with stirring and held.
3 parts of ammonium persulfate was dissolved in 21 parts of ion-exchanged water, and the solution was added dropwise to the polymerization flask over 15 minutes via a quantitative pump, and then the emulsion was added dropwise over 160 minutes via a quantitative pump.
Subsequently, the polymerization flask was kept at 75 ℃ for 3 hours with continuous slow stirring, and then returned to room temperature.
Thus, a styrene-based resin particle dispersion (St1) containing styrene-based resin particles was obtained, wherein the volume average particle diameter (D50v) of the resin particles was 174nm, the weight average molecular weight measured by 6PC (UV detection) was 49000, the glass transition temperature was 54 ℃, and the solid content was 42%.
The styrene-based resin particle dispersion (St1) was dried, and styrene-based resin particles were taken out, and thermal behavior in a temperature range of-100 ℃ to 100 ℃ was analyzed by a differential scanning calorimeter (DSC-60A manufactured by shimadzu corporation), and a glass transition temperature of 1 was observed. The glass transition temperatures are shown in table 1.
[ preparation of styrene resin particle Dispersion (St2) to (St13) ]
Styrene-based resin particle dispersions (St2) to (St13) were prepared in the same manner as the preparation of the styrene-based resin particle dispersion (St1) by changing the monomers as shown in table 1.
The monomers in table 1 are described by the following abbreviations.
Styrene: st, n-butyl acrylate: BA. 2-ethylhexyl acrylate: 2EHA, ethyl acrylate: EA. 4-hydroxybutyl acrylate: 4HBA, acrylic acid: AA. Methacrylic acid: MAA, 2-carboxyethyl acrylate: CEA
TABLE 1
< preparation of Dispersion containing composite resin particles >
[ preparation of composite resin particle Dispersion (M1) ]
Styrene-based resin particle dispersion (St 1): 1190 parts (solid content 500 parts)
2-ethylhexyl acrylate: 250 portions of
N-butyl acrylate: 250 portions of
Ion-exchanged water: 982 parts of
The above-mentioned material was put into a flask for polymerization, stirred at 25 ℃ for 1 hour, and then heated to 70 ℃.
2.5 parts of ammonium persulfate was dissolved in 75 parts of ion-exchanged water, and was added dropwise to the polymerization flask via a quantitative pump over 60 minutes.
Subsequently, the polymerization flask was kept at 70 ℃ for 3 hours while continuing to stir slowly, and then returned to room temperature.
This gave a composite resin particle dispersion (M1) containing composite resin particles having a volume average particle diameter (D50v) of 219nm, a weight average molecular weight of 219000 by GPC (UV detection), and a solid content of 32%.
The composite resin particle dispersion (M1) was dried, composite resin particles were taken out, and thermal behavior in a temperature range of-150 ℃ to 100 ℃ was analyzed by a differential scanning calorimeter (DSC-60A manufactured by shimadzu corporation), and 2 glass transition temperatures were observed. The glass transition temperatures are shown in table 2.
[ preparation of composite resin particle Dispersion (M2) to (M21) and (cM1) to (cM3) ]
Composite resin particle dispersions (M2) to (M21) and (cM1) to (cM3) were prepared in the same manner as in the preparation of composite resin particle dispersion (M1) by changing styrene resin particle dispersion (St1) as shown in table 2 or by changing the polymerization component of the (meth) acrylate resin as shown in table 2.
[ preparation of composite resin particle Dispersion (M22) to (M27) ]
Composite resin particle dispersions (M22) to (M27) were prepared in the same manner as the preparation of the composite resin particle dispersion (M1) by adjusting the amounts of 2-ethylhexyl acrylate and n-butyl acrylate.
The following monomers are described by the following abbreviations.
Styrene: st, n-butyl acrylate: BA. 2-ethylhexyl acrylate: 2EHA, ethyl acrylate: EA. 4-hydroxybutyl acrylate: 4HBA, acrylic acid: AA. Methacrylic acid: MAA, 2-carboxyethyl acrylate: CEA, hexyl acrylate: HA. Propyl acrylate: PA
TABLE 2
[ preparation of composite resin Fine particle Dispersion (M28) to (M30) ]
Composite resin particle dispersions (M28) to (M30) having different weight average molecular weights of composite resin particles were prepared in the same manner as the preparation of the composite resin particle dispersion (M1) except that the amount of ammonium persulfate was changed in the same manner as the preparation of the composite resin particle dispersion (M1) but in table 3.
TABLE 3
| Ammonium persulfate | |
| M28 | 3.0 parts of |
| M29 | 5.0 parts of |
| M30 | 7.5 parts of |
The composition and physical properties of the composite resin particle dispersion (M28) and the like are shown in table 4. The monomers in table 4 are described by the following abbreviations.
Styrene: st; n-butyl acrylate: BA; acrylic acid: AA; 2-ethylhexyl acrylate: 2EHA
[ Table 4]
< preparation of pressure-responsive particles >
[ preparation of pressure-responsive particles (1) ]
Composite resin particle dispersion (M1): 504 portions of
Ion-exchanged water: 710 portions of
Anionic surfactant (manufactured by dow chemical, Dowfax2a 1): 1 part of
The above materials were charged into a reaction vessel equipped with a thermometer and a pH meter, 1.0% nitric acid aqueous solution was added at 25 ℃ to adjust the pH to 3.0, and then dispersed at 5000rpm using a homogenizer (manufactured by IKA corporation, ULTRA-TURRAXT50), and 23 parts of 2.0% aluminum sulfate aqueous solution was added. Next, a stirrer and a heating mantle were placed in the reaction vessel, the temperature was raised to 40 ℃ at a temperature rise rate of 0.2 ℃/min, the temperature was raised at a temperature rise rate of 0.05 ℃/min after the temperature exceeded 40 ℃, and the particle size was measured at intervals of 10 minutes by means of a multisizer II (pore size 50 μm, manufactured by Beckmann Coulter). After the volume average particle diameter reached 5.0. mu.m, 170 parts of a styrene resin particle dispersion (St1) was charged for 5 minutes while keeping the temperature. After the completion of the charging, the mixture was held at 50 ℃ for 30 minutes, and then a 1.0% aqueous solution of sodium hydroxide was added to adjust the pH of the slurry to 6.0. Subsequently, the pH was adjusted to 6.0 every 5 ℃ and the temperature was raised to 90 ℃ at a rate of 1 ℃/min and maintained at 90 ℃. The shape and surface properties of the particles were observed by an optical microscope and a field emission scanning electron microscope (FE-SEM), and as a result, the combination of the particles was confirmed at 10 hours, so that it took 5 minutes to cool the vessel to 30 ℃ with cooling water.
The cooled slurry was passed through a nylon mesh having a mesh opening of 15 μm to remove coarse particles, and the slurry passed through the mesh was filtered under reduced pressure by an aspirator. The solid content remaining on the filter paper was finely kneaded as much as possible by hand, and the resultant was put into ion-exchanged water (temperature 30 ℃ C.) having a solid content of 10 times that of the filter paper and stirred for 30 minutes. Subsequently, the solid content remaining on the filter paper was finely ground as much as possible by hand by filtration under reduced pressure using an aspirator, and the resultant was put into ion-exchanged water (temperature 30 ℃ C.) having a solid content of 10 times, stirred for 30 minutes, and then again filtered under reduced pressure using an aspirator to measure the conductivity of the filtrate. This operation was repeated until the conductivity of the filtrate reached 10. mu.S/cm or less, and the solid content was washed.
The washed solid content was finely ground with a wet dry granulator (pulverizing granulator), and vacuum-dried in an oven at 25 ℃ for 36 hours to obtain pressure-responsive master pellets (1). The volume average particle diameter of the pressure-responsive mother particles (1) was 8.0. mu.m.
100 parts of the pressure-responsive master batch (1) was mixed with 1.5 parts of hydrophobic silica (RY 50, manufactured by nipponeerosil corporation), and mixed using a sample mill at a rotation speed of 13000rpm for 30 seconds. The pressure-responsive particles (1) were obtained by sieving with a vibrating sieve having a mesh opening of 45 μm.
The thermal behavior in the temperature range of-150 ℃ to 100 ℃ was analyzed by a differential scanning calorimeter (DSC-60A, manufactured by Shimadzu corporation) using the pressure-responsive particles (1) as a sample, and 2 glass transition temperatures were observed. The glass transition temperatures are shown in table 5.
The temperature T1 and the temperature T2 of the pressure-responsive particle (1) were determined by the above-mentioned measurement method, and as a result, the pressure-responsive particle (1) satisfied the expression 1 "T1-T2. degreeC.10-C".
The cross section of the pressure-responsive particle (1) was observed by a Scanning Electron Microscope (SEM), and as a result, the sea-island structure was observed. The pressure-responsive particle (1) has a core portion in which an island phase exists and a shell portion in which the island phase does not exist. The sea phase contains a styrene-based resin and the island phase contains a (meth) acrylate-based resin. The average diameter of the island phase was determined by the above-described measurement method. The average diameter of the island phases is shown in table 5.
[ production of pressure-responsive particles (2) to (27) ]
Pressure-responsive particles (2) to (27) were prepared in the same manner as in the preparation of the pressure-responsive particle (1) except that the composite resin particle dispersion and the styrene-based resin particle dispersion were changed as shown in table 5.
The temperature T1 and the temperature T2 of the pressure-responsive particles (2) to (27) were determined by the above-mentioned measurement method, and as a result, all of the pressure-responsive particles (2) to (27) satisfied the expression 1 "T1 to T2 at 10 ℃.
[ production of pressure-responsive particles (28) to (30) ]
The composite resin particle dispersion was changed as described in table 6 in the same manner as in the preparation of the pressure-responsive particles (1), to prepare the pressure-responsive particles (28) to (30).
The temperature T1 and the temperature T2 of the pressure-responsive particles (28) to (30) were determined by the above-described measurement method, and as a result, all of the pressure-responsive particles (28) to (30) satisfied the expression 1 "T1 to T2 at 10 ℃.
[ preparation of pressure-responsive particles (31) ]
The composite resin particle dispersion (M1) was dried, and the obtained composite resin particles (M31) were thermally kneaded by an extruder having a set temperature of 100 ℃, cooled, and then finely pulverized and classified to obtain pressure-responsive master particles (31) having a volume average particle diameter of 8.0. mu.m.
100 parts of the pressure-responsive master batch (31) was mixed with 1.5 parts of hydrophobic silica (RY 50, manufactured by nipponeerosil corporation), and mixed using a sample mill at a rotation speed of 13000rpm for 30 seconds. The pressure-responsive particles (31) were obtained by sieving with a vibrating sieve having a mesh opening of 45 μm.
The thermal behavior at a temperature ranging from 150 ℃ to 100 ℃ was analyzed by a differential scanning calorimeter (DSC-60A, manufactured by Shimadzu corporation) using the pressure-responsive particles (31) as a sample, and 2 glass transition temperatures were observed. The glass transition temperatures are shown in table 6.
The temperature T1 and the temperature T2 of the pressure-responsive particles (31) were determined by the above method, and as a result, the pressure-responsive particles (31) satisfied the expression 1 "T1-T2. degreeC.10-C".
[ production of pressure-responsive particles (c1) to (c3) for comparison ]
Pressure-responsive particles (c1) to (c3) were prepared in the same manner as in the preparation of the pressure-responsive particle (1) by changing the composite resin particle dispersion and the styrene-based resin particle dispersion as shown in table 3.
[ evaluation of pressure responsive phase Change ]
A temperature difference (T1-T3) is determined as an index indicating that the pressure-responsive particles are likely to undergo a phase change due to pressure. Each pressure-responsive pellet was used as a sample, and the temperature T1 and the temperature T3 were measured by a flow tester (CFT-500, manufactured by Shimadzu corporation) to calculate a temperature difference (T1-T3). The temperature differences (T1-T3) are shown in Table 6.
[ evaluation of adhesiveness ]
As a recording medium, postcard paper V424 manufactured by fuji xerox corporation was prepared. An image having an area density of 30% in which black characters and a full-color photographic image were mixed was formed on one surface of a sheet for postcard using a yellow toner, a magenta toner, a cyan toner, and a black toner, which are commercially available from fuji scholar co.
The pressure-responsive particles were incorporated at a given amount of 3g/m2The pressure-responsive particles are spread over the entire image forming surface of the postcard paper and passed through a belt roller type fixing machine to fix the pressure-responsive particles to the image forming surface of the postcard paper, thereby forming a layer of the pressure-responsive particles.
The postcard paper having the layer of the pressure-responsive particles on the image forming surface was folded in half using a capper PRESSLE multi ii manufactured by topbanforms corporation such that the image forming surface was inside, and pressure was applied to the postcard paper after folding in half to bond the image forming surfaces inside to each other at a pressure of 90 MPa.
10 postcards, which were folded in half so that the image forming surface was on the inside and the image forming surfaces were adhered to each other, were continuously produced under the above-described apparatus and conditions.
The 10 th postcard was cut out in the longitudinal direction at a width of 15mm to prepare a rectangular test piece, and a 90-degree peel test was performed. The load (N) from 10mm to 50mm after the start of measurement was sampled at 0.4mm intervals, and the average was calculated, assuming that the peeling rate in the 90-degree peeling test was 20 mm/min, and the load (N) of the three test pieces was further averaged. The load (N) required for peeling was classified as follows. The results are shown in tables 5 and 6.
A: 0.8N or more
B: more than 0.6N and less than 0.8N
C: 0.4N or more and less than 0.6N
D: 0.2N or more and less than 0.4N
E: less than 0.2N
TABLE 5
< preparation of Dispersion containing composite resin particles >
[ preparation of composite resin particle Dispersion (M50) ]
Styrene-based resin particle dispersion (St 1): 1190 parts (solid content 500 parts)
2-ethylhexyl acrylate: 200 portions of
N-butyl acrylate: 200 portions of
Ion-exchanged water: 1360 parts of
The above materials were put into a flask for polymerization, stirred at 25 ℃ for 1 hour, and then heated to 70 ℃.
2.5 parts of ammonium persulfate was dissolved in 75 parts of ion-exchanged water, and was added dropwise to the polymerization flask via a metering pump over 60 minutes.
Subsequently, the polymerization flask was kept at 70 ℃ for 2 hours with continuous slow stirring, and then a mixture of 85 parts of styrene and 15 parts of n-butyl acrylate was added dropwise thereto over 60 minutes. After the dropwise addition, the mixture was kept at 75 ℃ for 3 hours and then returned to room temperature.
This gave a composite resin particle dispersion (M50) containing composite resin particles, the volume average particle diameter (D50v) of the resin particles being 223nm, the weight average molecular weight by GPC (UV detection) being 220000, and the solid content being 32%.
The composite resin particle dispersion (M50) was dried, and composite resin particles were taken out and subjected to thermal behavior analysis at a temperature ranging from-150 ℃ to 100 ℃ by a differential scanning calorimeter (DSC-60A, manufactured by shimadzu corporation), and 2 glass transition temperatures were observed. The glass transition temperatures are shown in table 7.
[ preparation of composite resin particle Dispersion (M51) to (M55) ]
In the same manner as in the preparation of the composite resin particle dispersion liquid (M50), the materials were changed to the specifications shown in table 15, and composite resin particle dispersion liquids (M51) to (M55) were prepared.
The composition and physical properties of the composite resin particle dispersion (M50) and the like are shown in table 7. The monomers in table 7 are described by the following abbreviations.
Styrene: st; n-butyl acrylate: BA; acrylic acid: AA; 2-ethylhexyl acrylate: 2EHA
< preparation of pressure-responsive particles >
[ preparation of pressure-responsive particles (50) to (55) ]
Pressure-responsive particles (50) to (55) were prepared in the same manner as in the preparation of the pressure-responsive particle (1) except that the materials were changed to the specifications shown in table 8.
The thermal behavior at a temperature ranging from-150 ℃ to 100 ℃ was analyzed by a differential scanning calorimeter (DSC-60A, manufactured by Shimadzu corporation) using the pressure-responsive particles (50) to (55) as samples, and 2 glass transition temperatures were observed. The glass transition temperatures are shown in table 8.
The temperature T1 and the temperature T2 of the pressure-responsive particles (50) to (55) were determined by the above-mentioned measurement method, and as a result, all of the pressure-responsive particles (50) to (55) satisfied the expression 1 "T1 to T2 at 10 ℃.
The cross sections of the pressure-responsive particles (50) to (55) were observed by a Scanning Electron Microscope (SEM), and as a result, a sea-island structure was observed. The pressure-responsive particles (50) to (55) have a core portion in which an island phase is present and a shell portion in which an island phase is not present. The sea phase contains a styrene resin and the island phase contains a (meth) acrylate resin. The average diameter of the island phase was determined by the above-described measurement method. The average diameter of the island phase is shown in table 8.
[ evaluation of stress-responsive phase transition ]
Each pressure-responsive pellet was used as a sample, and the temperature T1 and the temperature T3 were measured by a flow tester (CFT-500, manufactured by Shimadzu corporation) to calculate a temperature difference (T1-T3). Table 8 shows the temperature differences (T1-T3).
[ evaluation of adhesiveness ]
The adhesiveness was evaluated by the above-described evaluation method of [ evaluation of adhesiveness ] similarly to the pressure-responsive particles (1). The results are shown in table 8.
< production of printed matter by electrophotography >
10 parts of any one of the pressure-responsive particles (1) to (31), (c1) to (c3), and (50) to (55) and 100 parts of the following resin-coated carrier (1) were charged into a V-blender and stirred for 20 minutes, followed by sieving with a vibrating sieve having a mesh opening of 212. mu.m, to obtain developers (1) to (31), (c1) to (c3), and (50) to (55), respectively.
Resin-coated carrier (1)
Mn-Mg-Sr ferrite particles (average particle size 40 μm): 100 portions of
Toluene: 14 portions of
Polymethyl methacrylate: 2 portions of
Carbon black (VXC 72: manufactured by Cabot): 0.12 portion
The above-mentioned materials except for the ferrite particles were mixed with glass beads (diameter: 1mm, same amount as toluene) and stirred for 30 minutes at a rotation speed of 1200rpm using a sand mill manufactured by Kansai Paint company to obtain a dispersion. The dispersion and ferrite particles were charged into a vacuum degassing kneader, and dried under reduced pressure with stirring, thereby obtaining a resin-coated carrier (1).
As a printed matter manufacturing apparatus, an apparatus of the embodiment shown in fig. 3 was prepared. That is, a device for manufacturing a printed matter is prepared, which includes a printing mechanism of a 5-drum tandem system and an intermediate transfer system that perform the arrangement of the pressure-responsive particles on the recording medium and the color image formation of the present embodiment in common, and a pressure-bonding mechanism having a folding device and a pressing device.
The developer (or the developer for comparison) of the present embodiment, the yellow developer, the magenta developer, the cyan developer, and the black developer are loaded into 5 developers included in the printing mechanism, respectively. A developer having various colors such as yellow is commercially available from fuji scholer co.
A postcard sheet V424 manufactured by fuji xerox corporation was prepared as a recording medium.
The image formed on the postcard paper is an image having an area density of 30% in which black characters and a full-color photographic image are mixed, and is formed on one side of the postcard paper.
The amount of pressure-responsive particles (or pressure-responsive particles for comparison) applied to the image forming area of the image forming surface of the postcard paper in the present embodiment is 3g/m2。
The folding device is a device that folds the postcard paper in half so that the image forming surface is on the inside.
The pressure of the pressurizing device is set to 90 MPa.
10 postcards, which were folded in half with the image forming surface on the inner side and the image forming surfaces of which were adhered to each other, were continuously produced under the above-described apparatus and conditions.
The 10 th postcard was cut out in the longitudinal direction at a width of 15mm to prepare a rectangular test piece, and a 90-degree peel test was performed. The peeling speed in the 90 degree peeling test was set to 20 mm/min, and the load (N) from 10mm to 50mm after the start of the measurement was sampled at intervals of 0.4mm, and the average was calculated, and the load (N) of the three test pieces was further averaged. The load (N) required for peeling was classified as follows. The results are shown in tables 9, 10 and 11.
A: 0.8N or more
B: more than 0.6N and less than 0.8N
C: 0.4N or more and less than 0.6N
D: 0.2N or more and less than 0.4N
E: less than 0.2N
[ Table 9]
| Developing agent | Pressure responsive particles | Adhesion Property | Remarks for note |
| c1 | c1 | D | Comparative example |
| c2 | c2 | D | Comparative example |
| c3 | c3 | D | Comparative example |
| 1 | 1 | A | The invention |
| 2 | 2 | A | The invention |
| 3 | 3 | A | The invention |
| 4 | 4 | A | The invention |
| 5 | 5 | A | The invention |
| 6 | 6 | A | The invention |
| 7 | 7 | A | The invention |
| 8 | 8 | A | The invention |
| 9 | 9 | A | The invention |
| 10 | 10 | A | The invention |
| 11 | 11 | A | The invention |
| 12 | 12 | A | The invention |
| 13 | 13 | A | The invention |
| 14 | 14 | B | The invention |
| 15 | 15 | B | The invention |
| 16 | 16 | B | The invention |
| 17 | 17 | A | The invention |
| 18 | 18 | A | The invention |
| 19 | 19 | A | The |
| 20 | 20 | A | The |
| 21 | 21 | B | The invention |
| 22 | 22 | C | The invention |
| 23 | 23 | B | The |
| 24 | 24 | A | The invention |
| 25 | 25 | A | The |
| 26 | 26 | A | The invention |
| 27 | 27 | A | The invention |
[ Table 10]
| Developing agent | Pressure responsive particles | Adhesion Property | Remarks for |
| 28 | 28 | A | The invention |
| 29 | 29 | A | The invention |
| 30 | 30 | B | The invention |
| 31 | 31 | B | The invention |
[ Table 11]
| Developing agent | Pressure responsive particles | Adhesion Property | Remarks for note |
| 50 | 50 | A | The invention |
| 51 | 51 | A | The invention |
| 52 | 52 | A | The invention |
| 53 | 53 | A | The invention |
| 54 | 54 | A | The invention |
| 55 | 55 | A | The invention |
[ examples ]
< production of resin particles for core portion >
(production of core resin particle Dispersion (A1))
Styrene: 440 portion of
N-butyl acrylate: 130 portions of
Acrylic acid: 20 portions of
Dodecanethiol: 5 portions of
The above components were mixed and dissolved to prepare a solution a.
Further, 10 parts of an anionic surfactant (DOWFAX 2a1, manufactured by dow chemical) was dissolved in 250 parts of ion-exchanged water, and the solution a was added to disperse the solution in a flask and emulsify the solution (monomer emulsion a).
Further, 1 part of the same anionic surfactant (DOWFAX 2a1, manufactured by dow chemical) was dissolved in 555 parts of ion-exchanged water, and charged into a polymerization flask. A reflux tube was placed in the polymerization flask, and the flask was heated to 75 ℃ in a water bath with stirring while injecting nitrogen gas, and the temperature was maintained.
9 parts of ammonium persulfate was dissolved in 43 parts of ion-exchanged water, and the solution was added dropwise to a polymerization flask into which an aqueous solution of an anionic surfactant was charged, over 20 minutes via a metering pump, followed by adding dropwise the monomer emulsion a over 200 minutes via the metering pump.
The flask for polymerization was then kept at 75 ℃ for 3 hours with continuous stirring, and the polymerization of stage 1 was completed. Thus, a precursor of a resin particle dispersion (A1) for core portion in which styrene resin particles having a volume average particle diameter of 195nm, a glass transition temperature of 53 ℃ and a weight average molecular weight of 32,000 were dispersed was obtained.
Subsequently, after the temperature was lowered to room temperature (25 ℃), 240 parts of 2-ethylhexyl acrylate, 160 parts of n-butyl acrylate, 7 parts of decanethiol, and 1200 parts of ion-exchanged water were added to the polymerization flask to which the precursor of the resin particle dispersion for core (a1) was added, and the mixture was stirred slowly for 2 hours. Then, the temperature was raised to 70 ℃ with continuous stirring, and 4.5 parts of ammonium persulfate and 100 parts of ion-exchanged water were added dropwise over 20 minutes via a quantitative pump. Then, the mixture was kept for 3 hours under continuous stirring, and the polymerization was terminated. The above procedure gave a core resin particle dispersion (a1) in which composite resin particles having a volume average particle diameter of 240nm, a weight average molecular weight of 133,000 and a number average molecular weight of 18,000 were dispersed and which was adjusted to a solid content of 30 wt% by adding ion-exchanged water.
The resin particles of the obtained resin particle dispersion for core portion (a1) were dried, and a sample in which the dried resin particles were embedded in an epoxy resin was prepared. Then, the sample was cut with a diamond knife to prepare a cut section of the resin pellet. Then, the cross section of the sample was stained with ruthenium tetroxide vapor and observed with a transmission electron microscope. From the results of the cross-sectional observation of the resin particles, it was confirmed that the resin particles had a structure in which a plurality of regions of a low Tg (meth) acrylate resin were dispersed in a high Tg styrene resin as a base material.
The dried resin particles were analyzed for their glass transition temperature Tg behavior at-150 ℃ to 100 ℃ by a Differential Scanning Calorimeter (DSC) manufactured by Shimadzu corporation, and the glass transition by the low Tg (meth) acrylate resin was observed at-59 ℃. Further, a glass transition (difference in glass transition temperature: 112 ℃) attributed to the high Tg styrene resin was observed at 53 ℃.
(production of core resin particle Dispersion (A2-A5))
Composite resin particles having a volume average particle diameter in the range of 200nm to 240nm were dispersed in the same manner as in the core resin particle dispersion liquid (a1) except that the amount of dodecanethiol added in the preparation of the core resin particle dispersion liquid (a1) precursor was changed as shown in table 1 and the amounts of 2-ethylhexyl acrylate and n-butyl acrylate added after the preparation of the core resin particle dispersion liquid (a1) precursor were changed as shown in table 12, and the solid content was adjusted to 30 wt% by adding ion-exchanged water, thereby obtaining core resin particle dispersions (a2) to a 5).
The weight average molecular weight, the number average molecular weight, and the glass transition temperature difference of the composite resin particles contained in the core resin particle dispersions (a2) to (a5) are shown in table 12.
TABLE 12
< preparation of resin particle Dispersion for Shell >
(production of resin particle Dispersion for Shell (B1))
Styrene: 450 portions of
N-butyl acrylate: 135 portions of
Acrylic acid: 10 portions of
Dodecanethiol: 5 portions of
The above components were mixed and dissolved to prepare a solution B.
Further, 10 parts of an anionic surfactant (DOWFAX 2a1, manufactured by dow chemical) was dissolved in 250 parts of ion-exchanged water, and the solution B was added to the solution to disperse and emulsify the solution in a flask (monomer emulsion B).
Further, 1 part of the same anionic surfactant (DOWFAX 2a1, manufactured by dow chemical) was dissolved in 555 parts of ion-exchanged water, and charged into a polymerization flask. A reflux tube was placed in the polymerization flask, and the flask was heated in a water bath to 75 ℃ while stirring slowly with nitrogen gas being injected.
9 parts of ammonium persulfate was dissolved in 43 parts of ion-exchanged water, and the solution was added dropwise to a polymerization flask into which an aqueous solution of an anionic surfactant was introduced, over 20 minutes via a metering pump, followed by adding dropwise the monomer emulsion B over 200 minutes via the metering pump.
Then, the flask for polymerization was kept at 75 ℃ for 3 hours with continuous stirring, and the polymerization in the 1 st stage was terminated. Thus, a resin particle dispersion for a shell (B1) in which styrene resin particles having a volume average particle diameter of 200nm, a glass transition temperature of 53 ℃, a weight average molecular weight of 33,000, and a number average molecular weight of 15,000 were dispersed and which was adjusted to a solid content of 30 wt% by adding ion-exchanged water was obtained.
< preparation of Release agent Dispersion >
(production of Release agent Dispersion (1))
Fischer-Tropsch wax: 270 portions of
(product name: FNP-0090, melting temperature: 90 ℃ manufactured by Nippon Seiro corporation)
Anionic surfactant: 1.0 part
(first Industrial pharmaceutical Co., Ltd., NEOGENRK)
Ion-exchanged water: 400 portions of
The above components were mixed, heated to 95 ℃ and dispersed using a homogenizer (ULTRA-TURRAXT50, manufactured by IKA corporation), and then a dispersion treatment was performed for 360 minutes using a MantonGaulin high pressure homogenizer (Gaulin corporation) to prepare a release agent dispersion (1) (solid content concentration: 20 wt%) in which release agent particles having a volume average particle diameter of 0.23 μm were dispersed.
< preparation of transparent pressure-responsive mother particle >
(preparation of transparent pressure-responsive mother particle (A1))
Resin particle dispersion liquid for core portion (a 1): 600 portions of
Release agent dispersion (1): 10 portions of
Aqueous colloidal silica solution: 13 portions of
(SnowtexOS, manufactured by Nissan chemical Co., Ltd.)
Ion-exchanged water: 1000 portions
Anionic surfactant: 1 part of
(Dowfax 2A1, manufactured by Dow chemical Co., Ltd.)
The above-mentioned components as a core portion-forming material were charged into a 3 liter reaction vessel equipped with a thermometer, a pH meter and a stirrer, 1.0 wt% nitric acid was added at 25 ℃ to adjust the pH to 3.0, and then 4 parts of the prepared 10 wt% polyaluminum chloride aqueous solution was added thereto and further dispersed for 6 minutes while dispersing at 5,000rpm by a homogenizer (manufactured by IKAJapan K.K., ULTRA-TURRAXT 50).
Then, a stirrer and a heating jacket were installed in the reaction vessel, the rotation speed of the stirrer was adjusted so as to sufficiently stir the slurry, the temperature was raised to 40 ℃ at a temperature rise rate of 0.2 ℃/min, and after the temperature exceeded 40 ℃, the temperature was raised at a temperature rise rate of 0.05 ℃/min, and the particle size was measured every 10 minutes by multisizer II (manufactured by Kulter, with a pore size of 50 μm). After the volume average particle diameter reached 7.5 μm, the temperature was maintained, and 115 parts of the resin particle dispersion for shell section (B1) as a material for shell section formation was charged over 5 minutes. After 30 minutes of holding, the pH was adjusted to 6.0 using a1 wt% aqueous solution of sodium hydroxide. Then, the pH was adjusted to 6.0 at 5 ℃ intervals in the same manner, and the temperature was raised to 90 ℃ at a rate of 1 ℃ per minute and maintained at 96 ℃. The shape and surface properties of the particles were observed by an optical microscope and a scanning electron microscope (FE-SEM), and as a result, since the combination (unification) of the particles was confirmed 2.0 hours after the start of the retention at 96 ℃, the vessel was cooled to 30 ℃ for 5 minutes with cooling water.
The cooled slurry was passed through a nylon mesh having a mesh opening of 30 μm to remove coarse powder, and the pressure-responsive particle slurry having passed through the mesh opening was subjected to vacuum filtration by means of an aspirator. The pressure responsive particles remaining on the filter paper were kneaded to be as finely divided as possible by hand, and put into ion-exchanged water 10 times the amount of the pressure responsive particles at a temperature of 30 ℃ and stirred and mixed for 30 minutes. Then, the mixture was subjected to reduced pressure filtration using an aspirator, the pressure-responsive particles remaining on the filter paper were kneaded into fine particles as much as possible by hand, and the fine particles were put into ion-exchanged water 10 times the amount of the pressure-responsive particles at a temperature of 30 ℃ and stirred and mixed for 30 minutes, and then, the mixture was subjected to reduced pressure filtration using an aspirator again, and the electric conductivity of the filtrate was measured. This operation was repeated until the conductivity of the filtrate reached 10. mu.S/cm or less, and the pressure-responsive particles were washed. The washed pressure-responsive particles were finely pulverized by a wet dry granulator (pulverizing granulator), and then dried in a desiccator at 25 ℃ under vacuum for 36 hours to obtain transparent pressure-responsive mother particles (a 1). The obtained transparent pressure-responsive mother particle (A1) had a volume average particle diameter of 8.5 μm, a weight average molecular weight of 125,000 and a number average molecular weight of 17,000.
Further, a cross section of the transparent pressure-responsive mother particle (a1) was observed by a Scanning Electron Microscope (SEM), and as a result, a sea-island structure was observed. The transparent pressure-responsive mother particle (a1) has a core portion in which an island phase exists and a shell portion in which the island phase does not exist. The sea phase contains a styrene resin and the island phase contains a (meth) acrylate resin. The average diameter of the island phase was determined by the above-described measurement method. Table 13 shows the average diameter of the island phases.
(preparation of transparent pressure-responsive mother particles (A2) - (A5))
Transparent pressure-responsive mother particles (a2) to (a6) were produced in the same manner as for the transparent pressure-responsive mother particle (a1) except that the resin particle dispersion liquid for a core shown in table 2 was used instead of the resin particle dispersion liquid for a core (a 1).
The weight average molecular weight, number average molecular weight, and temperature T of the transparent pressure-responsive mother particles (A2) to (A6)2Temperature difference (T)1-T2) And the results of measuring the average diameters of the island phases are shown in Table 13.
Watch 13
< preparation of surface-treated titanium oxide particles >
(preparation of surface-treated titanium oxide (T1))
200ml of methanol was charged into a 1L beaker, 10g of STT100(STT 100: 30nm in average primary particle diameter, manufactured by titanium industries, Ltd.) was charged, ultrasonic dispersion was carried out for 2 minutes, and then the mixture was stirred for 10 minutes by a stirrer. To the dispersion, 1g of dimethyldimethoxysilane as a surface treatment agent was added and the mixture was further stirred for 60 minutes. Then, the dispersion was subjected to suction filtration and solid-liquid separation, and the separated titanium oxide particle cake was reacted by heating at 120 ℃ for 60 minutes in a chamber (chamber).
The solidified titanium oxide particles were crushed by a planetary ball mill to obtain surface-treated titanium oxide particles (T1). The results are shown in Table 14.
(preparation of surface-treated titanium oxides (T2) to (T6))
Surface-treated titanium oxide particles (T2) to T6) were produced in the same manner as the surface-treated titanium oxide particles (T1) except that the average primary particle diameter, the surface treatment agent, and the treatment amount were changed as shown in table 14.
TABLE 14
< production of externally-added transparent pressure-responsive particles >
(preparation of externally-added transparent pressure-responsive particles (A1))
Then, 1.0 part of hydrophobic silica (manufactured by AEROSIL corporation, RY50, having an average primary particle diameter of 40nm) and 1.5 parts of surface-treated titanium oxide particles T1(1.5 parts) were added to 100 parts of the obtained transparent pressure-responsive master batch (1), and mixed at 13000rpm for 30 seconds using a sample mill. Then, the granules were sieved with a vibrating sieve having a mesh opening of 45 μm to prepare externally-added transparent pressure-responsive granules (A1). The volume average particle diameter of the obtained external transparent pressure-responsive particles (A1) was 8.5. mu.m. In addition, T1 and T2 in the externally added transparent pressure-responsive particles (A1) were found by the above method, and as a result, the externally added transparent pressure-responsive particles (A1) satisfied the expression 1 "T1-T2. degreeC.ltoreq.10 ℃.
< preparation of clear developer >
(preparation of transparent developer (A1))
8 parts of the externally added transparent pressure-responsive particles (A1) and 100 parts of the following carrier (1) were mixed by a V-blender to prepare a transparent developer (A1).
(preparation of Carrier (1))
Ferrite particles (volume average particle diameter: 36 μm): 100 portions of
Toluene: 14 portions of
Styrene-methyl methacrylate copolymer: 2 portions of
(composition ratio: 90/10, Mw 80000)
Carbon black (R330: manufactured by Cabot Co., Ltd.): 0.2 part
First, the above components except for ferrite particles were stirred with a stirrer for 10 minutes to prepare a dispersed coating solution, and then the coating solution and the ferrite particles were put into a vacuum degassing type kneader and stirred at 60 ℃ for 30 minutes, and then further degassed under reduced pressure under heating and dried to obtain a carrier.
(preparation of transparent developers (A2) - (A12))
Transparent developers (a2) to (a12) were produced in the same manner as the transparent developer (a1) except that the externally added transparent pressure-responsive particles including the pressure-responsive mother particles and the surface-treated titanium oxide particles shown in table 15 were used instead of the externally added transparent pressure-responsive particles (a 1).
Next, the production of a developer containing various colored toners (hereinafter also referred to as "colored developer") used in the present embodiment will be described.
< preparation of colored toner >
(preparation of Each Dispersion)
Crystalline polyester resin dispersion (A)
After a monomer component comprising 100 mol% of dimethyl sebacate and 100 mol% of nonanediol and 0.4 part of dibutyltin oxide as a catalyst per 100 parts of the monomer component were charged into a three-necked flask after heating and drying, the atmosphere in the vessel was changed to an inert atmosphere by a nitrogen gas through a pressure reduction operation, and stirring and refluxing were carried out at 180 ℃ for 4 hours by mechanical stirring.
Then, the temperature was gradually increased to 230 ℃ under reduced pressure, stirring was carried out for 2 hours, and after the mixture became viscous, the reaction was stopped by air cooling, and a crystalline polyester resin (1) was synthesized. The crystalline polyester resin (1) obtained was measured for molecular weight (in terms of polystyrene) by gel permeation chromatography to obtain a weight average molecular weight (Mw) of 15800, a number average molecular weight (Mn) of 3800 and an acid value of 13.2 mgKOH/g.
In addition, the melting point (Tm) of the crystalline polyester resin (1) was measured using a Differential Scanning Calorimeter (DSC), and a clear endothermic peak was shown, and the endothermic peak temperature was 77.0 ℃.
Next, using the crystalline polyester resin (1), a resin particle dispersion liquid was prepared.
Crystalline polyester resin (1): 90 portions of
Ionic surfactant (neogenerk, first industrial pharmaceutical): 1.8 parts of
Ion-exchanged water: 210 portions of
The above components were mixed, heated to 100 ℃ and dispersed by a homogenizer (ULTRA-TURRAXT50, IKA), and then heated to 110 ℃ by a pressure jet Gaulin homogenizer for 1 hour to obtain a crystalline polyester resin dispersion (A) having a volume average particle diameter of 210nm and a solid content of 30%.
Amorphous polyester resin dispersion (A)
Bisphenol a propylene oxide adduct: 80 mol% of
Bisphenol a ethylene oxide 2 mol adduct: 20 mol% of
Terephthalic acid: 60 mol%
Fumaric acid: 20 mol% of
Dodecenyl succinic anhydride: 20 mol% of
A5-liter flask equipped with a stirrer, a nitrogen inlet, a temperature sensor, and a rectifying column and having an internal volume was charged with the monomer components in the above proportions, and after the temperature was increased to 190 ℃ over 1 hour and no fluctuation in stirring in the reaction system was confirmed, 1.2 parts of dibutyltin oxide was charged per 100 parts of the monomer components. The resulting water was further distilled off, and from this temperature, the temperature was raised to 240 ℃ over 6 hours, and dehydration condensation reaction was further continued at 240 ℃ for 2 hours to obtain amorphous polyester resin (1) having a glass transition point of 63 ℃, an acid value of 10.5mgKOH/g, a weight-average molecular weight of 18000, and a number-average molecular weight of 4200.
Next, a resin particle dispersion liquid was prepared using the amorphous polyester resin (1).
Amorphous polyester resin (1): 100 portions of
Ethyl acetate: 50 portions of
Ethyl acetate was put into a 5-liter separable flask, and then the resin components were slowly put into the flask and stirred by a three-in-one motor to be completely dissolved, thereby obtaining an oil phase. To the stirred oil phase, a total of 2 parts of 10% aqueous ammonia solution was slowly dropped by a dropper, 230 parts of ion-exchanged water was further slowly dropped at a rate of 10ml/min, phase inversion emulsification was performed, and desolventization was performed while reducing the pressure by an evaporator to obtain an amorphous polyester resin dispersion (a). The volume average particle diameter of the amorphous polyester resin particles in this dispersion was 120nm, and the solid content concentration was adjusted to 30% by adding ion-exchanged water.
Amorphous polyester resin dispersion (B)
Bisphenol a propylene oxide adduct: 50 mol%
Bisphenol a ethylene oxide 2 mol adduct: 50 mol%
Trimellitic anhydride: 5 mol% of
Terephthalic acid: 85 mol%
Dodecenyl succinic anhydride: 10 mol% of
The monomers other than trimellitic anhydride among the monomer components in the above proportions were used, and the reaction was carried out in accordance with the synthesis of the amorphous polyester resin (3) until the softening point reached 110 ℃. Then, the temperature was lowered to 190 ℃, 5 mol% of trimellitic anhydride was slowly charged, and the reaction was continued at this temperature for 2 hours to obtain an amorphous polyester resin (2) having a glass transition point of 63 ℃, an acid value of 14.8mgKOH/g, a weight average molecular weight of 48000, and a number average molecular weight of 7000.
Next, a resin particle dispersion liquid was prepared using the amorphous polyester resin (2).
In the preparation of the amorphous polyester resin dispersion (a), the amorphous polyester resin dispersion (B) was obtained in accordance with the preparation of the amorphous polyester resin dispersion (a) except that the amorphous polyester resin (2) was used in place of the amorphous polyester resin (1). The volume average particle diameter of the amorphous polyester resin particles in this dispersion was 220nm, and the solid content concentration was adjusted to 30% by adding ion-exchanged water.
Colorant particle dispersion 1-
Carbon black (Legal 330, Cabot corporation): 50 portions of
An anionic surfactant (NewRexR, manufactured by japan oil corporation): 2 portions of
Ion-exchanged water: 198 portions of
The above components were mixed and dispersed for 10 minutes by a homogenizer (ULTRA-TURRAX, manufactured by IKA corporation), and then subjected to dispersion treatment at a pressure of 245MPa for 15 minutes by using an Ultimizer (impact resistant Wet Mill, manufactured by Sequoia machine) to obtain a colorant particle dispersion 1 having a volume average particle diameter of colorant particles of 354nm and a solid content of 20.0%.
Colorant particle dispersion 2-
Blue pigment (copper phthalocyanine c.i. pigment Blue 15: 3, daima refinement): 50 portions of
Ionic surfactant (neogenerk, first industrial pharmaceutical): 5 portions of
Ion-exchanged water: 195 parts
The above components were mixed and dispersed for 10 minutes by a homogenizer (ULTRA-TURRAX, manufactured by IKA corporation), and then subjected to dispersion treatment at a pressure of 245MPa for 15 minutes by using an Ultimizer (anti-collision wet pulverizer, manufactured by Sequoia machine Co., Ltd.) to obtain a colorant particle dispersion 2 having a volume average particle diameter of 462nm and a solid content of 20.0%.
Colorant particle dispersion 3-
Magenta pigment (c.i. pigment red 122): 80 portions
Anionic surfactant (NEOGENSC, first industrial pharmaceutical system): 8 portions of
Ion-exchanged water: 200 portions of
The above components were mixed and dissolved, and the mixture was dispersed for 10 minutes by using a homogenizer (ULTRA-TURRAXT50, IKA Co., Ltd.), followed by irradiating ultrasonic waves of 28kHz for 10 minutes by using an ultrasonic disperser to obtain a colorant particle dispersion 3 having a volume average particle diameter of 132nm and a solid content of 29.0%.
Colorant particle dispersion 4-
Yellow pigment (5GX03, manufactured by Clariant): 80 portions
Anionic surfactant (NEOGENSC, first industrial pharmaceutical system): 8 portions of
Ion-exchanged water: 200 portions of
The above components were mixed and dissolved, and the mixture was dispersed for 10 minutes by using a homogenizer (ULTRA-TURRAXT50, IKA corporation), followed by irradiation with ultrasonic waves of 28kHz for 20 minutes by using an ultrasonic disperser, to obtain a colorant particle dispersion 4 having a volume average particle diameter of 108nm and a solid content of 29.0%.
Release agent particle dispersions
Olefin wax (melting point: 88 ℃ C.): 90 portions of
Ionic surfactant (neogenerk, first industrial pharmaceutical): 1.8 parts of
Ion-exchanged water: 210 portions of
The above components were mixed, heated to 100 ℃ and dispersed in a homogenizer (ULTRA-TURRAXT50, IKA), and then heated to 110 ℃ in a pressure jet Gaulin homogenizer for 1 hour to obtain a release agent particle dispersion 1 having a volume average particle diameter of 180nm and a solid content of 30%.
< preparation of colored toner >
(preparation of Black toner 1)
Black toner particles 1-
Amorphous polyester resin dispersion (a): 166 portions of
Crystalline polyester resin dispersion liquid (a): 50 portions of
Colorant particle dispersion 1: 25 portions of
Release agent particle dispersion 1: 40 portions of
The above components were mixed and dispersed in a round stainless steel flask by means of a homogenizer (ULTRA-TURRAXT 50). Then, 0.20 part of polyaluminum chloride was added thereto, and the dispersion was continued by ULTRA-TURRAXT 50. The flask was stirred with a heating oil bath and simultaneously heated to 48 ℃. After the mixture was kept at 48 ℃ for 60 minutes, 60 parts of the amorphous polyester resin dispersion (A) was added little by little. Then, after the pH in the system was adjusted to 8.0 with a 0.5mol/1 aqueous sodium hydroxide solution, the flask made of stainless steel was closed, and heated to 90 ℃ for 3 hours while being continuously stirred with a magnetic piece.
After the reaction, the reaction mixture was cooled and filtered, washed with ion-exchanged water, and subjected to solid-liquid separation by filtration in a buchner funnel. The solid was further redispersed in 1 liter of ion-exchanged water at 40 ℃ and stirred and washed at 300rpm for 15 minutes. This operation was further repeated 5 times, and the pH of the filtrate reached 7.5 and the conductivity reached 7.0. mu.S/cm, followed by suction filtration through a Buchner funnel and solid-liquid separation using N05A filter paper. Subsequently, vacuum drying was continued for 12 hours, thereby obtaining black toner particles 1.
The particle diameter of the black toner particles 1 was measured by multisizer II, and the volume average particle diameter D50 was 6.4 μm and the volume particle size distribution index GSDv was 1.21.
(external additive treatment)
Black toner particles 1(100 parts), hydrophobic titanium dioxide treated with decyl silane having an average particle diameter of 15nm 0.8 parts, and hydrophobic silica having an average particle diameter of 30nm (NY50, manufactured by NIPPONAEROSIL corporation) 1.3 parts were mixed, and blended for 10 minutes at a peripheral speed of 32m/s using a Henschel mixer, and then coarse large particles were removed with a sieve having a 45 μm mesh to obtain black toner 1.
(preparation of Carrier)
Ferrite particles (volume average particle diameter: 50 μm, volume resistivity: 10)8Ω cm): 100 portions of
Toluene: 14 portions of
Perfluorooctylethyl acrylate/methyl methacrylate copolymer (copolymerization ratio 40/60, Mw: 5 ten thousand): 1.6 parts of
Carbon Black (VXC-72, manufactured by Cabot Co., Ltd.): 0.12 portion
Crosslinked melamine resin particles (number average particle diameter: 0.3 μm): 0.3 part
Among the above components, components other than the ferrite particles were mixed and dispersed for 10 minutes by a stirrer to prepare a coating film-forming liquid. The coating forming liquid and ferrite particles were charged into a vacuum degassing kneader, stirred at 60 ℃ for 30 minutes, and then toluene was distilled off under reduced pressure to form a resin coating on the surface of the ferrite particles, thereby producing a carrier.
< preparation of colored developer >
(preparation of Black developer 1)
The carrier 94 parts and the black toner 1(6 parts) were mixed, stirred at 40rpm for 20 minutes using a V-blender, and sieved through a sieve having 177 μm mesh to produce a black developer 1.
(preparation of respective color developers)
In the production of the black toner particles 1, the colorant particle dispersion liquid 1, the crystalline polyester resin dispersion liquid, and the amorphous polyester resin dispersion liquid (a) are changed, and in addition, toner particles 1 of each color are obtained in accordance with the production of the black toner particles 1. Each colored developer was obtained in the same manner except that the black toner particles 1 were changed to other toner particles in the external application process and the developer production. The contents are shown in Table 15.
In the columns of the amorphous polyester resin dispersion liquid (a) and the amorphous polyester resin dispersion liquid (B) in table 15, the parts indicated on the left side of the "+" symbol indicate the parts previously mixed in the round stainless steel flask, and the parts indicated on the right side of the "+" symbol indicate the parts added to the round stainless steel flask after the mixing/dispersing operation.
Watch 15
< evaluation >
The obtained transparent developers (i.e., transparent developers (a1) to (a10) and (a12)) were supplied to the 5 th developing unit of a Color1000Press modifier manufactured by fuji schle, which was filled with cyan, magenta, yellow, and black colored electrostatic image developers in advance in the 1 st to 4 th developing units.
Recording paper (OKPrince high-quality paper, manufactured by Okprince paper Co., Ltd.) was set, and the fixing temperature and fixing pressure were set at 170 ℃ and 4.0kg/cm2Next, the loading amount of the transparent pressure-responsive particles was set to 3g/m2An image (area density: 30%) in which characters and a photographic image are mixed was formed, and the image was fixed. A transparent pressure-responsive particle imparting section is disposed on the colored toner image.
The fixed image was folded so that the fixing surface was overlapped, and pressure-bonded using a pressure-bonding capper PRESSELELEADA (manufactured by topbanforms corporation) to produce a pressure-bonded printed product. The temperature at the time of pressure bonding was 20 ℃ and the pressure was 90 MPa.
The adhesion of the obtained pressure-sensitive printed matter was evaluated after leaving at 20 ℃ with a humidity of 50% for 1 day. For evaluation of the adhesiveness between toner layers of the printed matter, a rectangular sample having a width of 15mm was prepared by cutting the pressure-bonded printed matter in the longitudinal direction, and the peel force was measured by a 90-degree peel method. Assuming that the peeling speed of the 90 degree peeling test is 20 mm/min, the load (N) of 10mm to 50mm was measured at intervals of 0.4mm after the start of the measurement, and the average was calculated, and the load (N) of 3 test pieces was averaged. The results are shown in Table 16.
TABLE 16
< preparation of Dispersion containing styrenic resin particles >
[ preparation of styrene resin particle Dispersion (St1) ]
Styrene: 390 portions
N-butyl acrylate: 100 portions of
Acrylic acid: 10 portions of
Dodecanethiol: 7.5 parts of
The above materials were mixed and dissolved to prepare a monomer solution.
8 parts of an anionic surfactant (Dowfax 2A1, manufactured by Dow chemical Co.) was dissolved in 205 parts of ion-exchanged water, and the monomer solution was added to the solution to disperse and emulsify the solution, thereby obtaining an emulsion.
2.2 parts of an anionic surfactant (Dowfax 2A1, manufactured by Dow chemical Co., Ltd.) was dissolved in 462 parts of ion-exchanged water, and the solution was put into a polymerization flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen inlet tube, and heated to 73 ℃ with stirring and held.
3 parts of ammonium persulfate was dissolved in 21 parts of ion-exchanged water, and the solution was added dropwise to the polymerization flask over 15 minutes via a quantitative pump, and then the emulsion was added dropwise over 160 minutes via a quantitative pump.
Subsequently, the polymerization flask was kept at 75 ℃ for 3 hours with continuous slow stirring, and then returned to room temperature.
Thus, a styrene resin particle dispersion (St1) was obtained, which contained styrene resin particles, and had a volume average particle diameter (D50v) of 174nm, a weight average molecular weight as measured by GPC (UV detection) of 49000, a glass transition temperature of 54 ℃, and a solid content of 42%.
The styrene-based resin particle dispersion (St1) was dried to take out the styrene-based resin particles, and thermal behavior analysis was performed at a temperature ranging from-100 ℃ to 100 ℃ by a differential scanning calorimeter (DSC-60A, manufactured by shimadzu corporation), and 1 glass transition temperature was observed. The glass transition temperatures are shown in table 17.
[ preparation of styrene resin particle Dispersion (St2) to (St14) ]
Styrene-based resin particle dispersions (St2) to (St14) were prepared in the same manner as the preparation of the styrene-based resin particle dispersion (St1) by changing the monomers as shown in table 17.
TABLE 17
< preparation of Dispersion containing composite resin particles >
[ preparation of composite resin particle Dispersion (M1) ]
Styrene-based resin particle dispersion (St 1): 1190 parts (solid content 500 parts)
2-ethylhexyl acrylate: 250 portions of
N-butyl acrylate: 250 portions of
Ion-exchanged water: 982 parts of
The above materials were put into a flask for polymerization, stirred at 25 ℃ for 1 hour, and then heated to 70 ℃.
2.5 parts of ammonium persulfate was dissolved in 75 parts of ion-exchanged water, and was added dropwise to the polymerization flask via a metering pump over 60 minutes.
Subsequently, the polymerization flask was kept at 70 ℃ for 3 hours while continuing to stir slowly, and then returned to room temperature.
This gave a composite resin particle dispersion (M1) comprising composite resin particles, the volume average particle diameter (D50v) of the resin particles was 219nm, the weight average molecular weight by GPC (UV detection) was 219000, and the solid content was 32%.
The composite resin particle dispersion (M1) was dried, and composite resin particles were taken out and subjected to thermal behavior analysis at a temperature ranging from-150 ℃ to 100 ℃ by a differential scanning calorimeter (DSC-60A manufactured by shimadzu corporation), and 2 glass transition temperatures were observed. The glass transition temperatures are shown in table 18.
[ preparation of composite resin particle Dispersion (M2) to (M21), (M28) to (M32) and (cM1) to (cM3) ]
The styrene resin particle dispersion (St1) was changed as described in table 18, the polymerization component of the (meth) acrylate resin was changed as described in table 18, and the composite resin particle dispersions (M2) to (M21), (M28) to (M32), and (cM1) to (cM3) were combined in the same manner as in the preparation of the composite resin particle dispersion (M1).
[ preparation of composite resin particle Dispersion (M22) to (M27) ]
Composite resin particle dispersions (M22) to (M27) were prepared in the same manner as the preparation of the composite resin particle dispersion (M1) by adjusting the amounts of 2-ethylhexyl acrylate and n-butyl acrylate used.
Watch 18
< preparation of Release agent Dispersion >
Fischer-Tropsch wax: 270 portions of
(product name: FNP-0090, melting temperature: 90 ℃ manufactured by Nippon Seiro corporation)
Anionic surfactant: 1.0 part
(first Industrial pharmaceutical Co., Ltd., NEOGENRK)
Ion-exchanged water: 400 portions of
The above components were mixed, heated to 95 ℃ and dispersed by using a homogenizer (ULTRA-TURRAXT50, manufactured by IKA corporation), and then dispersion treatment was performed for 360 minutes by a MantonGaulin high pressure homogenizer (Gaulin corporation) to prepare a release agent dispersion (solid content concentration: 20%) in which a release agent having a volume average particle diameter of 0.23 μm was dispersed.
< preparation of silica particles having Large particle diameter >
(preparation of Large-diameter silica particles (S1))
Preparation of dispersions of large-diameter silica particles
300 parts of methanol and 70 parts of 10% ammonia water were added to and mixed with a 1.5L glass reaction vessel equipped with a stirrer, a dropper and a thermometer to obtain an alkali catalyst solution. After setting the temperature of the alkali catalyst solution to 30 ℃, 169 parts of Tetramethoxysilane (TMOS) and 45 parts of 8.0% ammonia water were simultaneously added dropwise to the stirred alkali catalyst solution to obtain a hydrophilic large-diameter silica particle dispersion (solid content concentration 12.0%). Here, the dropping time was 29 minutes. Then, the obtained large-diameter silica particle dispersion was concentrated to a solid content concentration of 40% by a rotary filter R-Fine (manufactured by shou industries Co., Ltd.). The concentrate was used as a dispersion of large-diameter silica particles.
Preparation of large-diameter silica particles having surface subjected to hydrophobic treatment-
To 250 parts of the above-mentioned large-diameter silica particle dispersion, 62 parts of Hexamethyldisilazane (HMDS) as a hydrophobizing agent was added, and the mixture was reacted at 130 ℃ for 2 hours. Then, the resultant is cooled and dried by spray drying, thereby obtaining hydrophobic large-diameter silica particles having surfaces subjected to hydrophobic treatment (S1).
(preparation of silica particles having Large particle diameters (S2) to (S7))
Large-diameter silica particles (S2) to (S7) were produced in the same manner as the large-diameter silica particles (S1) except that the conditions for preparing the large-diameter silica particle dispersion and the conditions for the hydrophobization treatment were set to the specifications shown in table 19. The average primary particle diameter (D50v) and the average circularity of each large-diameter silica particle were measured by the above-described method, and the results are shown in table 19.
Watch 19
< preparation of pressure-responsive particles >
[ preparation of pressure-responsive mother particle (1b) ]
Composite resin particle dispersion (M1): 504 portions of
Release agent dispersion: 7.5 parts of
Ion-exchanged water: 710 portions of
Anionic surfactant (Dowfax 2A1, manufactured by Dow chemical Co.): 1 part of
The above-mentioned materials were charged into a reaction vessel equipped with a thermometer and a pH meter, and after adjusting the pH to 3.0 by adding 1.0% aqueous nitric acid at 25 ℃, 23 parts of 2.0% aqueous aluminum sulfate was added while dispersing the mixture at 5000rpm using a homogenizer (manufactured by IKA corporation, ULTRA-TURRAXT 50). Next, a stirrer and a heating mantle were placed in the reaction vessel, the temperature was raised to 40 ℃ at a temperature rise rate of 0.2 ℃/min, the temperature was raised at a temperature rise rate of 0.05 ℃/min after the temperature exceeded 40 ℃, and the particle size was measured at intervals of 10 minutes by means of a multisizer II (pore size 50 μm, manufactured by Beckmann Coulter). After the volume average particle diameter reached 5.0. mu.m, 170 parts of a styrene resin particle dispersion (St1) was charged for 5 minutes while keeping the temperature. After the completion of the charging, the mixture was held at 50 ℃ for 30 minutes, and then a 1.0% aqueous solution of sodium hydroxide was added to adjust the pH of the slurry to 6.0. Subsequently, the pH was adjusted to 6.0 every 5 ℃ and the temperature was raised to 90 ℃ at a rate of 1 ℃/min and maintained at 90 ℃. The shape and surface properties of the particles were observed by an optical microscope and a field emission scanning electron microscope (FE-SEM), and as a result, the combination of the particles was confirmed at 10 hours, so that it took 5 minutes to cool the vessel to 30 ℃ with cooling water.
The cooled slurry was passed through a nylon mesh having a mesh opening of 15 μm to remove coarse particles, and the slurry passed through the mesh was filtered under reduced pressure by an aspirator. The solid content remaining on the filter paper was finely kneaded as much as possible by hand, and the resultant was put into ion-exchanged water (temperature 30 ℃ C.) having a solid content of 10 times that of the filter paper and stirred for 30 minutes. Subsequently, the solid content remaining on the filter paper was finely ground as much as possible by hand by filtration under reduced pressure using an aspirator, and the resultant was put into ion-exchanged water (temperature 30 ℃ C.) having a solid content of 10 times, stirred for 30 minutes, and then again filtered under reduced pressure using an aspirator to measure the conductivity of the filtrate. This operation was repeated until the conductivity of the filtrate reached 10. mu.S/cm or less, and the solid content was washed.
The washed solid content was finely ground with a wet dry granulator (pulverizing granulator), and vacuum-dried in an oven at 25 ℃ for 36 hours to obtain pressure-responsive mother particles (1 b). The volume average particle diameter of the pressure-responsive mother particle (1b) was 8.0. mu.m.
100 parts of the pressure-responsive master particles (1b), 1.5 parts of large-diameter silica particles (S1), and 0.5 part of silica particles having an average primary particle diameter of 40nm (hydrophobic silica, RY50, manufactured by NIPPONEROSIL Co., Ltd.) were mixed, and mixed using a sample mill at a rotation speed of 13000rpm for 30 seconds. The pressure-responsive particles (1b) were obtained by sieving with a vibrating sieve having a mesh opening of 45 μm.
The thermal behavior in the temperature range of-150 ℃ to 100 ℃ was analyzed by a differential scanning calorimeter (DSC-60A, manufactured by Shimadzu corporation) using the pressure-responsive particles (1b) as a sample, and 2 glass transition temperatures were observed. The glass transition temperatures are shown in table 20.
The temperature T1 and the temperature T2 of the pressure-responsive particle (1b) were determined by the above-mentioned method, and as a result, the pressure-responsive particle (1b) satisfied the expression 1 "T1-T2. degreeC.ltoreq.10".
The cross section of the pressure-responsive particle (1b) was observed by a Scanning Electron Microscope (SEM), and as a result, the sea-island structure was observed. The pressure-responsive particle (1b) has a core portion in which an island phase exists and a shell portion in which the island phase does not exist. The sea phase contains a styrene-based resin and the island phase contains a (meth) acrylate-based resin. The average diameter of the island phase was determined by the above-described measurement method. The average diameters of the island phases are shown in table 20.
10 parts of the pressure-responsive particles (1b) and 100 parts of the resin-coated carrier described below were placed in a V-blender and stirred for 20 minutes, followed by sieving with a vibrating sieve having a mesh opening of 212. mu.m, to obtain a developer (1 b).
Mn-Mg-Sr ferrite particles (average particle size 40 μm): 100 portions of
Toluene: 14 portions of
Polymethyl methacrylate: 2 portions of
Carbon black (VXC 72: manufactured by Cabot): 0.12 portion
The above-mentioned materials except for ferrite particles were mixed with glass beads (diameter 1mm, same amount as toluene) and stirred for 30 minutes at a rotation speed of 1200rpm using a sand mill manufactured by Kansaipaint corporation to obtain a dispersion. The dispersion and ferrite particles were charged into a vacuum degassing kneader, and dried under reduced pressure with stirring, thereby obtaining a resin-coated carrier.
[ production of pressure-responsive particles (2b) to (40b) and developers (2b) to (40b) ]
Pressure-responsive particles (2b) to (40b) and developers (2b) to (40b) were prepared in the same manner as the preparation of the pressure-responsive particle (1b) by changing the kinds and amounts of the composite resin particle dispersion, the styrene-based resin particle dispersion and the large-diameter silica particle dispersion as shown in tables 20 and 21.
The temperature T1 and the temperature T2 of the pressure-responsive particles (2b) to (40b) were determined by the above-mentioned measurement method, and as a result, all of the pressure-responsive particles (2b) to (40b) satisfied the expression 1 "T1-T2. degreeC.10 ℃.
[ production of pressure-responsive particles (c1b) to (c3b) and developers (c1b) to (c3b) for comparison ]
The pressure-responsive particles (c1b) to (c3b) and the developers (c1b) to (c3b) were prepared in the same manner as in the preparation of the pressure-responsive particle (1b) by changing the composite resin particle dispersion and the styrene-based resin particle dispersion as shown in tables 20 and 21.
[ evaluation of pressure responsive phase Change
A temperature difference (T1-T3) was obtained, and the temperature difference (T1-T3) was an index showing that the pressure-responsive particles are likely to undergo a phase change by pressure. Each pressure-responsive pellet was used as a sample, and the temperature T1 and the temperature T3 were measured by a flow tester (CFT-500, manufactured by Shimadzu corporation) to calculate a temperature difference (T1-T3). The temperature differences (T1-T3) are shown in tables 20 and 21.
[ evaluation of adhesiveness and releasability and evaluation of image transfer to a surface-printed matter ]
As a printed matter manufacturing apparatus, an apparatus of the embodiment shown in fig. 3 was prepared. That is, a printed matter manufacturing apparatus is prepared, and the printed matter manufacturing apparatus includes: a printing mechanism of a 5-drum tandem system and an intermediate transfer system, which collectively perform the arrangement of the pressure-responsive particles on the recording medium and the color image formation of the present embodiment, and a pressure-bonding mechanism having a folding device and a pressing device.
The pressure-responsive particles (or pressure-responsive particles for comparison) of the present embodiment, yellow toner, magenta toner, cyan toner, and black toner are loaded into 5 developing devices of a printing mechanism, respectively. The yellow toner, the magenta toner, the cyan toner, and the black toner were commercially available from Fuji Schuler corporation.
The image formed on the postcard paper was formed on one side of the postcard paper, assuming that the image had an area density of 20% where black text and a full-color photographic image were mixed.
The amount of pressure-responsive particles (or pressure-responsive particles for comparison) applied in the present embodiment is set to 3g/m in the image forming area on the image forming surface of the postcard paper2。
The folding device is a device that folds the postcard paper in half so that the image forming surface is on the inside.
The pressure of the pressurizing device is set to 90 MPa.
Under the above-described apparatus and conditions, 10 postcards were continuously produced which were folded in half with the image forming surfaces being inside and with the image forming surfaces being adhered to each other.
The 10 th postcard was cut out in the longitudinal direction at a width of 15mm to produce a rectangular test piece, and a 90-degree peel test was performed. The peeling speed in the 90 degree peeling test was set at 20 mm/min, and the load (N) from 10mm to 50mm after the start of the measurement was sampled at 0.4mm intervals, and the average was calculated, and the load (N) of the three test pieces was further averaged. The load (N) required for peeling was graded as follows. The results are shown in tables 20 and 21. In addition, whether or not an image formed on the postcard paper on the pressure-contact facing surface has been transferred is visually observed on the postcard paper after the separation. Then, the case where the image transfer occurred was evaluated as "occurred", and the case where the image transfer did not occur was evaluated as "not occurred".
A: 1.6N or more
B: 1.4N or more and less than 1.6N
C: 1.0N or more and less than 1.4N
D: 0.5N or more and less than 1.0N
E: less than 0.5N
As shown in tables 20 and 21, in the pressure-responsive particles of the examples, when pressure-bonded printed products were obtained by pressure-bonding using the pressure-responsive particles, both the adhesiveness and the releasability between the pressure-responsive particle layers were achieved.
Claims (19)
1. A pressure-responsive particle, wherein,
the pressure-responsive particles contain a styrene-based resin and a (meth) acrylate resin,
the (meth) acrylate resin contains 2 (meth) acrylates as polymerization components, and the mass ratio of the (meth) acrylate to the total polymerization components of the (meth) acrylate resin is 90 mass% or more
The pressure-responsive particles have 2 glass transition points, and the difference between the lowest glass transition temperature and the highest glass transition temperature is 30 ℃ or more.
2. The pressure-responsive particles according to claim 1, wherein the styrene accounts for 60 to 95% by mass of the total polymerization components of the styrene resin.
3. The pressure-responsive particles according to claim 1, wherein the mass ratio of the 2 (meth) acrylates contained as a polymerization component in the (meth) acrylate resin is in the range of 80:20 to 20: 80.
4. The pressure-responsive particles according to claim 1, wherein the difference in the number of carbon atoms of the alkyl groups of the 2 types of (meth) acrylates contained as the polymerization component in the (meth) acrylate resin is in the range of 1 to 4.
5. The pressure-responsive particles according to claim 1, wherein the styrene resin further contains a (meth) acrylate as a polymerization component.
6. The pressure-responsive particles according to claim 5, wherein the (meth) acrylic acid ester contained as a polymerization component in the styrene resin is selected from n-butyl acrylate and 2-ethylhexyl acrylate.
7. The pressure-responsive particles according to claim 5, wherein the styrene-based resin and the (meth) acrylate resin contain the same (meth) acrylate as a polymerization component.
8. The pressure-responsive particles according to claim 1, wherein the (meth) acrylate resin contains 2-ethylhexyl acrylate and n-butyl acrylate as polymerization components.
9. The pressure-responsive particles according to claim 1, wherein the content of the styrene resin is larger than the content of the (meth) acrylate resin.
10. The pressure responsive particle of claim 1, comprising:
a sea phase comprising the above-mentioned styrenic resin, and
an island phase comprising the above (meth) acrylate resin dispersed in the above sea phase.
11. The pressure-responsive particle according to claim 10, wherein the average diameter of said island phase is in the range of 200nm to 500 nm.
12. The pressure-responsive particle according to claim 1, which comprises a core portion comprising the styrene resin and the (meth) acrylate resin, and a shell layer covering the core portion.
13. The pressure-responsive particle according to claim 12, wherein the shell layer contains the styrene resin.
14. The pressure-responsive particle according to claim 1, which exhibits a viscosity of 10000 Pa-s at a pressure of 4MPa at a temperature of 90 ℃ or less.
15. The pressure-responsive particles according to any one of claims 1 to 14, which contain, as an external additive, silica particles having an average primary particle diameter of 1nm or more and 300nm or less, or titanium oxide particles.
16. The pressure-responsive particles according to claim 15, wherein the titanium oxide particles have an average primary particle diameter of 10nm to 100 nm.
17. The pressure-responsive particles according to claim 15, wherein the amount of the silica particles added is in the range of 1 to 3 parts by mass with respect to 100 parts by mass of the pressure-responsive mother particles contained in the pressure-responsive particles.
18. The pressure-responsive particles according to claim 15, wherein the content of the titanium oxide particles is in a range of 0.5 to 5 parts by mass with respect to 100 parts by mass of the pressure-responsive parent particles contained in the pressure-responsive particles.
19. A method for manufacturing a printed matter, comprising the steps of:
a disposing step of disposing the pressure-responsive particles described in any one of claims 1 to 14 on a recording medium; and
and a pressure bonding step of folding and pressure bonding the recording medium or overlapping the recording medium with another recording medium and pressure bonding the recording medium.
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
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| JP2019132145 | 2019-07-17 | ||
| JP2019132146 | 2019-07-17 | ||
| JP2019-132140 | 2019-07-17 | ||
| JP2019-132146 | 2019-07-17 | ||
| JP2019132140 | 2019-07-17 | ||
| JP2019-132145 | 2019-07-17 | ||
| JP2020102613A JP2021018425A (en) | 2019-07-17 | 2020-06-12 | Pressure responsive particle, cartridge, manufacturing device of printed matter, manufacturing method of printed matter, printed matter, sheet for manufacturing printed matter and manufacturing method of sheet for manufacturing printed matter |
| JP2020-102613 | 2020-06-12 |
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| Publication Number | Publication Date |
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| CN112239581A true CN112239581A (en) | 2021-01-19 |
| CN112239581B CN112239581B (en) | 2024-07-02 |
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