JP2014115505A - Method for preparing sticky note - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for preparing a sticky note in which the degree of freedom of specification design of the sticky note is high, and capable of being prepared even in a small quantity.SOLUTION: A method for preparing a sticky note in which an adhesive layer is formed on at least a part of a base material sheet by utilizing an image forming method by an electrophotography includes: a charging step; an exposing step; a developing step; a transfer step; and an adhesive layer forming step of forming the adhesive layer with a core exposed by breaking or melting a shell in a toner particle. The core contains an adhesive material made of an ester-acrylate polymer. The ester-acrylate polymer has the Young's modulus of not less than 5×10dyn/cmand not more than 5×10dyn/cm, and a weight average molecular weight of not less than 200 thousand and not more than a million. The shell contains a resin having the weight average molecular weight of not less than five thousand and not more than 50 thousand.

Description

  The present invention relates to a method for producing a sticky note, and more particularly, to a method for producing a sticky note using an image forming method by electrophotography.

Currently, so-called “sticky notes” are widely used to temporarily attach memos and the like to documents and books.
The sticky note paper is formed, for example, by forming an adhesive layer on one end of the back surface of a strip-shaped paper piece. A plurality of such sticky notes are usually stacked in the thickness direction and configured as a bundle of sticky notes. Then, the sticky notes are peeled from the sticky note bundle one by one, and the peeled sticky notes are attached to an arbitrary place for use.

In recent years, diversification of specification design, for example, the shape and size of the sticky note itself, the position and range of the adhesive layer, the size, the adhesive strength, and the like is required depending on the usage and purpose of the sticky note.
In response to such a request, for example, a product that imparts adhesiveness by spraying or applying an adhesive material to the back surface of a document or the like to be attached is known.
Further, for example, a technique is known in which the adhesion amount of the adhesive material is applied with a stepwise transition (gradation), thereby adjusting the adhesive strength and suppressing curling at the time of peeling (see, for example, Patent Document 1). ).
Furthermore, for example, a technique capable of printing on a completed sticky note is known (see, for example, Patent Document 2).

  However, in the method of spraying or applying the above-mentioned adhesive material, there is a possibility that the work is troublesome and the paper surface and the operator's hand may be soiled. Even in the technique of applying an adhesive material in a gradation or the technique capable of printing on a completed sticky note paper, only pre-defined sticky note papers can be used and cannot be freely customized.

  Accordingly, while there are a wide variety of uses and purposes, the degree of freedom of specification design such as the size and shape of the sticky note itself, the position and range of the adhesive layer, the size, and the adhesive strength is extremely low.

JP 2009-119789 A JP 2010-023993 A

  The present invention has been made based on the circumstances as described above, and its purpose is to have a high degree of freedom in design and design of sticky notes, and a sticky note preparation method that can be easily produced even in a small amount. Is to provide.

The sticky note making method of the present invention is a method for making a sticky note in which an adhesive layer is formed on at least a part of a base sheet using an electrophotographic image forming method,
A charging step for charging the photoreceptor;
An exposure step of forming an electrostatic latent image by exposing the photoreceptor;
Developing the electrostatic latent image with an adhesive layer-forming toner comprising core-shell structured toner particles, thereby forming an adhesive layer-forming toner image;
A transfer step of transferring the adhesive layer forming toner image to a substrate sheet;
An adhesive layer forming step in which the core is exposed to form an adhesive layer by breaking or melting the shells in the toner particles forming the adhesive layer forming toner image;
The core contains an adhesive material made of an acrylate ester polymer, and the acrylate ester polymer has a Young's modulus of 5 × 10 ⁵ dyn / cm ² or more and 5 × 10 ⁸ dyn / cm ² or less. Having a weight average molecular weight of 200,000 to 1,000,000,
The shell contains a resin having a weight average molecular weight of 5,000 or more and 50,000 or less.

  In the sticky note making method of the present invention, the acrylate polymer has a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2), The total is preferably contained in the acrylic ester polymer in a proportion of 75% by mass or more.

[In the above formulas (1) and (2), R ¹ and R ³ each independently represent a hydrogen atom, a methyl group or an ethyl group, and may be the same or different from each other. . R ² and R ⁴ each independently represent an alkyl group having 2 to 12 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms, and are different from each other. ]

  In the sticky note making method of the present invention, it is preferable that the adhesive layer forming step is performed using at least one of a pressurizing unit and a heating unit.

In the sticky note making method of the present invention, in the acrylate polymer, R ¹ and R ³ in the above formulas (1) and (2) are each independently a hydrogen atom or a methyl group, and R ² and R ⁴ are polymers having structural units which are different alkyl groups having 4 to 10 carbon atoms, the weight average molecular weight is 400,000 or more and 600,000 or less, and the glass transition point is −50 ° C. or more. It is preferable that it is 20 degrees C or less.

  In the sticky note making method of the present invention, it is preferable that the resin contained in the shell has a weight average molecular weight of 10,000 or more and 30,000 or less and a glass transition point of 35 ° C. or more and 75 ° C. or less.

  In the sticky note making method of the present invention, the resin contained in the shell is at least one selected from styrene-acrylic copolymer resin, (meth) acrylic ester copolymer resin, polyester resin and polyurethane resin. Preferably there is.

  In the sticky note preparation method of the present invention, the toner particles of the core-shell structure are added to a dispersion of fine particles of an acrylic ester polymer prepared by an emulsion polymerization method, whereby the acrylic ester series is added. The fine particles of the polymer are agglomerated to form core particles, and the dispersion of fine particles of the resin forming the shell is added to the dispersion of the fine particles of the core, so that the fine particles of the resin of the shell are attached to the core particles. It is preferable that it is obtained by forming a shell layer.

  According to the method for producing a sticky note of the present invention, an adhesive layer that is arbitrarily set can be formed by using a specific toner for forming an adhesive layer and utilizing an electrophotographic image forming method. There is a high degree of freedom in the design of specifications such as the size and shape of the paper itself, the position and range of the adhesive layer, the size, and the adhesive strength, and it can be easily produced even in a small amount.

It is an explanatory top view which shows an example of a structure of the tag paper obtained by the tag paper preparation method of this invention. FIG. 3 is a cross-sectional view for explaining a part of the configuration of an electrophotographic image forming apparatus used in the sticky note making method of the present invention. It is sectional drawing for description which shows the structure of the image forming apparatus by the electrophotographic method used for the sticky note preparation method of this invention. It is a top view which shows the screen pattern in the adhesion layer formation area used in an Example.

  Hereinafter, the present invention will be described in detail.

[How to make sticky notes]
The sticky note making method of the present invention is a method for making a sticky note in which an adhesive layer is formed on at least a part of a base sheet using an electrophotographic image forming method, and charges a photoreceptor. A charging step, an exposure step of forming an electrostatic latent image by exposing the photoconductor, and developing the electrostatic latent image with an adhesive layer forming toner comprising toner particles having a core-shell structure. A development step for forming a toner image for forming, a transfer step for transferring the toner image for forming an adhesive layer to a base sheet, and a shell in the toner particles forming the toner image for forming an adhesive layer are destroyed or melted to form a core. And a pressure-sensitive adhesive layer forming step of forming a pressure-sensitive adhesive layer, wherein the core contains a pressure-sensitive adhesive material made of an acrylate-based polymer as the pressure-sensitive adhesive layer forming toner. Ester-based polymer, there is the Young's modulus of ⁵ × 10 5 dyn / cm ² or more 5 × 10 ⁸ dyn / cm ² or less, and a weight average molecular weight of 200,000 to 1,000,000, Shell And a resin containing a resin having a weight average molecular weight of 5,000 or more and 50,000 or less.

As shown in FIG. 1, the sticky note obtained by the sticky note making method of the present invention is one in which an adhesive layer S is formed in the adhesive layer forming region A of the base sheet P. The position, range and size of the adhesive layer forming area A are arbitrarily set.
The sticky note paper on which the adhesive layer S is formed on the base sheet P can be peeled from the surface to be pasted.

[Charging process]
The charging step is performed by uniformly charging the photoconductor. As a method for charging the photosensitive member, a method similar to a charging method generally used in a conventionally known electrophotographic method can be employed.
The photoconductor is not particularly limited, and examples thereof include an inorganic photoconductor such as amorphous silicon and selenium, or a drum-like one made of an organic photoconductor such as polysilane and phthalopolymethine.

[Exposure process]
The exposure step is performed by imagewise exposing the surface of the photoconductor uniformly charged in the charging step, thereby forming an electrostatic latent image corresponding to the adhesive layer forming region. As a method for exposing the photosensitive member, a method similar to the exposure method that is generally performed in a conventionally known electrophotographic method can be employed.

[Development process]
The development step is performed by developing the electrostatic latent image with an adhesive layer forming toner composed of core-shell toner particles, thereby forming an adhesive layer forming toner image corresponding to the adhesive layer forming region. . As the developing method using the toner for forming the adhesive layer, a method similar to a developing method generally executed in a conventionally known electrophotographic method can be employed.

[Adhesive layer forming toner]
The toner for forming an adhesive layer used in the method for producing a sticky note of the present invention is composed of toner particles having a core-shell structure. The toner particles having the core-shell structure are formed by forming a shell (hereinafter also referred to as “shell layer”) on the surface of a core (hereinafter also referred to as “core particle”). The toner particles may contain a colorant and an internal additive such as a release agent and a charge control agent as necessary. Further, an external additive such as a fluidizing agent or a cleaning aid may be added to the toner particles.

  The core particles constituting the core-shell structure toner particles contain at least an adhesive material made of an acrylate polymer (hereinafter also referred to as “core resin”), and if necessary, resins other than the core resin or coloring An internal additive such as an agent, a release agent and a charge control agent may be contained.

The pressure-sensitive adhesive material contained in the core particle is composed of an acrylate polymer, and is formed by polymerizing an acrylate monomer derived from the structural unit represented by the above formula (1), for example. preferable. In addition, the acrylate ester polymer may be a polymer composed only of an acrylate ester monomer, but may be another monomer copolymerizable with the acrylate ester monomer. It may be a copolymer with a monomer.
By using an acrylate polymer as the adhesive, the formed adhesive layer has good adhesiveness.

The acrylic ester polymer constituting the adhesive material has, in particular, a structural unit represented by the above formula (1) and a structural unit represented by the above formula (2), that is, two types of acrylic ester. A copolymer formed by polymerizing a monomer is preferable. And it is preferable that the sum total of these structural units is contained in the acrylic ester polymer at a ratio of 75 mass% or more, particularly 85 mass% or more and 100 mass% or less.
When the acrylic ester polymer contains the structural unit represented by the above formula (1) and the structural unit represented by the above formula (2) in a proportion within the above range, the pressure-sensitive adhesive layer formed is even better. It will have good adhesiveness.
In the above formulas (1) and (2), R ¹ and R ³ each independently represent a hydrogen atom, a methyl group or an ethyl group, and may be the same or different from each other. A hydrogen atom or a methyl group is particularly preferable. R ² and R ⁴ each independently represent an alkyl group having 2 to 12 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms, and an alkyl group having 4 to 10 carbon atoms is particularly preferable. However, R ² and R ⁴ are different from each other.

Examples of the acrylate monomer derived from the structural unit represented by the above formula (1) include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, isononyl acrylate, and ethyl methacrylate. N-butyl methacrylate, isobutyl methacrylate, ter-butyl methacrylate, 2-ethylhexyl methacrylate, n-lauryl methacrylate, cyclohexyl methacrylate, methyl ethacrylate, ethyl ethacrylate and the like. The acrylic ester polymer is preferably a copolymer formed from two or more monomers selected from these. Particularly preferred is a copolymer of n-butyl acrylate and 2-ethylhexyl acrylate.
Examples of other monomers copolymerizable with acrylate esters include styrene or styrene derivatives, and acrylate esters other than acrylate ester monomers derived from the structural unit represented by the above formula (1) or (2) And monomers having an ionic dissociation group such as acrylic monomers (eg, benzyl methacrylate and stearyl methacrylate).

The Young's modulus of the acrylic ester polymer is 5 × 10 ⁵ dyn / cm ² or more and 5 × 10 ⁸ dyn / cm ² or less, preferably 10 ⁷ dyn / cm ² or more and 10 ⁸ dyn / cm ² or less. is there.
When the Young's modulus of the acrylic ester polymer is within the above range, the formed adhesive layer has good adhesiveness.
On the other hand, when the Young's modulus of the acrylate polymer is less than 5 × 10 ⁵ dyn / cm ² , the adhesive layer may be torn during peeling, and the Young's modulus of the acrylate polymer is In the case where it exceeds 5 × 10 ⁸ dyn / cm ² , there is a possibility that sufficient adhesive performance cannot be expressed on the surface to be applied.

In the present invention, the Young's modulus of the acrylate polymer is measured as follows.
A sample (acrylic ester polymer) 0.5 g is pressure-molded under a load of 1 t, and further heated on a hot plate set at 120 ° C. for 1 hour to prepare a sample for Young's modulus measurement. The Young's modulus of the sample cooled at room temperature is measured using a dynamic viscoelasticity measuring device in an environment of 25 ° C.

The weight average molecular weight (Mw) of the acrylic ester polymer is 200,000 or more and 1,000,000 or less, and preferably 400,000 or more and 600,000 or less.
When the weight average molecular weight (Mw) of the acrylic ester polymer is within the above range, the formed adhesive layer has good adhesiveness.
On the other hand, when the weight average molecular weight (Mw) of the acrylate polymer is less than 200,000, the adhesive layer may be broken at the time of peeling, and the weight average molecular weight (Mw) of the acrylate polymer. ) Exceeds 1,000,000, there is a possibility that sufficient adhesive performance cannot be expressed on the surface to be applied.

  In the present invention, the weight average molecular weight (Mw) of the acrylate ester polymer is measured by gel permeation chromatography (GPC). Specifically, using an apparatus “HLC-8220” (manufactured by Tosoh Corporation) and a column “TSKguardcolumn + TSKgelSuperHZM-M3 series” (manufactured by Tosoh Corporation), while maintaining the column temperature at 40 ° C., tetrahydrofuran (THF) was used as a carrier solvent. The sample was flowed at a flow rate of 0.2 mL / min, and the sample (acrylic ester polymer) was dissolved in THF to a concentration of 1 mg / mL under a dissolution condition in which treatment was performed for 5 minutes using an ultrasonic disperser at room temperature. Then, a sample solution is obtained by processing with a membrane filter having a pore size of 0.2 μm, and 10 μL of this sample solution is injected into the apparatus together with the above carrier solvent and detected using a refractive index detector (RI detector). The molecular weight distribution is calculated using a calibration curve measured using monodisperse polystyrene standard particles. It is what Ten polystyrenes are used for calibration curve measurement.

The glass transition point (Tg) of the acrylic ester polymer is preferably −50 ° C. or higher and 20 ° C. or lower, and more preferably −40 to 0 ° C.
When the glass transition point (Tg) of the acrylic ester polymer is within the above range, the formed adhesive layer has good adhesiveness and can be peeled off.

In the present invention, the glass transition point (Tg) of the acrylic ester polymer is measured using a differential scanning calorimeter “Diamond DSC” (manufactured by Perkin Elmer).
Specifically, 4.5 mg of a sample (acrylic ester polymer) is precisely weighed to two digits after the decimal point, sealed in an aluminum pan, and set in a DSC-7 sample holder. For the reference, an empty aluminum pan was used, and heat-cool-heat temperature control was performed at a measurement temperature of 0 to 200 ° C., a temperature increase rate of 10 ° C./min, and a temperature decrease rate of 10 ° C./min. Analysis is performed based on the data in Heat. The glass transition point is the value of the intersection of the baseline extension before the first endothermic peak rises and the tangent line that shows the maximum slope between the first endothermic peak rising portion and the peak apex.

The softening point (Tsp) of the acrylic ester polymer is preferably 35 to 90 ° C, more preferably 45 to 75 ° C.
When the softening point (Tsp) of the acrylic ester polymer is within the above range, the adhesive layer can be re-peeled without being broken or being damaged in the normal use environment.

In the present invention, the softening point (Tsp) of the acrylic ester polymer is measured as follows.
First, in an environment of 20 ° C. ± 1 ° C. and 50% ± 5% RH, 1.1 g of a sample (acrylic ester polymer) was placed in a petri dish and left flat for 12 hours or more. SSP-10A "(manufactured by Shimadzu Corporation) was pressed with a force of 3820 kg / cm ² for 30 seconds to produce a cylindrical molded sample having a diameter of 1 cm, and this molded sample was then subjected to 24 ° C ± 5 ° C, 50% ± In an environment of 20% RH, a cylinder was tested with a flow tester “CFT-500D” (manufactured by Shimadzu Corporation) under the conditions of a load of 196 N (20 kgf), a starting temperature of 60 ° C., a preheating time of 300 seconds, and a heating rate of 6 ° C./min. Offset from a die hole (1 mm diameter x 1 mm), using a piston with a diameter of 1 cm from the end of preheating, and measured with a melting temperature measurement method using a temperature rising method with an offset value of 5 mm Temperature T _offset is the softening point of the acrylic acid ester polymer.

  The shell layer constituting the toner particles having the core-shell structure is formed on the core particles and contains at least a resin (hereinafter also referred to as “shell resin”), and if necessary, a colorant and a release agent. An internal additive such as a mold agent and a charge control agent may be contained.

  The shell resin is not particularly limited, and examples thereof include a styrene-acrylic copolymer resin, a polyester resin, for example, a modified polyester resin in which the terminal of the polyester segment is modified, a polyurethane resin, and the like.

Examples of the monomer for forming the styrene-acrylic copolymer resin include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, and p-ethyl. Styrene, 2,4-dimethylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene Styrene or styrene derivatives such as: methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate , Lauryl methacrylate, meta Methacrylic acid ester derivatives such as phenyl acrylate, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, acrylic Acrylic acid ester derivatives such as n-octyl acid, 2-ethylhexyl acrylate and phenyl acrylate; olefins such as ethylene, propylene and isobutylene; vinyl based materials such as acrylic acid and methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide A monomer can be mentioned.
Moreover, what has an ionic dissociation group can also be used in combination with said monomer. The polymerizable monomer having an ionic dissociation group has, for example, a substituent such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group as a constituent group, and specifically includes acrylic acid, methacrylic acid, maleic acid. Examples include acid, itaconic acid, cinnamic acid, fumaric acid, maleic acid monoalkyl ester, itaconic acid monoalkyl ester, styrenesulfonic acid, allylsulfosuccinic acid, 2-acrylamido-2-methylpropanesulfonic acid, and the like.
Furthermore, as monomers, divinylbenzene, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate It is also possible to obtain a resin having a crosslinked structure using polyfunctional vinyls such as acrylate.

When a polyester resin is used as the shell resin, the polyester resin can be obtained from a known polyhydric alcohol and a known polyvalent carboxylic acid.
Examples of the polyhydric alcohol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8- Octanediol, 1,9-nonanediol, 1,10-dodecanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18- Aliphatic diols such as octadecanediol and 1,20-eicosanediol; bisphenols such as bisphenol A and bisphenol F; and alkylene oxide adducts of bisphenols such as ethylene oxide adducts and propylene oxide adducts. It is done. Examples of the trihydric or higher polyhydric alcohol include glycerin, pentaerythritol, trimethylolpropane, and sorbitol. Examples of the polyhydric alcohol having an unsaturated group include 2-butene-1,4-diol, 3-butene-1,6-diol, 4-butene-1,8-diol, and 9-octadecene-7,12. Those having an unsaturated double bond such as diol; those having an unsaturated triple bond such as 2-butyne-1,4-diol, 3-butyne-1,4-diol, and the like. These polyhydric alcohols can be used alone or in combination of two or more.
Examples of the polyvalent carboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelic acid, sebacic acid, 1,9-nonanedicarboxylic acid, and 1,10-decanedicarboxylic acid. Acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid Aliphatic carboxylic acids such as lower alkyl esters and anhydrides of these aliphatic carboxylic acids; phthalic acid, isophthalic acid, terephthalic acid, orthophthalic acid, t-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4 Aromatic carboxylic acids such as' -biphenyldicarboxylic acid; trimet acid, pyromellitic acid Examples thereof include trivalent or higher polyvalent carboxylic acids such as toic acid. Examples of the polyvalent carboxylic acid having an unsaturated group include unsaturated fatty acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, isododecenyl succinic acid, n-dodecenyl succinic acid, and n-octenyl succinic acid. Carboxylic acids; and acid anhydrides or acid chlorides thereof; unsaturated aromatic carboxylic acids such as caffeic acid. These polyvalent carboxylic acids can be used alone or in combination of two or more.

The weight average molecular weight (Mw) of the shell resin is 5,000 or more and 50,000 or less, and preferably 10,000 or more and 30,000 or less.
When the weight average molecular weight (Mw) of the shell resin is within the above range, the mechanical and thermal durability can be maintained, and fixing stability can be ensured.
On the other hand, when the weight average molecular weight (Mw) of the shell resin is less than 5,000, the shell layer is insufficient in strength, which may cause transfer failure due to in-machine contamination or toner aggregation. When the weight average molecular weight (Mw) exceeds 50,000, the core particles cannot be sufficiently released in the pressure-sensitive adhesive layer forming step, and sufficient pressure-sensitive adhesive performance may not be exhibited.

  In the present invention, the weight average molecular weight (Mw) of the shell resin is measured by gel permeation chromatography (GPC), and in the above-described method for measuring the weight average molecular weight (Mw) of the acrylate polymer. The measurement is performed in the same manner except that the sample is changed to shell resin.

It is preferable that the glass transition point (Tg) of shell resin is 35-75 degreeC, More preferably, it is 45-65 degreeC.
Moreover, it is preferable that the softening point (Tsp) of shell resin is 70-125 degreeC, More preferably, it is 90-110 degreeC.
When the glass transition point (Tg) of the shell resin is within the above range, the heat resistance can be maintained. Moreover, when the softening point (Tsp) of the shell resin is within the above range, the adhesiveness and re-peelability of the formed adhesive layer are not inhibited.

  In the present invention, the glass transition point (Tg) and softening point (Tsp) of the shell resin are obtained by changing the sample to the shell resin in the method for measuring the glass transition point and softening point of the acrylate polymer. Others are measured similarly.

  In the present invention, the colorant when the toner particles are configured to contain a colorant is not particularly limited, and examples thereof include carbon black, C.I. I. Pigment Red 5, 48: 1, 48: 3, 53: 1, 57: 1, 81: 4, 122, 139, 144, 149, 166, 177, 178, 222, C.I. I. Pigment Orange 31 and 43, C.I. Pigment Yellow 14, 17, 17, 74, 93, 94, 138, 139, 155, 180, 185, C.I. I. Pigment green 7, C.I. Pigment Blue 15: 3, 15: 4, 60, and the like can be used. These can be used alone or in combination of two or more.

  The content of the colorant is preferably 4 to 10% by mass in the toner particles, and more preferably 5 to 9% by mass.

  In the present invention, the release agent when the toner particles are configured to contain a colorant includes, for example, low molecular weight polyethylene wax, low molecular weight polypropylene wax, Fischer-Tropsch wax, microcrystalline wax, and paraffin wax. Examples thereof include hydrocarbon waxes, carnauba wax, ester waxes such as pentaerythritol behenate, behenyl behenate and behenyl citrate. These can be used individually by 1 type or in combination of 2 or more types.

  The content of the release agent is preferably 2 to 20% by mass in the toner particles, more preferably 3 to 18% by mass, and still more preferably 4 to 15% by mass.

  In the present invention, various known compounds that can be dispersed in an aqueous medium can be used as the charge control agent when the toner particles are configured to contain a colorant. Specifically, Examples thereof include nigrosine dyes, naphthenic acid or higher fatty acid metal salts, alkoxylated amines, quaternary ammonium salt compounds, azo metal complexes, salicylic acid metal salts or metal complexes thereof.

  The content ratio of the charge control agent is preferably 0.1 to 10% by mass in the toner particles, and more preferably 0.5 to 5% by mass.

In the present invention, the average particle diameter of the toner for forming the adhesive layer is preferably, for example, 3 to 10 μm in volume-based median diameter (D ₅₀ ). This particle size can be controlled by the concentration of the coagulant used, the amount of organic solvent added, the fusing time, and the composition of the polymer, for example, when the emulsion polymerization aggregation method described later is employed.
When the volume-based median diameter is in the above range, for example, a very minute dot image at a level of 1200 dpi (dpi; number of dots per inch (2.54 cm)) can be faithfully reproduced.

  The volume-based median diameter of the toner for forming the adhesive layer is measured using a measuring apparatus in which a computer system equipped with data processing software “Software V3.51” is connected to “Multisizer 3” (manufactured by Beckman Coulter).・ It is calculated. Specifically, 0.02 g of the adhesive layer forming toner was added to 20 mL of a surfactant solution (for example, a surfactant obtained by diluting a neutral detergent containing a surfactant component 10 times with pure water for the purpose of dispersing toner particles). Solution) and ultrasonically disperse for 1 minute to prepare a toner particle dispersion. This toner particle dispersion is placed in “ISOTONII” (manufactured by Beckman Coulter) in the sample stand. Pipette into a beaker until the displayed concentration of the measuring device is 8%. Here, a reproducible measurement value can be obtained by setting the concentration range. In the measuring apparatus, the frequency value is calculated by setting the number of measured particle counts to 25000 and the aperture diameter to 100 μm, and the particle diameter of 50% from the larger volume integrated fraction is the volume-based median diameter.

In the present invention, the arithmetic average value of the circularity represented by the following formula (T) is 0.850 to 0.990 for the individual toner particles constituting the toner for forming the adhesive layer from the viewpoint of improving transfer efficiency. It is preferable.
Formula (T): Circularity = perimeter of perfect circle having projection area equivalent to particle projection image / perimeter of particle projection image

Here, the average circularity of the toner particles is a value measured using “FPIA-2100” (manufactured by Sysmex).
Specifically, the toner particles are moistened with an aqueous surfactant solution, and ultrasonic dispersion is performed for 1 minute. After dispersion, HPFP detection is performed in the measurement condition HPF (high magnification imaging) mode using “FPIA-2100”. Measurement is performed at appropriate concentrations of several thousand to 10,000. Within this range, reproducible measurement values can be obtained.

The adhesive layer forming toner as described above can be used as a toner as it is. However, from the viewpoint of improving the charging performance, fluidity, or cleaning property of the toner, known inorganic fine particles or It is preferable to add particles such as organic fine particles and a lubricant as external additives.
Various external additives may be used in combination.

Examples of the inorganic fine particles include inorganic oxide fine particles such as silica fine particles, alumina fine particles, and titanium oxide fine particles, inorganic stearate compound fine particles such as aluminum stearate fine particles and zinc stearate fine particles, or strontium titanate and zinc titanate. An inorganic titanic acid compound fine particle etc. are mentioned.
These inorganic fine particles are preferably those subjected to surface treatment with a silane coupling agent, a titanium coupling agent, a higher fatty acid, silicone oil, or the like from the viewpoint of heat-resistant storage stability and environmental stability.

The amount of these external additives added is 0.05 to 5 parts by mass, preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the toner particles.
Examples of the method for adding the external additive include a dry method in which the external additive is added in powder form to the dried toner particles. Examples of the mixing device include mechanical mixing devices such as a Henschel mixer and a coffee mill. .

[Method for producing toner for forming adhesive layer]
The toner for forming an adhesive layer used in the present invention can be produced by various known methods. Since a shell layer can be uniformly formed on the surface of the core particles, acrylic acid dispersed in an aqueous medium is used. Manufacturing by an emulsion polymerization aggregation method in which toner particles are obtained by agglomerating and fusing ester polymer fine particles to form core particles, and agglomerating and fusing shell resin fine particles on the surface of the core particles. Is preferred.

Concretely showing the production example in the case of producing the adhesive layer forming toner by the emulsion polymerization aggregation method,
(1-1) Preparation of a shell resin fine particle dispersion in which fine particles of a shell resin (hereinafter also referred to as “shell resin fine particles”) are formed in an aqueous medium to prepare a dispersion in which the shell resin fine particles are dispersed. Process,
(1-2) In a water-based medium, acrylate polymer fine particles (hereinafter also referred to as “core resin fine particles”) are formed by polymerization to prepare a dispersion liquid in which the core resin fine particles are dispersed. Core resin fine particle dispersion preparation process,
(2) a core particle forming step of aggregating core resin fine particles in an aqueous medium to form core particles;
(3) A shelling step in which shell resin fine particles are added to an aqueous medium in which the core particles are dispersed, and the shell resin fine particles are aggregated and fused on the surface of the core particles to form toner particles having a core-shell structure;
(4) An aging step of adjusting the shape of the toner particles by aging with heat energy;
(5) a cleaning step of separating the toner particles from the toner particle dispersion (aqueous medium) and removing the surfactant from the toner particles;
(6) a drying step of drying the washed toner particles;
Consisting of, if necessary,
(7) An external additive adding step of adding an external additive to the dried toner particles can be added.

(1-1) Shell Resin Fine Particle Dispersion Preparation Step In this shell resin fine particle dispersion preparation step, the dispersion of the shell resin fine particles is a surfactant by, for example, an emulsion polymerization method, an ultrasonic dispersion method, a bead mill dispersion method, or the like. Can be obtained by an aqueous direct dispersion method to which is added.

The average particle diameter of the shell resin fine particles obtained in the shell resin fine particle dispersion preparing step is preferably in the range of, for example, 50 to 500 nm in terms of volume-based median diameter.
The volume-based median diameter of the shell resin fine particles is measured using “UPA-150” (manufactured by Microtrack).

  In the present invention, the “aqueous medium” refers to a medium comprising 50 to 100% by mass of water and 0 to 50% by mass of a water-soluble organic solvent. Examples of the water-soluble organic solvent include methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, and tetrahydrofuran, and alcohol-based organic solvents that do not dissolve the resulting resin are preferable.

[Surfactant]
A dispersion stabilizer is preferably added to the aqueous medium in order to prevent aggregation of dispersed fine particles.
As the dispersion stabilizer, various known surfactants such as a cationic surfactant, an anionic surfactant, and a nonionic surfactant can be used.
Specific examples of the cationic surfactant include dodecyl ammonium bromide, dodecyl trimethyl ammonium bromide, dodecyl pyridinium chloride, dodecyl pyridinium bromide, hexadecyl trimethyl anonium bromide and the like.
Specific examples of nonionic surfactants include dodecyl polyoxyethylene ether, hexadecyl polyoxyethylene ether, norylphenyl polyoxyethylene ether, lauryl polyoxyethylene ether, sorbitan monooleate polyoxyethylene ether, styrylphenyl poly Examples thereof include oxyethylene ether and monodecanoyl sucrose.
Specific examples of the anionic surfactant include aliphatic soaps such as sodium stearate and sodium laurate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, polyoxyethylene (2) sodium lauryl ether sulfate and the like. it can.
The above surfactants can be used singly or in combination of two or more as desired.

(1-2) Core resin fine particle dispersion preparation step In this core resin fine particle dispersion preparation step, the core resin fine particles are preferably prepared by an emulsion polymerization method.
Specifically, the core resin fine particles are necessary for an acrylate monomer for forming an acrylate polymer in an aqueous medium containing a surfactant having a critical micelle concentration (CMC) or less. In response, a monomer solution in which toner constituents such as a release agent and a charge control agent are dissolved or dispersed is added, mechanical energy is applied to form droplets, and then a water-soluble radical polymerization initiator is added. The polymerization reaction is allowed to proceed in the droplets. Note that an oil-soluble polymerization initiator may be contained in the droplet. In such a core resin fine particle dispersion preparing step, mechanical energy is imparted and forcedly emulsified (formation of droplets) is essential. Examples of the means for applying mechanical energy include means for applying strong stirring or ultrasonic vibration energy such as homomixer, ultrasonic wave, and manton gorin.

  The core resin fine particles formed in the core resin fine particle dispersion preparation step can be composed of two or more layers made of resins having different compositions. In this case, an emulsion polymerization process (first step) It is possible to employ a method in which a polymerization initiator and a polymerizable monomer are added to the dispersion of the first resin particles prepared by polymerization), and this system is polymerized (second stage polymerization).

  When using a surfactant in the core resin fine particle dispersion preparation step, use the same surfactant as the surfactant that can be used in the above-mentioned shell resin fine particle dispersion preparation step, for example. can do.

The toner particles according to the present invention may contain an internal additive such as a colorant, a release agent, a charge control agent, and a magnetic powder as necessary. Such an internal additive includes, for example, In this core resin fine particle dispersion preparation step, it can be introduced into the toner particles by dissolving or dispersing in advance in a monomer solution for forming an acrylate polymer.
In addition, such an internal additive is prepared by separately preparing a dispersion of internal additive fine particles consisting only of the internal additive, and aggregating the internal additive fine particles together with the core resin fine particles in the core particle forming step. Although it can be introduced in, it is preferable to adopt a method of introducing in advance in the core resin fine particle dispersion preparation step.

(Polymerization initiator)
As the polymerization initiator used in the core resin fine particle dispersion preparation step, the same ones as described above can be used.

[Chain transfer agent]
In the core resin fine particle dispersion preparing step, a generally used chain transfer agent can be used for the purpose of adjusting the molecular weight of the acrylate polymer. As the chain transfer agent, the same ones as described above can be used.

The average particle diameter of the core resin fine particles obtained in this core resin fine particle dispersion preparing step is preferably in the range of, for example, 50 to 500 nm in terms of volume-based median diameter.
The volume-based median diameter of the core resin fine particles was measured using “UPA-150” (manufactured by Microtrack).

(2) Core particle forming step In this core particle forming step, if necessary, fine particles of other toner constituent components such as a release agent and a charge control agent can be aggregated together with the core resin fine particles.

  As a specific method for agglomerating and fusing the core resin fine particles, a flocculant is added to the aqueous medium so as to have a critical aggregation concentration or higher, and then the glass transition point of the core resin fine particles or higher, and these By heating the mixture to a temperature equal to or higher than the melting peak temperature (° C), the core resin fine particles are salted out at the same time as the fusion is progressed in parallel. Then, the particle growth is stopped, and further, heating is continuously performed to control the particle shape as necessary.

  In this method, the time allowed to stand after the addition of the flocculant is shortened as much as possible, and immediately above the glass transition point of the resin fine particles related to the acrylate polymer, and the melting peak temperature (° C.) of these mixtures. It is preferable to heat to the above temperature. The reason for this is not clear, but depending on the standing time after salting out, the aggregation state of the particles may fluctuate and the particle size distribution may become unstable, and the surface properties of the fused particles may vary. This is because there is concern about the occurrence. The time until this temperature rise is usually preferably within 30 minutes, and more preferably within 10 minutes. Moreover, it is preferable that it is 1 degree-C / min or more as a temperature increase rate. The upper limit of the heating rate is not particularly specified, but is preferably 15 ° C./min or less from the viewpoint of suppressing the generation of coarse particles due to rapid progress of fusion. Furthermore, after the reaction system reaches a temperature equal to or higher than the glass transition point, it is important to continue the fusion by maintaining the temperature of the reaction system for a certain time. Thereby, the growth and fusion of the core particles can be effectively advanced, and the durability of the toner particles finally obtained can be improved.

[Flocculant]
The flocculant used in the core particle forming step is not particularly limited, but a material selected from metal salts is preferably used. Examples of the metal salt include monovalent metal salts such as alkali metal salts such as sodium, potassium and lithium; divalent metal salts such as calcium, magnesium, manganese and copper; and trivalent metal salts such as iron and aluminum. Etc. Specific metal salts can include sodium chloride, potassium chloride, lithium chloride, calcium chloride, magnesium chloride, zinc chloride, copper sulfate, magnesium sulfate, manganese sulfate, and the like. It is particularly preferable to use a divalent metal salt. These can be used individually by 1 type or in combination of 2 or more types.

  When using a surfactant in the core particle forming step, it is possible to use, for example, the same surfactant as the surfactant that can be used in the above-mentioned shell resin fine particle dispersion preparation step. it can.

As for the particle size of the core particles obtained in this core particle forming step, for example, the volume-based median diameter (D ₅₀ ) is preferably 2 to 9 μm, more preferably 4 to 7 μm.
The volume-based median diameter of the core particles is measured by “Coulter Multisizer 3” (manufactured by Coulter Beckman).

(3) Shelling step In this shelling step, shell resin fine particles are added to the dispersion of core particles to aggregate and fuse the shell resin fine particles on the surface of the core particles, and a shell layer is formed on the surface of the core particles. The toner particles are formed by coating.
Specifically, the dispersion of the core particles is added to the dispersion of the shell resin fine particles while maintaining the temperature in the core particle formation step, and the shell resin fine particles are slowly removed over several hours while continuing the heating and stirring. The toner particles are formed by aggregating and fusing the surfaces of the core particles with a shell layer having a thickness of 100 to 300 nm on the surface of the core particles. The heating and stirring time is preferably 1 to 7 hours, particularly preferably 3 to 5 hours.

(4) Ripening step The shape of the toner particles in the toner can be made uniform to some extent by controlling the heating temperature in the core particle forming step and the shelling step, but in order to further make the shape uniform, the ripening step Go through.
This aging step is controlled by controlling the heating temperature and time so that the surface of the toner particles formed with a constant particle size and a narrow distribution has a smooth but uniform shape. Specifically, the heating temperature is lowered in the core particle forming step and the shelling step to suppress the progress of fusion between the resin fine particles to promote leveling, and in this aging step, the heating temperature is lowered. In addition, the toner particles are controlled so as to have a desired average circularity, that is, a surface having a uniform shape by extending the time.

(5) Washing step to (6) Drying step The washing step and the drying step can be performed by employing various known methods.

(7) External additive addition step This external additive addition step is a step of preparing toner particles by adding and mixing external additives as necessary to the dried toner particles.

(Developer)
The toner for forming an adhesive layer used in the present invention can be used as a magnetic or non-magnetic one-component developer, but may be mixed with a carrier and used as a two-component developer.
As the carrier, for example, magnetic particles made of conventionally known materials such as metals such as iron, ferrite and magnetite, and alloys of these metals with metals such as aluminum and lead can be used. Among these, ferrite particles Is preferably used. As the carrier, a coated carrier in which the surface of magnetic particles is coated with a coating agent such as a resin, a resin-dispersed carrier in which a magnetic fine powder is dispersed in a binder resin, or the like may be used.
The carrier preferably has a volume average particle diameter of 15 to 100 μm, more preferably 25 to 80 μm.

[Transfer process]
The transfer process is performed by transferring an adhesive layer forming toner image corresponding to the adhesive layer forming region to the base sheet P. As a method for transferring the toner image for forming the adhesive layer to the base material sheet P, a method similar to a transfer method generally performed in a conventionally known electrophotographic method can be employed. Etc.
In the transfer step, for example, an intermediate transfer member is used, and after the primary transfer of the adhesive layer forming toner image onto the intermediate transfer member, the adhesive layer forming toner image is secondarily transferred onto the base sheet P. The toner image for forming an adhesive layer formed on the photoreceptor can also be transferred directly to the substrate sheet P.

[Base material sheet]
The base sheet P used in the sticky note manufacturing method of the present invention is not particularly limited as long as it is a recording medium that can be generally used in a conventionally known electrophotographic method. For example, plain paper, cardboard, fine paper, art Paper substrates such as coated printing paper such as paper or coated paper, cardboard paper, etc .; resin base materials such as vinyl chloride resin, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, polyimide resin, etc. .
The thickness of the base sheet P can be set to 0.01 to 0.5 mm, for example. Moreover, the magnitude | size and shape of the base material sheet P can be set arbitrarily.

[Adhesive layer forming step]
The adhesive layer forming step is performed by breaking or melting the shell layer in the toner particles forming the adhesive layer forming toner image, whereby the core particles are exposed and the adhesive layer S is formed. In this pressure-sensitive adhesive layer forming step, the pressure-sensitive adhesive material (acrylic ester polymer) contained in the exposed core particles exhibits pressure-sensitive adhesive properties, and the pressure-sensitive adhesive layer S is formed.
As a method for destroying or melting the shell layer, it can be carried out by using a fixing means generally used in a conventionally known electrophotographic method, specifically, a fixing means such as a heat and pressure roller. It is preferable to carry out using at least one of the pressurizing means and the heating means. Examples of the pressurizing unit include a pair of roller members and a belt member, and examples of the heating unit include a roller member and a belt member having a heat generating mechanism, and an ultraviolet irradiation device.
In the pressure-sensitive adhesive layer forming step, it is particularly preferable that the pressure-sensitive adhesive layer forming toner image is performed in a non-contact state with a pressurizing unit, a heating unit, or the like. Therefore, it is particularly preferable to melt the shell layer of the toner particles by irradiating the toner image for forming the adhesive layer with ultraviolet rays by a non-contact heating means such as an ultraviolet irradiation device.

The heating conditions by the heating means vary depending on the type of adhesive layer forming toner to be used (type of shell resin). For example, when using a roller member or belt member having a heating mechanism, the heating temperature (the surface of the heating means) Temperature) is preferably 150 to 220 ° C., and the nip time is preferably 10 to 200 msec. When an ultraviolet irradiation device is used, the UV illuminance is preferably 100 to 5000 mW / cm ² and the irradiation time is preferably 10 to 200 msec. . The nip time is calculated from the length in the conveyance direction (mm) / linear velocity (mm / sec) × 1000 of the nip portion N of the roller member or the belt member.

  The pressurizing condition by the pressurizing unit varies depending on the type of adhesive layer forming toner to be used (the type of shell resin), but for example, the applied pressure is preferably 80 to 600 Pa.

(Adhesive layer)
The adhesive layer S formed in this fixing step is formed based on the position, range, and size of the adhesive layer forming area A that is arbitrarily set.

The adhesion amount of the adhesive layer forming toner in the adhesive layer S varies depending on the type of the adhesive layer forming toner to be used and the screen pattern of the adhesive layer forming region, but is preferably 0.5 to 20 g / m ² , for example.
When the adhesion amount of the adhesive layer forming toner in the adhesive layer S is within the above range, the adhesive layer has an appropriate adhesive strength.

The thickness of the adhesive layer S is preferably 3 to 30 μm, for example.
When the thickness of the adhesive layer S is within the above range, the adhesive layer S has an appropriate adhesive strength. On the other hand, when the thickness of the adhesive layer S is too small, there is a possibility that the adhesive strength is insufficient and the adhesive layer S cannot be applied to any application target surface. In addition, when the thickness of the adhesive layer S is excessive, the adhesive strength is excessive, and there is a possibility that a part of the adhesive layer S remains on the surface to be pasted when peeled.

The adhesive strength of the adhesive layer S can be arbitrarily set, but is preferably 0.1 N / cm ² or more and 10 N / cm ² or less, more preferably 0.5 N / cm ² or more and 7 N / cm ^2. It is as follows.
The adhesive strength can be controlled by adjusting the adhesion amount of the adhesive layer forming toner to be used and the pattern of the adhesive layer forming region.
The adhesive strength of the adhesive layer S can be measured by a 90-degree tape peeling test under a 23 ° C. environment based on JIS Z0237 standard.

  The sticky note making method of the present invention can be executed using an image forming apparatus generally used in electrophotography.

FIG. 2 is a cross-sectional view for explaining a part of the configuration of an electrophotographic image forming apparatus used in the sticky note manufacturing method of the present invention.
The image forming apparatus includes an adhesive layer forming toner image forming unit 20 that forms an adhesive layer forming toner image corresponding to a set adhesive layer forming region and transfers the toner image to the base sheet P, and an adhesive layer forming toner. The pressure-sensitive adhesive layer forming apparatus 50 breaks and melts the shell layer of the toner particles forming the pressure-sensitive adhesive layer forming toner image by applying pressure while heating the image.

  The toner image forming unit 20 for forming an adhesive layer includes a photosensitive member 15 that is an electrostatic latent image carrier, a charging unit 11 that applies a uniform potential to the surface of the photosensitive member 15, and a uniformly charged photosensitive member. An exposure unit 12 including a semiconductor laser light source 12A, a polygon mirror 12B, and an fθ lens 12C, which forms an electrostatic latent image corresponding to the adhesive layer forming area A, and an adhesive layer forming toner on the photoconductor 15. Developing means 13 for conveying and developing the electrostatic latent image; transfer means 14 for transferring the adhesive layer forming toner image formed by the developing means 13 to the base sheet P; and adhesive layer forming toner Separation means 16 for separating the substrate sheet having the image transferred thereon from the photoreceptor 15 and a cleaning blade 19A having a cleaning blade 19A made of a rubber-like elastic body for collecting residual toner remaining on the photoreceptor 15 after the transfer. And it means 19, in which and a pre-charging exposure means (PCL) 17.

  The pressure-sensitive adhesive layer forming apparatus 50 is provided in a state where a pair of heat and pressure rollers 51 and 52 are brought into pressure contact with each other and a nip portion N is formed in the pressure contact portion.

In the adhesive layer forming toner image forming unit 20 and the adhesive layer forming apparatus 50 of such an image forming apparatus, the following processing is performed.
First, in the toner image forming unit 20 for forming the adhesive layer, an electrostatic latent image corresponding to the adhesive layer forming region is formed on the photoconductor 15 by being charged by the charging unit 11 and exposed by the exposure unit 12. The electrostatic latent image is developed by the developing unit 13 with the adhesive layer forming toner, whereby an adhesive layer forming toner image is formed.
On the other hand, an arbitrarily selected base sheet P accommodated in a paper feeding cassette (not shown) is conveyed to the transfer region R in time by a conveying means (not shown), and the transfer means 14 in the transfer region R The base sheet P on which the adhesive layer forming toner image on the photoconductor 15 is transferred to a position corresponding to the adhesive layer forming area on the base sheet P, and further, the adhesive layer forming toner image is transferred by the separating means 16. Is separated from the photoreceptor 15.
Next, the separated base sheet P is conveyed to the nip portion N of the adhesive layer forming apparatus 50, and the shell layer constituting the toner particles is broken or melted by pressurization and heating in the nip portion N, so that the core particles are formed. The pressure-sensitive adhesive material (acrylic ester polymer) of the core particles is exposed to form a pressure-sensitive adhesive layer S, and the pressure-sensitive adhesive layer S is adhered to the heat and pressure roller 51 by a separation claw (not shown). It is discharged outside while suppressing. As described above, a sticky note in which the adhesive layer S is formed on at least a part of the base sheet P can be obtained.

  After the adhesive layer forming toner image is transferred to the base sheet, the adhesive layer forming toner remaining on the surface is removed by the cleaning unit 19, and the residual charge is removed by the pre-charging exposure unit 17. After that, it is used for forming the next toner image for forming an adhesive layer.

The heating and pressing conditions in the pressure-sensitive adhesive layer forming apparatus 50 differ depending on the type of pressure-sensitive adhesive layer forming toner used, but can be as follows, for example.
-Heating temperature: 150-220 ° C
・ Nip time: 10-200msec
The nip time is calculated from the conveyance direction length (mm) / linear velocity (mm / sec) of the nip portion N of the heat and pressure rollers 51 and 52 × 1000.
The heating temperature refers to the surface temperature of the heating and pressing roller 51 that contacts the surface of the base sheet on which the adhesive layer forming toner image is transferred.

  The sticky note making method of the present invention uses an electrophotographic image forming apparatus, and by mounting color toners such as yellow toner, cyan toner, magenta toner and black toner together with an adhesive layer forming toner, Formation of the adhesive layer with the adhesive layer forming toner and printing with the color toner can be performed simultaneously or continuously.

FIG. 3 is an explanatory cross-sectional view showing an example of the configuration of an electrophotographic image forming apparatus used in the sticky note manufacturing method of the present invention.
The image forming apparatus can continuously execute an adhesive layer forming process using an adhesive layer forming toner and a print forming process using a color toner such as yellow toner, cyan toner, magenta toner, and black toner. This is a tandem type color image forming apparatus.

  The image forming apparatus forms an adhesive layer forming toner image forming unit 20S that forms an adhesive layer forming toner image corresponding to the set adhesive layer forming region, and forms yellow, magenta, cyan, or black toner images, respectively. Formed in the colored toner image forming portions 20Y, 20M, 20C, and 20Bk and the adhesive layer forming toner images or colored toner image forming portions 20Y, 20M, 20C, and 20Bk formed in the adhesive layer forming toner image forming portion 20S. An intermediate transfer unit 10 that transfers the colored toner image onto the base sheet P, an adhesive layer forming device 50 that destroys or melts the shell layer of the toner particles that form the adhesive layer forming toner image, and a colored toner image. And a fixing device 70 that fixes the substrate sheet P by applying pressure while heating.

  The colored toner image forming unit 20Y forms a yellow toner image, the colored toner image forming unit 20M forms a magenta toner image, and the colored toner image forming unit 20C forms a cyan toner image. Then, a black toner image is formed in the colored toner image forming unit 20Bk.

  The toner image forming unit 20S for forming an adhesive layer includes a photoreceptor 15S that is an electrostatic latent image carrier, a charging unit 11S that applies a uniform potential to the surface of the photoreceptor 15S, and a uniformly charged photoreceptor. An exposure unit 12S that forms an electrostatic latent image corresponding to the adhesive layer forming area A on 15S, and a developing unit 13S that conveys the adhesive layer forming toner onto the photoreceptor 15S to visualize the electrostatic latent image. And a cleaning means 19S for collecting residual toner remaining on the photoconductor 15S after the primary transfer.

  Also, the colored toner image forming units 20Y, 20M, 20C, and 20Bk have the same configuration as the adhesive layer forming toner image forming unit 20S.

  The intermediate transfer unit 10 includes an intermediate transfer member 26, a primary transfer roller 27S for transferring the adhesive layer forming toner image formed by the adhesive layer forming toner image forming unit 20S to the intermediate transfer member 26, and a colored toner image. The colored toner images formed by the forming portions 20Y, 20M, 20C, and 20Bk are transferred onto the intermediate transfer member 26 by the primary transfer rollers 27Y, 27M, 27C, and 27Bk for transferring the colored toner image to the intermediate transfer member 26, and the primary transfer roller 27S. A secondary transfer roller 29 for transferring the formed adhesive layer toner image or the colored toner image transferred onto the intermediate transfer body 26 by the primary transfer rollers 27Y, 27M, 27C, 27Bk onto the base sheet P; And a cleaning unit 261 that collects residual toner remaining on the intermediate transfer member 26.

The pressure-sensitive adhesive layer forming apparatus 50 is provided in a state in which a pair of heat and pressure rollers are pressed against each other and a nip portion N is formed at the pressure contact portion.
The fixing device 70 is also provided in a state where a pair of heat and pressure rollers are pressed against each other and a nip portion N is formed at the pressure contact portion.

In such an image forming apparatus, for example, the following adhesive layer forming step and print forming step are performed.
First, a print forming process using colored toner is performed. Specifically, in the colored toner image forming units 20Y, 20M, 20C, and 20Bk, electrostatic latent images are formed on the photosensitive member by being charged by the charging unit and exposed by the exposure unit, respectively. A colored toner image is formed by developing the image with colored toner in the developing means. The colored toner image is transferred to the intermediate transfer body 26 by the primary transfer rollers 27Y, 27M, 27C, and 27Bk in order of the yellow toner image, the magenta toner image, the cyan toner image, and the black toner image, and the respective toner images are superimposed. Then, the arbitrarily selected base sheet P accommodated in the paper feed cassette 40 is transported in time by the transport means, and is transferred to the base sheet P by the secondary transfer roller 29 on the intermediate transfer body 26. A colored toner image is transferred. Next, the base sheet P to which the colored toner image has been transferred is conveyed to the nip portion N of the fixing device 70, and the colored toner image is fixed to one surface of the base sheet P by pressurization and heating in the nip portion N. .
Thereafter, the base sheet P on which the colored toner image is fixed is supplied to the adhesive layer forming step via the conveyance path 71. Specifically, in the adhesive layer forming toner image forming unit 20S, the electrostatic latent image corresponding to the adhesive layer forming region is charged on the photoreceptor 15S by the charging unit 11S and exposed by the exposure unit 12S. The electrostatic latent image is formed and developed by the developing means 13S with the adhesive layer forming toner, whereby an adhesive layer forming toner image is formed. This adhesive layer forming toner image is transferred to the intermediate transfer member 26 by the primary transfer roller 27S. Then, the adhesive layer forming toner image on the photoconductor 15S is transferred to a position corresponding to the adhesive layer forming region on the other surface of the base sheet P that has been conveyed in time by the conveying means via the conveying path 71. Is done. Next, the base sheet P to which the toner image for forming the adhesive layer is transferred is conveyed to the nip portion N of the adhesive layer forming device 50, and the shell layer constituting the toner particles is destroyed by the pressurization and heating in the nip portion N. Alternatively, the core particles are exposed by being melted, and adhesiveness is expressed by the adhesive material of the core particles, whereby the adhesive layer S is formed. As described above, a sticky note in which printing with color toner is formed on one surface of the base sheet P and the adhesive layer S is formed on the other surface can be obtained.

  As mentioned above, although embodiment of this invention was described concretely, it is not limited to said example, A various change can be added.

  Hereinafter, specific examples of the present invention will be described, but the present invention is not limited thereto.

<Preparation Example 1 of Toner for Forming Adhesive Layer>
(1) Preparation of fine particle dispersion of shell resin 2900 parts of an anionic surfactant (sodium dodecylbenzenesulfonate: SDS) was added to ion-exchanged water 2900 in a reaction vessel equipped with a stirrer, temperature sensor, cooling tube and nitrogen introducing device. A surfactant aqueous solution dissolved in parts by mass was prepared. While this surfactant aqueous solution was stirred at a stirring speed of 230 rpm under a nitrogen stream, the temperature was raised to 80 ° C.
After adding 9.5 parts by mass of a polymerization initiator (KPS) to the surfactant aqueous solution, 560 parts by mass of styrene, 206 parts by mass of n-butyl acrylate, 58 parts by mass of methyl methacrylate and 13.5 parts by mass of n-octyl mercaptan. A monomer solution consisting of parts was added dropwise over 3 hours.
After the dropwise addition of this monomer solution, the liquid temperature was maintained at 78 ° C. for 1 hour to prepare a dispersion of shell resin fine particles [S1] (hereinafter referred to as “shell resin fine particle dispersion [S1]”). The volume-based median diameter of the shell resin fine particles [S1] was 120 nm, the glass transition point (Tg) was 56 ° C., the softening point (Tsp) was 109 ° C., and the weight average molecular weight (Mw) was 17,000.

(2) Preparation of core resin fine particle dispersion A reactor equipped with a stirrer, temperature sensor, cooling tube and nitrogen introduction device in a 5 L reaction vessel was charged with a surfactant solution in advance, While stirring at a rotational speed of 230 rpm, the liquid temperature was raised to 80 ° C. As the surfactant solution, 0.8 part by mass of an anionic surfactant (SDS) and 2820 parts by mass of ion-exchanged water were used. After adding 9 parts by mass of a polymerization initiator (KPS) to the surfactant solution, 40 parts by mass of acrylic acid, 400 parts by mass of n-butyl acrylate, 40 parts by mass of methyl methacrylate and 320 parts by mass of 2-ethylhexyl acrylate were added for 3 hours. After completion of dropping, the mixture was kept at 75 ° C. for 1 hour to prepare a dispersion of core resin fine particles [C1] (hereinafter referred to as “core resin fine particle dispersion [C1]”). The volume-based median diameter of the core resin fine particles [C1] is 230 nm, the glass transition point is (Tg) −22 ° C., the softening point (Tsp) is 56 ° C., the Young's modulus is 3 × 10 ⁷ dyn / cm ² , and the weight average molecular weight. (Mw) was 450,000.

(3) Preparation of core-shell toner particles In a reaction vessel equipped with a stirrer, a temperature sensor and a cooling tube, 370 parts by mass of core resin fine particle dispersion [C1] (solid content conversion) and 2015 parts by mass of ion-exchanged water are added. Charged and stirred. A 25% by mass aqueous sodium hydroxide solution was added to this solution to adjust the pH to 10 to 10.3.
Subsequently, 125 mass parts of magnesium chloride hexahydrate aqueous solution (50 mass%) was added over 20 minutes under stirring. After the addition, the temperature was raised and the temperature was raised to 50-60 ° C. over about 30 minutes. Using “Multisizer 3” (manufactured by Beckman Coulter, Inc.), the particle size of the particles growing in the reactor was measured, and when reaching 6.4 μm, 110 parts by mass of a sodium chloride aqueous solution (25% by mass) was added. Addition was made to stop the agglomeration reaction of the particle size to obtain a dispersion [1] of core particles [1]. Thereafter, stirring was continued for 30 minutes while maintaining the temperature, and the core particles [1] were fused.
Next, 92 parts by mass (in terms of solid content) of shell resin fine particle dispersion [S1] was added over 45 minutes. After the addition, the temperature was raised to 75 ° C., and stirring was continued for 2 hours to agglomerate and fuse the shell resin fine particles [S1] to the core particles [1] to form a shell layer to obtain toner particles [1].
Then, 255 mass parts of 25 mass% sodium chloride aqueous solution was added, the fusion | melting was stopped, and the ageing | curing | ripening process heated up to 85 degreeC was performed. After the toner particle [1] dispersion was cooled at 4 ° C./min, it was thoroughly washed with ion-exchanged water at 20 ° C. and dried at room temperature to prepare an adhesive layer forming toner [1]. The particle diameter of the toner particles [1] was 6.5 μm in terms of volume-based median diameter.

<Preparation Example 2 of Toner for Forming Adhesive Layer>
In Preparation Example 1 of the adhesive layer forming toner, (2) the type and amount of the monomer in the preparation of the core resin fine particle dispersion were changed to those shown in Table 1, and the core resin fine particle dispersion [C2] was prepared. An adhesive layer forming toner [2] was prepared in the same manner except that this was used.

<Preparation Example 3 of Toner for Forming Adhesive Layer>
In Preparation Example 1 of the adhesive layer forming toner, (2) the types and addition amounts of the monomers in the preparation of the core resin fine particle dispersion were changed to those shown in Table 1, and 1.5 parts by mass of n-octyl mercaptan was further added. An adhesive layer forming toner [3] was prepared in the same manner except that the core resin fine particle dispersion [C3] was prepared and used.

<Preparation Example 4 of Toner for Adhesive Layer Formation>
An adhesive layer forming toner [4] was prepared in the same manner as in Preparation Example 1 of the adhesive layer forming toner except that the core resin fine particle dispersion [C1] was changed to the following core resin fine particle dispersion [C4]. did.

-Preparation of core resin fine particle dispersion [C4] Using a reaction apparatus equipped with a stirring device, a temperature sensor, a cooling pipe and a nitrogen introduction apparatus in a 5 L reaction vessel, a surfactant solution was charged in advance into the reaction apparatus, and a nitrogen stream The liquid temperature was raised to 80 ° C. while stirring at a rotation speed of 230 rpm. As the surfactant solution, 0.8 part by mass of an anionic surfactant (SDS) and 2820 parts by mass of ion-exchanged water were used. After adding 7 parts by weight of a polymerization initiator (KPS) to the surfactant solution, 40 parts by weight of acrylic acid, 400 parts by weight of n-butyl acrylate, 40 parts by weight of methyl methacrylate and 320 parts by weight of 2-ethylhexyl acrylate are added for 3 hours. After completion of dropping, the mixture was kept at 80 ° C. for 2 hours to prepare a dispersion of core resin fine particles [C4] (hereinafter referred to as “core resin fine particle dispersion [C4]”).

<Preparation Example 5 of Toner for Forming Adhesive Layer>
In Preparation Example 1 of the adhesive layer forming toner, (1) the addition amount of the polymerization initiator (KPS) in the preparation of the shell resin fine particle dispersion was changed to 12 parts by mass, and the addition amount of n-octyl mercaptan was 20 The adhesive layer forming toner [5] was prepared in the same manner except that the shell resin fine particle dispersion [S2] was prepared and used.

<Preparation Example 6 of Adhesive Layer-Forming Toner>
In Preparation Example 1 of the adhesive layer forming toner, (1) the addition amount of the polymerization initiator (KPS) in the preparation of the shell resin fine particle dispersion was changed to 7.5 parts by mass, and the addition amount of n-octyl mercaptan Was changed to 11.5 parts by mass to prepare an adhesive layer forming toner [6], except that a shell resin fine particle dispersion [S3] was prepared and used.

<Preparation Example 7 of Toner for Forming Adhesive Layer>
In Preparation Example 1 of the adhesive layer forming toner, (2) the types and addition amounts of the monomers in the preparation of the core resin fine particle dispersion were changed to those shown in Table 1, and the core resin fine particle dispersion [C5] was prepared. An adhesive layer forming toner [7] was prepared in the same manner except that this was used.

<Preparation Example 8 of Toner for Forming Adhesive Layer>
In Preparation Example 1 of the adhesive layer forming toner, (2) the monomer type and addition amount in the preparation of the core resin fine particle dispersion were changed to those shown in Table 1, and 10.5 parts by mass of n-octyl mercaptan was further added. A toner for forming an adhesive layer [8] was prepared in the same manner except that the core resin fine particle dispersion [C6] was prepared and used.

<Preparation Example 9 of Toner for Adhesive Layer Formation>
An adhesive layer forming toner [9] was prepared in the same manner as in Preparation Example 1 of the adhesive layer forming toner except that the core resin fine particle dispersion [C1] was changed to the following core resin fine particle dispersion [C7]. did.

-Preparation of core resin fine particle dispersion [C7] Using a reaction apparatus equipped with a stirrer, temperature sensor, cooling pipe and nitrogen introduction apparatus in a 5 L reaction vessel, a surfactant solution was charged in the reaction apparatus in advance, and a nitrogen stream The liquid temperature was raised to 80 ° C. while stirring at a rotation speed of 230 rpm. As the surfactant solution, 0.8 part by mass of an anionic surfactant (SDS) and 2820 parts by mass of ion-exchanged water were used. After adding 6 parts by weight of a polymerization initiator (KPS) to the surfactant solution, 40 parts by weight of acrylic acid, 400 parts by weight of n-butyl acrylate, 40 parts by weight of methyl methacrylate and 320 parts by weight of 2-ethylhexyl acrylate are added for 3 hours. After completion of dropping, the mixture was kept at 80 ° C. for 2 hours to prepare a dispersion of core resin fine particles [C7] (hereinafter referred to as “core resin fine particle dispersion [C7]”).

<Example 10 of Preparation of Toner for Adhesive Layer Formation>
In Production Example 1 of the adhesive layer forming toner, (1) the addition amount of the polymerization initiator (KPS) in the preparation of the shell resin fine particle dispersion was changed to 17 parts by mass, and the addition amount of n-octyl mercaptan was 25. The adhesive layer forming toner [10] was prepared in the same manner except that the shell resin fine particle dispersion [S4] was prepared and used.

<Adhesion layer forming toner production example 11>
In Preparation Example 1 of the adhesive layer forming toner, (1) the addition amount of the polymerization initiator (KPS) in the preparation of the shell resin fine particle dispersion was changed to 4.5 parts by mass, and the addition amount of n-octyl mercaptan Was changed to 3.5 parts by mass, and a toner for forming an adhesive layer [11] was prepared in the same manner except that a shell resin fine particle dispersion [S5] was prepared and used.

<Development Examples 1 to 11>
For the adhesive layer forming toners [1] to [11], a ferrite carrier having a volume-based median diameter of 60 μm coated with a silicone resin is used, and the concentration of the adhesive layer forming toner is 6 mass% using a V-type mixer. The adhesive layer forming developers [1] to [11] were prepared.

<Examples 1-6, Comparative Examples 1-5>
An image forming apparatus "bizhub PRESS C6000" (manufactured by Konica Minolta Business Technologies) uses a modified developing means and a fixing device as in the image forming apparatus shown in FIG. [1] to [11] were mounted, and an adhesive layer as shown in FIG. 1 was formed on one side of the A4 size CF paper to produce sticky notes [1] to [11]. The adhesive layer forming region A was set to 3.0 cm × 27.0 cm and the toner adhesion amount was 12 g / m ² . Evaluation 1 and 2 were performed about the obtained sticky note paper.

[Evaluation 1: Adhesiveness]
A3 size white CF paper was used as a mount, and the sticky notes [1] to [11] were respectively attached to the mount, and the mount was fixed vertically with the sticky notes attached, and left for 12 hours.
After 12 hours, "A" if the sticky note remains fixed on the backing sheet, "B" if the sticky paper has an adhesive layer that is lifted or tilted from the backing, and the sticky note is peeled off from the backing paper. It was evaluated as “C”.

[Evaluation 2: Peelability]
In the above evaluation 1, with respect to those not peeled off from the mount (those evaluated as “A” and “B”), the end of the sticky note (the portion where the adhesive layer is not formed) is held by hand and 3 Peel off over a second, peel off by hand, “A” if there is no curl on the sticky note, “B” if it peels off by hand but causes curl, and “C” if it does not peel or break by hand evaluated.

[Evaluation 3: Adhesive properties]
Using the image forming apparatus used in the above evaluations 1 and 2, the screen pattern in the adhesive layer forming region is changed to the screen patterns A to C shown in FIG. 4, and the sticky notes [A1] to [A11], [B1] to [B1] B11] and [C1] to [C11] were respectively produced. The toner adhesion amount was set to be 10 g / m ^{2 in} all cases. Of the obtained sticky notes, “A” indicates that the sticky paper is sufficiently sticky and does not curl after peeling, “B” indicates that the sticking is sufficient but the curling occurs, and the adhesive strength is insufficient (the adhesive layer of the sticky note paper) However, it was evaluated as “C” when there was no curling, and “D” when there was a problem with adhesion and peelability (not peeled off, dropped from the mount, and broken when peeled). .
The pattern A shown in FIG. 4 is a pattern that uniformly forms a toner image for forming an adhesive layer on the paper surface, the pattern B is a pattern that forms a line of about 40 μm on the paper surface, and the pattern C has a diameter on the paper surface. This is a pattern for forming dots of about 80 μm.

10 Intermediate transfer section 11, 11S Charging means 12, 12S Exposure means 12A Semiconductor laser light source 12A
12B Polygon mirror 12C fθ lens 13, 13S Developing unit 14, 14S Transfer unit 15, 15S Photoconductor 16 Separating unit 17 Pre-charging exposure unit 19, 19S Cleaning unit 19A Cleaning blade 20, 20S Adhesive layer forming toner image forming unit 20Y, 20M, 20C, 20Bk Colored toner image forming unit 26 Intermediate transfer member 261 Cleaning means 27S, 27Y, 27M, 27C, 27Bk Primary transfer roller 29 Secondary transfer roller 40 Paper feed cassette 50 Adhesive layer forming device 51 Heating and pressure roller 52 Heating Pressure roller 70 Fixing device 71 Conveying path A Adhesive layer forming region P Base sheet S Adhesive layer

Claims (7)

An adhesive layer on at least a part of a base sheet is a method for producing a sticky note formed using an image forming method by electrophotography,
A charging step for charging the photoreceptor;
An exposure step of forming an electrostatic latent image by exposing the photoreceptor;
Developing the electrostatic latent image with an adhesive layer-forming toner comprising core-shell structured toner particles, thereby forming an adhesive layer-forming toner image;
A transfer step of transferring the adhesive layer forming toner image to a substrate sheet;
An adhesive layer forming step in which the core is exposed to form an adhesive layer by breaking or melting the shells in the toner particles forming the adhesive layer forming toner image;
The core contains an adhesive material made of an acrylate ester polymer, and the acrylate ester polymer has a Young's modulus of 5 × 10 ⁵ dyn / cm ² or more and 5 × 10 ⁸ dyn / cm ² or less. Having a weight average molecular weight of 200,000 to 1,000,000,
The method for producing a sticky note, wherein the shell contains a resin having a weight average molecular weight of 5,000 or more and 50,000 or less. The acrylic ester polymer has a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2), and the total of these structural units is in the acrylic ester polymer. The sticky note making method according to claim 1, wherein the sticky paper is contained in a ratio of 75% by mass or more.

[In the above formulas (1) and (2), R ¹ and R ³ each independently represent a hydrogen atom, a methyl group or an ethyl group, and may be the same or different from each other. . R ² and R ⁴ each independently represent an alkyl group having 2 to 12 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms, and are different from each other. ]   The sticky note making method according to claim 1 or 2, wherein the adhesive layer forming step is performed using at least one of a pressurizing unit and a heating unit. In the acrylate polymer, R ¹ and R ³ in the above formulas (1) and (2) are each independently a hydrogen atom or a methyl group, and R ² and R ⁴ are different from each other. A polymer having a structural unit which is an alkyl group of several 4 to 10 and has a weight average molecular weight of 400,000 or more and 600,000 or less and a glass transition point of −50 ° C. or more and 20 ° C. or less. The sticky note making method according to claim 2 or 3.   The resin contained in the shell has a weight average molecular weight of 10,000 or more and 30,000 or less, and a glass transition point of 35 ° C or more and 75 ° C or less. A method of making sticky notes according to crab.   The resin contained in the shell is at least one selected from a styrene-acrylic copolymer resin, a (meth) acrylic ester copolymer resin, a polyester resin, and a polyurethane resin. The sticky note making method according to claim 5.   The core-shell toner particles are added to a dispersion of acrylate polymer fine particles prepared by an emulsion polymerization method to agglomerate the acrylate polymer fine particles to form core particles. And by adding a dispersion of resin fine particles forming a shell to the core particle dispersion, the shell resin fine particles are adhered to the core particles to form a shell layer. The sticky note making method according to claim 1, wherein the sticky note is made.

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