JP2021018425A - 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 - Google Patents
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 Download PDFInfo
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- JP2021018425A JP2021018425A JP2020102613A JP2020102613A JP2021018425A JP 2021018425 A JP2021018425 A JP 2021018425A JP 2020102613 A JP2020102613 A JP 2020102613A JP 2020102613 A JP2020102613 A JP 2020102613A JP 2021018425 A JP2021018425 A JP 2021018425A
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- pressure
- meth
- acrylic acid
- responsive particles
- responsive
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- 239000004215 Carbon black (E152) Substances 0.000 description 1
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- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
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- 239000011575 calcium Substances 0.000 description 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
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- 239000010949 copper Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
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- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- IUJAMGNYPWYUPM-UHFFFAOYSA-N hentriacontane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC IUJAMGNYPWYUPM-UHFFFAOYSA-N 0.000 description 1
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- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000012184 mineral wax Substances 0.000 description 1
- 235000013872 montan acid ester Nutrition 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
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- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
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- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
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- 238000003825 pressing Methods 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
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Landscapes
- Fixing For Electrophotography (AREA)
- Electrophotography Configuration And Component (AREA)
- Color Electrophotography (AREA)
- Developing Agents For Electrophotography (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、圧力応答性粒子、カートリッジ、印刷物の製造装置、印刷物の製造方法、印刷物、印刷物製造用シート、及び印刷物製造用シートの製造方法に関する。 The present invention relates to pressure-responsive particles, a cartridge, a printed matter manufacturing apparatus, a printed matter manufacturing method, a printed matter, a printed matter manufacturing sheet, and a printed matter manufacturing sheet manufacturing method.
特許文献1には、水性溶媒中に2種類のアクリル系ポリマーを含む水分散型粘着剤組成物が記載されている。 Patent Document 1 describes an aqueous dispersion type pressure-sensitive adhesive composition containing two types of acrylic polymers in an aqueous solvent.
特許文献2には、式「20℃≦T(1MPa)−T(10MPa)」(T(1MPa)は印加圧力1MPaにおいて粘度が104Pa・sになるときの温度を表し、T(10MPa)は印加圧力10MPaにおいて粘度が104Pa・sになるときの温度を表す。)を満たす接着材料が記載されている。 Patent Document 2, the expression "20 ℃ ≦ T (1MPa) -T (10MPa) " (T (1MPa) represents the temperature at which the viscosity at an applied pressure 1MPa becomes 10 4 Pa · s, T ( 10MPa) It is described adhesive material that satisfies the representative.) the temperature at which the viscosity becomes 10 4 Pa · s at an applied pressure 10MPa is.
特許文献3には、スチレン樹脂及び当該スチレン樹脂よりもガラス転移温度が30℃以上低い(メタ)アクリル酸エステル樹脂を含み、スチレン樹脂を含む海部及び(メタ)アクリル酸エステル樹脂を含む島部で構成された海島構造を有し、島部の長径が200nm以上500nm以下であるコア部と、コア部を被覆しガラス転移温度が50℃以上の樹脂を含むシェル層と、を有する圧力定着トナーが記載されている。 Patent Document 3 includes a styrene resin and a (meth) acrylic acid ester resin having a glass transition temperature lower than that of the styrene resin by 30 ° C. or more, and in a sea portion containing the styrene resin and an island portion containing the (meth) acrylic acid ester resin. A pressure-fixing toner having a configured sea-island structure, a core portion having a major axis of 200 nm or more and 500 nm or less, and a shell layer covering the core portion and containing a resin having a glass transition temperature of 50 ° C. or more. Have been described.
特許文献4には、モノマー原料(A)の重合物であるアクリル系ポリマー(A)と、モノマー原料(B)の重合物であるアクリル系ポリマー(B)とを含み、アクリル系ポリマー(B)のガラス転移温度は0℃以上であり、アクリル系ポリマー(B)の重量平均分子量は0.3×104より大きく5×104以下であり、アクリル系ポリマー(A)の重量平均分子量は40×104以上であり、アクリル系ポリマー(B)のガラス転移温度とアクリル系ポリマー(A)のガラス転移温度との差は70℃以上であり、モノマー原料(B)はカルボキシル基含有モノマーを3重量%以上20重量%以下の割合で含む、水分散型粘着剤組成物が記載されている。 Patent Document 4 includes an acrylic polymer (A) which is a polymer of the monomer raw material (A) and an acrylic polymer (B) which is a polymer of the monomer raw material (B), and the acrylic polymer (B) glass transition temperature is 0 ℃ or more, weight average molecular weight of the acrylic polymer (B) is at 0.3 × 10 4 greater than 5 × 10 4 or less, the weight average molecular weight of the acrylic polymer (a) is 40 × is 10 4 or more, the difference between the glass transition temperature of the glass transition temperature and the acrylic polymer (a) of the acrylic polymer (B) is at 70 ° C. or more, the monomer material (B) is a carboxyl group-containing monomer 3 A water-dispersible pressure-sensitive adhesive composition containing a weight% or more and 20% by weight or less is described.
特許文献5には、接着層がアクリル酸・メタクリル酸アルキル共重合物を含有する圧着葉書用紙が記載されている。 Patent Document 5 describes a crimped postcard paper in which the adhesive layer contains an acrylic acid / alkyl methacrylate copolymer.
本開示は、スチレン系樹脂及び(メタ)アクリル酸エステル系樹脂を含む圧力応答性粒子であって、(メタ)アクリル酸エステル系樹脂が(メタ)アクリル酸エステルのホモポリマーである圧力応答性粒子に比べて、圧力によって相転移しやすく且つ接着性に優れる圧力応答性粒子を提供することを課題とする。 The present disclosure is a pressure-responsive particle containing a styrene resin and a (meth) acrylic acid ester-based resin, wherein the (meth) acrylic acid ester-based resin is a homopolymer of the (meth) acrylic acid ester. It is an object of the present invention to provide pressure-responsive particles which are easily phase-translated by pressure and have excellent adhesiveness.
前記課題を解決するための具体的手段には、下記の態様が含まれる。 Specific means for solving the above problems include the following aspects.
<1> スチレン及びその他のビニルモノマーを重合成分に含むスチレン系樹脂と、
少なくとも2種の(メタ)アクリル酸エステルを重合成分に含み、重合成分全体に占める(メタ)アクリル酸エステルの質量割合が90質量%以上である(メタ)アクリル酸エステル系樹脂と、を含み、
少なくとも2つのガラス転移温度を有し、最も低いガラス転移温度と最も高いガラス転移温度との差が30℃以上である、
圧力応答性粒子。
<2> 前記スチレン系樹脂の重合成分全体に占めるスチレンの質量割合が60質量%以上95質量%以下である、<1>に圧力応答性粒子。
<3> 前記(メタ)アクリル酸エステル系樹脂に重合成分として含まれる前記少なくとも2種の(メタ)アクリル酸エステルのうち最も質量割合の多い2種の質量比が80:20〜20:80である、<1>又は<2>に記載の圧力応答性粒子。
<4> 前記(メタ)アクリル酸エステル系樹脂に重合成分として含まれる前記少なくとも2種の(メタ)アクリル酸エステルのうち最も質量割合の多い2種が(メタ)アクリル酸アルキルエステルであり、当該2種の(メタ)アクリル酸アルキルエステルのアルキル基の炭素数の差が1個以上4個以下である、<1>〜<3>のいずれか1項に記載の圧力応答性粒子。
<5> 前記スチレン系樹脂に重合成分として含まれる前記その他のビニルモノマーが(メタ)アクリル酸エステルを含む、<1>〜<4>のいずれか1項に記載の圧力応答性粒子。
<6> 前記スチレン系樹脂に重合成分として含まれる前記その他のビニルモノマーがアクリル酸n−ブチル及びアクリル酸2−エチルヘキシルの少なくとも一方を含む、<1>〜<5>のいずれか1項に記載の圧力応答性粒子。
<7> 前記スチレン系樹脂と前記(メタ)アクリル酸エステル系樹脂とが同種の(メタ)アクリル酸エステルを重合成分として含む、<1>〜<6>のいずれか1項に記載の圧力応答性粒子。
<8> 前記(メタ)アクリル酸エステル系樹脂が重合成分としてアクリル酸2−エチルヘキシル及びアクリル酸n−ブチルを含む、<1>〜<7>のいずれか1項に記載の圧力応答性粒子。
<9> 前記スチレン系樹脂の含有量が前記(メタ)アクリル酸エステル系樹脂の含有量よりも多い、<1>〜<8>のいずれか1項に記載の圧力応答性粒子。
<10> 前記スチレン系樹脂を含む海相と、前記海相に分散した前記(メタ)アクリル酸エステル系樹脂を含む島相とを有する、<1>〜<9>のいずれか1項に記載の圧力応答性粒子。
<11> 前記島相の平均径が200nm以上500nm以下である、<10>に記載の圧力応答性粒子。
<12> 前記スチレン系樹脂及び前記(メタ)アクリル酸エステル系樹脂を含有するコア部と、前記コア部を被覆するシェル層と、を有する、<1>〜<11>のいずれか1項に記載の圧力応答性粒子。
<13> 前記シェル層が前記スチレン系樹脂を含有する、<12>に記載の圧力応答性粒子。
<14> 圧力4MPa下に粘度10000Pa・sを示す温度が90℃以下である、<1>〜<13>のいずれか1項に記載の圧力応答性粒子。
<1> Styrene-based resin containing styrene and other vinyl monomers as polymerization components,
A (meth) acrylic acid ester-based resin containing at least two kinds of (meth) acrylic acid esters in the polymerization component and having a mass ratio of the (meth) acrylic acid ester to the total polymerization component of 90% by mass or more is included.
It has at least two glass transition temperatures, and the difference between the lowest glass transition temperature and the highest glass transition temperature is 30 ° C. or more.
Pressure responsive particles.
<2> Pressure-responsive particles according to <1>, wherein the mass ratio of styrene to the total polymerized components of the styrene resin is 60% by mass or more and 95% by mass or less.
<3> The mass ratio of the two types having the largest mass ratio among the at least two types of (meth) acrylic acid esters contained as a polymerization component in the (meth) acrylic acid ester resin is 80:20 to 20:80. The pressure-responsive particles according to <1> or <2>.
<4> Of the at least two (meth) acrylic acid esters contained in the (meth) acrylic acid ester-based resin as a polymerization component, the two having the largest mass ratio are (meth) acrylic acid alkyl esters. The pressure-responsive particle according to any one of <1> to <3>, wherein the difference in the number of carbon atoms of the alkyl groups of the two types of (meth) acrylic acid alkyl esters is 1 or more and 4 or less.
<5> The pressure-responsive particles according to any one of <1> to <4>, wherein the other vinyl monomer contained as a polymerization component in the styrene resin contains a (meth) acrylic acid ester.
<6> The item according to any one of <1> to <5>, wherein the other vinyl monomer contained in the styrene resin as a polymerization component contains at least one of n-butyl acrylate and 2-ethylhexyl acrylate. Pressure responsive particles.
<7> The pressure response according to any one of <1> to <6>, wherein the styrene resin and the (meth) acrylic acid ester resin contain the same type of (meth) acrylic acid ester as a polymerization component. Sex particles.
<8> The pressure-responsive particles according to any one of <1> to <7>, wherein the (meth) acrylic acid ester-based resin contains 2-ethylhexyl acrylate and n-butyl acrylate as polymerization components.
<9> The pressure-responsive particles according to any one of <1> to <8>, wherein the content of the styrene resin is higher than the content of the (meth) acrylic acid ester resin.
<10> The item according to any one of <1> to <9>, which has a sea phase containing the styrene resin and an island phase containing the (meth) acrylic acid ester resin dispersed in the sea phase. Pressure responsive particles.
<11> The pressure-responsive particles according to <10>, wherein the island phase has an average diameter of 200 nm or more and 500 nm or less.
<12> In any one of <1> to <11>, which has a core portion containing the styrene resin and the (meth) acrylic acid ester resin, and a shell layer covering the core portion. The pressure-responsive particles described.
<13> The pressure-responsive particles according to <12>, wherein the shell layer contains the styrene resin.
<14> The pressure-responsive particles according to any one of <1> to <13>, wherein the temperature showing a viscosity of 10000 Pa · s under a pressure of 4 MPa is 90 ° C. or lower.
<15> <1>〜<14>のいずれか1項に記載の圧力応答性粒子を収容し、印刷物の製造装置に着脱されるカートリッジ。
<16> <1>〜<14>のいずれか1項に記載の圧力応答性粒子を収容し、前記圧力応答性粒子を記録媒体上に配置する配置手段と、
前記記録媒体を折り重ねて圧着する、又は、前記記録媒体と別の記録媒体とを重ねて圧着する圧着手段と、
を含む印刷物の製造装置。
<17> 色材を用いて記録媒体上に有色画像を形成する有色画像形成手段をさらに含む、<16>に記載の印刷物の製造装置。
<18> <1>〜<14>のいずれか1項に記載の圧力応答性粒子を用いて、前記圧力応答性粒子を記録媒体上に配置する配置工程と、
前記記録媒体を折り重ねて圧着する、又は、前記記録媒体と別の記録媒体とを重ねて圧着する圧着工程と、
を含む印刷物の製造方法。
<19> 色材を用いて記録媒体上に有色画像を形成する有色画像形成工程をさらに含む、<17>に記載の印刷物の製造方法。
<15> A cartridge that contains the pressure-responsive particles according to any one of <1> to <14> and is attached to and detached from a printed matter manufacturing apparatus.
<16> An arrangement means for accommodating the pressure-responsive particles according to any one of <1> to <14> and arranging the pressure-responsive particles on a recording medium.
A crimping means for folding and crimping the recording medium, or stacking and crimping the recording medium and another recording medium.
Printed matter manufacturing equipment including.
<17> The printed matter manufacturing apparatus according to <16>, further comprising a colored image forming means for forming a colored image on a recording medium using a coloring material.
<18> 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>.
A crimping step in which the recording medium is folded and crimped, or the recording medium and another recording medium are overlapped and crimped.
A method for manufacturing printed matter including.
<19> The method for producing a printed matter according to <17>, further comprising a colored image forming step of forming a colored image on a recording medium using a coloring material.
<20> 折り重なった記録媒体が、対向する面において、<1>〜<14>のいずれか1項に記載の圧力応答性粒子によって接着されてなる印刷物。
<21> 重なった複数の記録媒体が、対向する面において、<1>〜<14>のいずれか1項に記載の圧力応答性粒子によって接着されてなる印刷物。
<20> A printed matter in which folded recording media are adhered to each other on opposite surfaces by the pressure-responsive particles according to any one of <1> to <14>.
<21> A printed matter in which a plurality of overlapping recording media are adhered to each other on facing surfaces by the pressure-responsive particles according to any one of <1> to <14>.
<22> <1>〜<14>のいずれか1項に記載の圧力応答性粒子が用いられ、
基材と、前記基材上に配置された前記圧力応答性粒子と、を有する印刷物製造用シート。
<23> <1>〜<14>のいずれか1項に記載の圧力応答性粒子を用いて、前記圧力応答性粒子を基材上に配置する配置工程を含む、
印刷物製造用シートの製造方法。
<22> The pressure-responsive particles according to any one of <1> to <14> are used.
A printed matter manufacturing sheet having a base material and the pressure-responsive particles arranged on the base material.
<23> A step of arranging the pressure-responsive particles on a substrate by using the pressure-responsive particles according to any one of <1> to <14> is included.
A method for manufacturing a sheet for manufacturing printed matter.
<1>に係る発明によれば、スチレン系樹脂及び(メタ)アクリル酸エステル系樹脂を含む圧力応答性粒子であって、(メタ)アクリル酸エステル系樹脂が(メタ)アクリル酸エステルのホモポリマーである圧力応答性粒子に比べて、圧力によって相転移しやすく且つ接着性に優れる圧力応答性粒子が提供される。
<2>に係る発明によれば、スチレン系樹脂の重合成分全体に占めるスチレンの質量割合が95質量%超である場合に比べて、圧力によって相転移しやすい圧力応答性粒子が提供される。
<3>に係る発明によれば、(メタ)アクリル酸エステル系樹脂に重合成分として含まれる少なくとも2種の(メタ)アクリル酸エステルのうち最も質量割合の多い2種の質量比が80:20〜20:80の範囲を外れる場合に比べて、圧力によって相転移しやすく且つ接着性に優れる圧力応答性粒子が提供される。
<4>に係る発明によれば、前記2種の(メタ)アクリル酸アルキルエステルのアルキル基の炭素数の差が5個以上である場合に比べて、圧力によって相転移しやすく且つ接着性に優れる圧力応答性粒子が提供される。
<5>、<6>又は<7>に係る発明によれば、スチレン系樹脂の代わりにポリスチレンを含む圧力応答性粒子に比べて、圧力によって相転移しやすい圧力応答性粒子が提供される。
<8>に係る発明によれば、スチレン系樹脂及び(メタ)アクリル酸エステル系樹脂を含む圧力応答性粒子であって、(メタ)アクリル酸エステル系樹脂がアクリル酸2−エチルヘキシルのホモポリマーである圧力応答性粒子に比べて、接着性に優れる圧力応答性粒子が提供される。
<9>に係る発明によれば、スチレン系樹脂の含有量が(メタ)アクリル酸エステル系樹脂の含有量よりも少ない場合に比べて、接着性が維持される圧力応答性粒子が提供される。
<10>に係る発明によれば、前記海島構造を有しない場合に比べて、圧力によって相転移しやすく且つ接着性に優れる圧力応答性粒子が提供される。
<11>に係る発明によれば、島相の平均径が500nm超である場合に比べて、圧力によって相転移しやすい圧力応答性粒子が提供される。
<12>に係る発明によれば、コア部にスチレン系樹脂のみ又は(メタ)アクリル酸エステル系樹脂のみを含有するコア・シェル構造である場合に比べて、圧力によって相転移しやすい圧力応答性粒子が提供される。
<13>に係る発明によれば、シェル層がスチレン系樹脂を含有せずそれ以外の樹脂を含有する場合に比べて、圧力によって相転移しやすい圧力応答性粒子が提供される。
<14>に係る発明によれば、圧力4MPa下に粘度10000Pa・sを示す温度が90℃超である場合に比べて、圧力によって相転移しやすい圧力応答性粒子が提供される。
According to the invention according to <1>, pressure-responsive particles containing a styrene resin and a (meth) acrylic acid ester resin, wherein the (meth) acrylic acid ester resin is a homopolymer of the (meth) acrylic acid ester. Provided are pressure-responsive particles that are more likely to undergo a phase transition due to pressure and have excellent adhesiveness than the pressure-responsive particles.
According to the invention according to <2>, pressure-responsive particles that are more likely to undergo a phase transition due to pressure are provided as compared with the case where the mass ratio of styrene to the total polymerization component of the styrene resin is more than 95% by mass.
According to the invention according to <3>, the mass ratio of the two types having the largest mass ratio among at least two types of (meth) acrylic acid esters contained as a polymerization component in the (meth) acrylic acid ester-based resin is 80:20. Pressure-responsive particles that are more likely to undergo a phase transition due to pressure and have excellent adhesiveness are provided as compared with the case where the range is out of the range of about 20:80.
According to the invention according to <4>, the phase transition is more likely to occur due to pressure and the adhesiveness is improved as compared with the case where the difference in the number of carbon atoms of the alkyl groups of the two types of (meth) acrylic acid alkyl esters is 5 or more. Excellent pressure responsive particles are provided.
According to the invention according to <5>, <6> or <7>, pressure-responsive particles that are more likely to undergo a phase transition due to pressure are provided as compared with pressure-responsive particles containing polystyrene instead of a styrene resin.
According to the invention according to <8>, the pressure-responsive particles include a styrene resin and a (meth) acrylic acid ester resin, and the (meth) acrylic acid ester resin is a homopolymer of 2-ethylhexyl acrylate. Provided are pressure-responsive particles having better adhesiveness than certain pressure-responsive particles.
According to the invention according to <9>, pressure-responsive particles whose adhesiveness is maintained as compared with the case where the content of the styrene resin is smaller than the content of the (meth) acrylic acid ester resin are provided. ..
According to the invention according to <10>, pressure-responsive particles that are more likely to undergo a phase transition due to pressure and have excellent adhesiveness are provided as compared with the case where the sea-island structure is not provided.
According to the invention according to <11>, pressure-responsive particles that are more likely to undergo a phase transition due to pressure are provided as compared with the case where the average diameter of the island phase is more than 500 nm.
According to the invention according to <12>, the pressure responsiveness is more likely to undergo a phase transition due to pressure as compared with the case where the core portion has a core-shell structure containing only a styrene resin or a (meth) acrylic acid ester resin. Particles are provided.
According to the invention of <13>, pressure-responsive particles that are more likely to undergo a phase transition due to pressure are provided as compared with the case where the shell layer does not contain a styrene-based resin and contains other resins.
According to the invention according to <14>, pressure-responsive particles that are more likely to undergo a phase transition due to pressure are provided as compared with the case where the temperature showing a viscosity of 10000 Pa · s under a pressure of 4 MPa is over 90 ° C.
<15>に係る発明によれば、スチレン系樹脂及び(メタ)アクリル酸エステル系樹脂を含む圧力応答性粒子であって、(メタ)アクリル酸エステル系樹脂が(メタ)アクリル酸エステルのホモポリマーである圧力応答性粒子に比べて、圧力によって相転移しやすく且つ接着性に優れる圧力応答性粒子を収容したカートリッジが提供される。
<16>又は<17>に係る発明によれば、スチレン系樹脂及び(メタ)アクリル酸エステル系樹脂を含む圧力応答性粒子であって、(メタ)アクリル酸エステル系樹脂が(メタ)アクリル酸エステルのホモポリマーである圧力応答性粒子に比べて、圧力によって相転移しやすく且つ接着性に優れる圧力応答性粒子を適用した印刷物の製造装置が提供される。
<18>又は<19>に係る発明によれば、スチレン系樹脂及び(メタ)アクリル酸エステル系樹脂を含む圧力応答性粒子であって、(メタ)アクリル酸エステル系樹脂が(メタ)アクリル酸エステルのホモポリマーである圧力応答性粒子に比べて、圧力によって相転移しやすく且つ接着性に優れる圧力応答性粒子を適用した印刷物の製造方法が提供される。
According to the invention according to <15>, the pressure-responsive particles containing a styrene resin and a (meth) acrylic acid ester resin, wherein the (meth) acrylic acid ester resin is a homopolymer of the (meth) acrylic acid ester. Provided is a cartridge containing pressure-responsive particles that are more likely to undergo a phase transition due to pressure and have excellent adhesiveness than the pressure-responsive particles.
According to the invention according to <16> or <17>, the pressure-responsive particles containing a styrene resin and a (meth) acrylic acid ester resin, wherein the (meth) acrylic acid ester resin is (meth) acrylic acid. Provided is an apparatus for producing a printed matter to which pressure-responsive particles which are easily undergoing a phase transition due to pressure and have excellent adhesiveness as compared with pressure-responsive particles which are homopolymers of an ester are applied.
According to the invention according to <18> or <19>, the pressure-responsive particles containing a styrene resin and a (meth) acrylic acid ester resin, wherein the (meth) acrylic acid ester resin is (meth) acrylic acid. Provided is a method for producing a printed matter to which pressure-responsive particles which are easily undergoing a phase transition by pressure and have excellent adhesiveness as compared with pressure-responsive particles which are homopolymers of an ester are applied.
<20>又は<21>に係る発明によれば、スチレン系樹脂及び(メタ)アクリル酸エステル系樹脂を含む圧力応答性粒子であって、(メタ)アクリル酸エステル系樹脂が(メタ)アクリル酸エステルのホモポリマーである圧力応答性粒子に比べて、圧力によって相転移しやすく且つ接着性に優れる圧力応答性粒子を適用した印刷物が提供される。 According to the invention according to <20> or <21>, the pressure-responsive particles containing a styrene resin and a (meth) acrylic acid ester resin, wherein the (meth) acrylic acid ester resin is (meth) acrylic acid. A printed matter to which pressure-responsive particles, which are homopolymers of esters, are applied, which are easily phase-translated by pressure and have excellent adhesiveness, is provided.
<22>に係る発明によれば、スチレン系樹脂及び(メタ)アクリル酸エステル系樹脂を含む圧力応答性粒子であって、(メタ)アクリル酸エステル系樹脂が(メタ)アクリル酸エステルのホモポリマーである圧力応答性粒子に比べて、圧力によって相転移しやすく且つ接着性に優れる圧力応答性粒子を適用した印刷物製造用シートが提供される。
<23>に係る発明によれば、スチレン系樹脂及び(メタ)アクリル酸エステル系樹脂を含む圧力応答性粒子であって、(メタ)アクリル酸エステル系樹脂が(メタ)アクリル酸エステルのホモポリマーである圧力応答性粒子に比べて、圧力によって相転移しやすく且つ接着性に優れる圧力応答性粒子を適用した印刷物製造用シートの製造方法が提供される。
According to the invention according to <22>, the pressure-responsive particles containing a styrene resin and a (meth) acrylic acid ester resin, wherein the (meth) acrylic acid ester resin is a homopolymer of the (meth) acrylic acid ester. Provided is a sheet for producing a printed matter to which pressure-responsive particles that are easily phase-translated by pressure and have excellent adhesiveness are applied as compared with the pressure-responsive particles.
According to the invention according to <23>, pressure-responsive particles containing a styrene resin and a (meth) acrylic acid ester resin, wherein the (meth) acrylic acid ester resin is a homopolymer of a (meth) acrylic acid ester. Provided is a method for producing a sheet for producing a printed matter, to which pressure-responsive particles which are easily phase-translated by pressure and have excellent adhesiveness are applied as compared with the pressure-responsive particles.
以下に、本開示の実施形態について説明する。これらの説明及び実施例は実施形態を例示するものであり、実施形態の範囲を制限するものではない。 The embodiments of the present disclosure will be described below. These descriptions and examples exemplify the embodiments and do not limit the scope of the embodiments.
本開示において「〜」を用いて示された数値範囲は、「〜」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。 The numerical range indicated by using "~" in the present disclosure indicates a range including the numerical values before and after "~" as the minimum value and the maximum value, respectively.
本開示中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本開示中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。 In the numerical range described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. .. Further, in the numerical range described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
本開示において「工程」との語は、独立した工程だけでなく、他の工程と明確に区別できない場合であってもその工程の所期の目的が達成されれば、本用語に含まれる。 In the present disclosure, the term "process" is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes.
本開示において実施形態を、図面を参照して説明する場合、当該実施形態の構成は図面に示された構成に限定されない。また、各図における部材の大きさは概念的なものであり、部材間の大きさの相対的な関係はこれに限定されない。 When the embodiment is described in the present disclosure with reference to the drawings, the configuration of the embodiment is not limited to the configuration shown in the drawings. Further, the size of the members in each figure is conceptual, and the relative relationship between the sizes of the members is not limited to this.
本開示において各成分は該当する物質を複数種含んでいてもよい。本開示において組成物中の各成分の量について言及する場合、組成物中に各成分に該当する物質が複数種存在する場合には、特に断らない限り、組成物中に存在する当該複数種の物質の合計量を意味する。 In the present disclosure, each component may contain a plurality of applicable substances. When referring to the amount of each component in the composition in the present disclosure, if a plurality of substances corresponding to each component are present in the composition, unless otherwise specified, the plurality of species present in the composition. It means the total amount of substances.
本開示において各成分に該当する粒子は複数種含んでいてもよい。組成物中に各成分に該当する粒子が複数種存在する場合、各成分の粒子径は、特に断らない限り、組成物中に存在する当該複数種の粒子の混合物についての値を意味する。 In the present disclosure, a plurality of types of particles corresponding to each component may be contained. When a plurality of particles corresponding to each component are present in the composition, the particle size of each component means a value for a mixture of the plurality of particles present in the composition unless otherwise specified.
本開示において「(メタ)アクリル」との表記は「アクリル」及び「メタクリル」のいずれでもよいことを意味する。 In the present disclosure, the notation "(meth) acrylic" means that either "acrylic" or "methacrylic" may be used.
本開示において、「静電荷像現像用トナー」を単に「トナー」ともいい、「静電荷像現像剤」を単に「現像剤」ともいう。 In the present disclosure, the "toner for static charge image development" is also simply referred to as "toner", and the "static charge image developer" is also simply referred to as "developer".
本開示において、記録媒体を折り重ね対向する面どうしを接着して形成した印刷物、又は、2以上の記録媒体を重ね対向する面どうしを接着して形成した印刷物を、「圧着印刷物」という。 In the present disclosure, a printed matter formed by folding and adhering facing surfaces of recording media or a printed matter formed by adhering two or more recording media and facing each other is referred to as a "crimped printed matter".
<圧力応答性粒子>
本実施形態に係る圧力応答性粒子は、
スチレン及びその他のビニルモノマーを重合成分に含むスチレン系樹脂と、
少なくとも2種の(メタ)アクリル酸エステルを重合成分に含み、重合成分全体に占める(メタ)アクリル酸エステルの質量割合が90質量%以上である(メタ)アクリル酸エステル系樹脂と、を含み、
少なくとも2つのガラス転移温度を有し、最も低いガラス転移温度と最も高いガラス転移温度との差が30℃以上である。
<Pressure-responsive particles>
The pressure-responsive particles according to this embodiment are
Styrene-based resin containing styrene and other vinyl monomers as polymerization components,
A (meth) acrylic acid ester-based resin containing at least two kinds of (meth) acrylic acid esters in the polymerization component and having a mass ratio of the (meth) acrylic acid ester to the total polymerization component of 90% by mass or more is included.
It has at least two glass transition temperatures, and the difference between the lowest glass transition temperature and the highest glass transition temperature is 30 ° C. or more.
本実施形態に係る圧力応答性粒子は、「少なくとも2つのガラス転移温度を有し、最も低いガラス転移温度と最も高いガラス転移温度との差が30℃以上である」との熱的特性を示すことにより、圧力によって相転移する。本開示において、圧力によって相転移する圧力応答性粒子とは、下記の式1を満たす圧力応答性粒子を意味する。 The pressure-responsive particles according to the present embodiment exhibit thermal characteristics that "have at least two glass transition temperatures, and the difference between the lowest glass transition temperature and the highest glass transition temperature is 30 ° C. or more". As a result, the phase transition is caused by pressure. In the present disclosure, the pressure-responsive particles that undergo a phase transition due to pressure mean pressure-responsive particles that satisfy the following formula 1.
式1・・・10℃≦T1−T2
式1において、T1は、圧力1MPa下に粘度10000Pa・sを示す温度であり、T2は、圧力10MPa下に粘度10000Pa・sを示す温度である。温度T1及び温度T2の求め方は後述する。
Equation 1 ... 10 ° C. ≤ T1-T2
In the formula 1, T1 is a temperature showing a viscosity of 10000 Pa · s under a pressure of 1 MPa, and T2 is a temperature showing a viscosity of 10000 Pa · s under a pressure of 10 MPa. How to obtain the temperature T1 and the temperature T2 will be described later.
本実施形態に係る圧力応答性粒子は、「スチレン及びその他のビニルモノマーを重合成分に含むスチレン系樹脂」と、「少なくとも2種の(メタ)アクリル酸エステルを重合成分に含み、重合成分全体に占める(メタ)アクリル酸エステルの質量割合が90質量%以上である(メタ)アクリル酸エステル系樹脂」と、を含むことにより、圧力によって相転移しやすく且つ接着性に優れる。その機序として、次のことが推測される。 The pressure-responsive particles according to the present embodiment include "a styrene resin containing styrene and other vinyl monomers as the polymerization component" and "at least two kinds of (meth) acrylic acid esters in the polymerization component, and the entire polymerization component contains. By including "a (meth) acrylic acid ester-based resin" in which the mass ratio of the (meth) acrylic acid ester is 90% by mass or more, the phase transition is easy due to pressure and the adhesiveness is excellent. The following is presumed as the mechanism.
一般的にスチレン系樹脂と(メタ)アクリル酸エステル系樹脂とは互いに対する相溶性が低いので、両樹脂は圧力応答性母粒子中に相分離した状態で含まれていると考えられる。また、圧力応答性母粒子が加圧されると、ガラス転移温度が比較的低い(メタ)アクリル酸エステル系樹脂がまず流動化し、その流動化がスチレン系樹脂に波及し、両樹脂ともに流動化すると考えられる。また、圧力応答性母粒子中の両樹脂は、加圧によって流動化したのち減圧にしたがい固化して樹脂層を形成する際に、相溶性の低さゆえ、再び相分離状態を形成すると考えられる。
少なくとも2種の(メタ)アクリル酸エステルを重合成分に含む(メタ)アクリル酸エステル系樹脂は、主鎖に結合しているエステル基の種類が少なくとも2種類であることにより、(メタ)アクリル酸エステルのホモポリマーに比べて、固体状態での分子の整列度が低く、それゆえ加圧によって流動化しやすいと推測される。さらに、重合成分全体に占める(メタ)アクリル酸エステルの質量割合が90質量%以上であると、エステル基が少なくとも2種類、密度高く存在することになるので、固体状態での分子の整列度がより低くなり、それゆえ加圧によってより流動化しやすいと推測される。したがって、本実施形態に係る圧力応答性粒子は、(メタ)アクリル酸エステル系樹脂が(メタ)アクリル酸エステルのホモポリマーである圧力応答性粒子に比べて、圧力によって流動化しやすい、つまり圧力によって相転移しやすいと推測される。
そして、少なくとも2種の(メタ)アクリル酸エステルを重合成分に含み、重合成分全体に占める(メタ)アクリル酸エステルの質量割合が90質量%以上である(メタ)アクリル酸エステル系樹脂は、再び固化する際においても分子の整列度が低いので、スチレン系樹脂との相分離が微小な相分離になると推測される。スチレン系樹脂と(メタ)アクリル酸エステル系樹脂との相分離の状態が微小であるほど、被接着物に対する接着面の状態が均一性高くなり、接着性に優れると推測される。したがって、本実施形態に係る圧力応答性粒子は、(メタ)アクリル酸エステル系樹脂が(メタ)アクリル酸エステルのホモポリマーである圧力応答性粒子に比べて、接着性に優れると推測される。
Generally, since the styrene resin and the (meth) acrylic acid ester resin have low compatibility with each other, it is considered that both resins are contained in the pressure-responsive mother particles in a phase-separated state. Further, when the pressure-responsive mother particles are pressurized, the (meth) acrylic acid ester resin having a relatively low glass transition temperature first fluidizes, and the fluidization spreads to the styrene resin, and both resins fluidize. It is thought that. Further, both resins in the pressure-responsive mother particles are considered to form a phase-separated state again due to their low compatibility when they are fluidized by pressurization and then solidified under reduced pressure to form a resin layer. ..
A (meth) acrylic acid ester-based resin containing at least two types of (meth) acrylic acid esters as a polymerization component has (meth) acrylic acid because there are at least two types of ester groups bonded to the main chain. It is presumed that the molecular alignment in the solid state is lower than that of the ester homopolymer, and therefore it is easily fluidized by pressurization. Furthermore, when the mass ratio of the (meth) acrylic acid ester to the entire polymerized component is 90% by mass or more, at least two types of ester groups are present at high density, so that the degree of molecular alignment in the solid state is high. It is presumed to be lower and therefore more fluidized by pressurization. Therefore, the pressure-responsive particles according to the present embodiment are more easily fluidized by pressure than the pressure-responsive particles in which the (meth) acrylic acid ester-based resin is a homopolymer of (meth) acrylic acid ester, that is, by pressure. It is presumed that the phase transition is likely to occur.
Then, the (meth) acrylic acid ester-based resin containing at least two kinds of (meth) acrylic acid esters in the polymerization component and having a mass ratio of the (meth) acrylic acid ester to the entire polymerization component of 90% by mass or more is again used. Since the degree of molecular alignment is low even during solidification, it is presumed that the phase separation from the styrene resin becomes a minute phase separation. It is presumed that the smaller the phase separation state between the styrene resin and the (meth) acrylic acid ester resin, the higher the uniformity of the adhesive surface with respect to the object to be adhered, and the better the adhesiveness. Therefore, it is presumed that the pressure-responsive particles according to the present embodiment are superior in adhesiveness to the pressure-responsive particles in which the (meth) acrylic acid ester-based resin is a homopolymer of the (meth) acrylic acid ester.
以下、本実施形態に係る圧力応答性粒子の成分、構造及び特性について詳細に説明する。以下の説明において、特に断らない限り、「スチレン系樹脂」は「スチレン及びその他のビニルモノマーを重合成分に含むスチレン系樹脂」を意味し、「(メタ)アクリル酸エステル系樹脂」は「少なくとも2種の(メタ)アクリル酸エステルを重合成分に含み、重合成分全体に占める(メタ)アクリル酸エステルの質量割合が90質量%以上である(メタ)アクリル酸エステル系樹脂」を意味する。 Hereinafter, the components, structures, and characteristics of the pressure-responsive particles according to the present embodiment will be described in detail. In the following description, unless otherwise specified, "styrene resin" means "styrene resin containing styrene and other vinyl monomers as polymerization components", and "(meth) acrylic acid ester resin" means "at least 2". It means a (meth) acrylic acid ester-based resin containing a seed (meth) acrylic acid ester as a polymerization component and having a mass ratio of the (meth) acrylic acid ester to the entire polymerization component of 90% by mass or more.
本実施形態に係る圧力応答性粒子は、少なくとも圧力応答性母粒子を含み、必要に応じて外添剤を含む。 The pressure-responsive particles according to the present embodiment include at least pressure-responsive mother particles and, if necessary, an external additive.
[圧力応答性母粒子]
圧力応答性母粒子は、少なくともスチレン系樹脂及び(メタ)アクリル酸エステル系樹脂を含有する。圧力応答性母粒子は、着色剤、離型剤、その他添加剤を含有していてもよい。
[Pressure-responsive mother particles]
The pressure-responsive mother particles contain at least a styrene resin and a (meth) acrylic acid ester resin. The pressure-responsive mother particles may contain a colorant, a mold release agent, and other additives.
圧力応答性母粒子は、接着性を維持する観点から、スチレン系樹脂の含有量が(メタ)アクリル酸エステル系樹脂の含有量よりも多いことが好ましい。スチレン系樹脂の含有量は、スチレン系樹脂と(メタ)アクリル酸エステル系樹脂の合計含有量に対して、55質量%以上80質量%以下が好ましく、60質量%以上75質量%以下がより好ましく、65質量%以上70質量%以下が更に好ましい。 From the viewpoint of maintaining adhesiveness, the pressure-responsive mother particles preferably have a higher content of the styrene resin than the content of the (meth) acrylic acid ester resin. The content of the styrene resin is preferably 55% by mass or more and 80% by mass or less, more preferably 60% by mass or more and 75% by mass or less, based on the total content of the styrene resin and the (meth) acrylic acid ester resin. , 65% by mass or more and 70% by mass or less is more preferable.
−スチレン系樹脂−
本実施形態に係る圧力応答性粒子を構成する圧力応答性母粒子は、スチレン及びその他のビニルモノマーを重合成分に含むスチレン系樹脂を含有する。
-Styrene resin-
The pressure-responsive mother particles constituting the pressure-responsive particles according to the present embodiment contain a styrene-based resin containing styrene and other vinyl monomers as a polymerization component.
スチレン系樹脂の重合成分全体に占めるスチレンの質量割合は、加圧されていない状態で圧力応答性粒子が流動化することを抑制する観点から、60質量%以上が好ましく、70質量%以上がより好ましく、75質量%以上が更に好ましく、圧力によって相転移しやすい圧力応答性粒子を形成する観点から、95質量%以下が好ましく、90質量%以下がより好ましく、85質量%以下が更に好ましい。 The mass ratio of styrene to the total polymerized components of the styrene resin is preferably 60% by mass or more, more preferably 70% by mass or more, from the viewpoint of suppressing the fluidization of pressure-responsive particles in a non-pressurized state. It is more preferably 75% by mass or more, more preferably 95% by mass or less, still more preferably 90% by mass or less, still more preferably 85% by mass or less, from the viewpoint of forming pressure-responsive particles that easily undergo a phase transition due to pressure.
スチレン系樹脂を構成するスチレン以外のその他のビニルモノマーとしては、例えば、スチレン以外のスチレン系モノマー、アクリル系モノマーが挙げられる。 Examples of other vinyl monomers other than styrene constituting the styrene resin include styrene-based monomers other than styrene and acrylic monomers.
スチレン以外のスチレン系モノマーとしては、例えば、ビニルナフタレン;α−メチルスチレン、o−メチルスチレン、m−メチルスチレン、p−メチルスチレン、p−エチルスチレン、2,4−ジメチルスチレン、p−n−ブチルスチレン、p−tert−ブチルスチレン、p−n−ヘキシルスチレン、p−n−オクチルスチレン、p−n−ノニルスチレン、p−n−デシルスチレン、p−n−ドデシルスチレン等のアルキル置換スチレン;p−フェニルスチレン等のアリール置換スチレン;p−メトキシスチレン等のアルコキシ置換スチレン;p−クロロスチレン、3,4−ジクロロスチレン、p−フルオロスチレン、2,5−ジフルオロスチレン等のハロゲン置換スチレン;m−ニトロスチレン、o−ニトロスチレン、p−ニトロスチレン等のニトロ置換スチレン;などが挙げられる。スチレン系モノマーは、1種を単独で使用してもよいし、2種以上を併用してもよい。 Examples of styrene-based monomers other than styrene include vinylnaphthalene; α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-. Alkyl-substituted styrenes such as butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene; Aryl-substituted styrene such as p-phenylstyrene; alkoxy-substituted styrene such as p-methoxystyrene; halogen-substituted styrene such as p-chlorostyrene, 3,4-dichlorostyrene, p-fluorostyrene, 2,5-difluorostyrene; m -Nitro-substituted styrenes such as nitrostyrene, o-nitrostyrene, p-nitrostyrene; and the like. One type of styrene-based monomer may be used alone, or two or more types may be used in combination.
アクリル系モノマーとしては、(メタ)アクリル酸及び(メタ)アクリル酸エステルからなる群から選ばれる少なくとも1種のアクリル系モノマーが好ましい。(メタ)アクリル酸エステルとしては、(メタ)アクリル酸アルキルエステル、(メタ)アクリル酸カルボキシ置換アルキルエステル、(メタ)アクリル酸ヒドロキシ置換アルキルエステル、(メタ)アクリル酸アルコキシ置換アルキルエステル、ジ(メタ)アクリル酸エステル等が挙げられる。アクリル系モノマーは、1種を単独で使用してもよいし、2種以上を併用してもよい。 As the acrylic monomer, at least one acrylic monomer selected from the group consisting of (meth) acrylic acid and (meth) acrylic acid ester is preferable. Examples of the (meth) acrylic acid ester include (meth) acrylic acid alkyl ester, (meth) acrylic acid carboxy-substituted alkyl ester, (meth) acrylic acid hydroxy-substituted alkyl ester, (meth) acrylic acid alkoxy-substituted alkyl ester, and di (meth). ) Acrylic acid ester and the like can be mentioned. One type of acrylic monomer may be used alone, or two or more types may be used in combination.
(メタ)アクリル酸アルキルエステルとしては、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸n−ブチル、(メタ)メタクリル酸イソブチル、(メタ)アクリル酸n−ヘキシル、(メタ)アクリル酸2−エチルヘキシル、(メタ)アクリル酸ラウリル、(メタ)アクリル酸ステアリル、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸ジシクロペンタニル、(メタ)アクリル酸イソボルニル等が挙げられる。
(メタ)アクリル酸カルボキシ置換アルキルエステルとしては、(メタ)アクリル酸2−カルボキシエチル等が挙げられる。
(メタ)アクリル酸ヒドロキシ置換アルキルエステルとしては、(メタ)アクリル酸2−ヒドロキシエチル、(メタ)アクリル酸2−ヒドロキシプロピル、(メタ)アクリル酸3−ヒドロキシプロピル、(メタ)アクリル酸2−ヒドロキシブチル、(メタ)アクリル酸3−ヒドロキシブチル、(メタ)アクリル酸4−ヒドロキシブチル等が挙げられる。
(メタ)アクリル酸アルコキシ置換アルキルエステルとしては、(メタ)アクリル酸2−メトキシエチル等が挙げられる。
ジ(メタ)アクリル酸エステルとしては、エチレングリコールジ(メタ)アクリラート、ジエチレングリコールジ(メタ)アクリラート、トリエチレングリコールジ(メタ)アクリラート、ブタンジオールジ(メタ)アクリラート、ペンタンジオールジ(メタ)アクリラート、ヘキサンジオールジ(メタ)アクリラート、ノナンジオールジ(メタ)アクリラート、デカンジオールジ(メタ)アクリラート等が挙げられる。
Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, n-butyl (meth) acrylic acid, and (meth). Isobutyl methacrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclo (meth) acrylate Examples thereof include pentanyl and isobornyl (meth) acrylate.
Examples of the (meth) acrylic acid carboxy-substituted alkyl ester include 2-carboxyethyl (meth) acrylic acid.
Examples of the (meth) acrylic acid hydroxy-substituted alkyl ester include (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 3-hydroxypropyl, and (meth) acrylic acid 2-hydroxy. Examples thereof include butyl, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
Examples of the (meth) acrylic acid alkoxy-substituted alkyl ester include 2-methoxyethyl (meth) acrylic acid.
Examples of the di (meth) acrylic acid ester include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, and pentanediol di (meth) acrylate. Examples thereof include hexanediol di (meth) acrylate, nonanediol di (meth) acrylate, and decanediol di (meth) acrylate.
(メタ)アクリル酸エステルとしては、(メタ)アクリル酸2−(ジエチルアミノ)エチル、(メタ)アクリル酸ベンジル、メトキシポリエチレングリコール(メタ)アクリラート等も挙げられる。 Examples of the (meth) acrylic acid ester include 2- (diethylamino) ethyl (diethylamino) ethyl (meth) acrylate, benzyl (meth) acrylate, and methoxypolyethylene glycol (meth) acrylate.
スチレン系樹脂を構成するその他のビニルモノマーとしては、スチレン系モノマー及びアクリル系モノマーのほかに、例えば、(メタ)アクリロニトリル;ビニルメチルエーテル、ビニルイソブチルエーテル等のビニルエーテル;ビニルメチルケトン、ビニルエチルケトン、ビニルイソプロペニルケトン等のビニルケトン;イソプレン、ブテン、ブタジエン等のオレフィン;も挙げられる。 Other vinyl monomers constituting the styrene resin include, for example, (meth) acrylonitrile; vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; vinyl methyl ketone, vinyl ethyl ketone, and the like, in addition to the styrene monomer and the acrylic monomer. Vinyl ketones such as vinylisopropenylketone; olefins such as isoprene, butene and butadiene; are also included.
スチレン系樹脂は、圧力によって相転移しやすい圧力応答性粒子を形成する観点から、重合成分として(メタ)アクリル酸エステルを含むことが好ましく、(メタ)アクリル酸アルキルエステルを含むことがより好ましく、アルキル基の炭素数が2個以上10個以下である(メタ)アクリル酸アルキルエステルを含むことが更に好ましく、アルキル基の炭素数が4個以上8個以下である(メタ)アクリル酸アルキルエステルを含むことが更に好ましく、アクリル酸n−ブチル及びアクリル酸2−エチルヘキシルの少なくとも一方を含むことが特に好ましい。スチレン系樹脂と(メタ)アクリル酸エステル系樹脂とは、圧力によって相転移しやすい圧力応答性粒子を形成する観点から、同種の(メタ)アクリル酸エステルを重合成分として含むことが好ましい。 The styrene resin preferably contains a (meth) acrylic acid ester as a polymerization component, and more preferably contains a (meth) acrylic acid alkyl ester, from the viewpoint of forming pressure-responsive particles that easily undergo a phase transition due to pressure. It is more preferable to contain a (meth) acrylic acid alkyl ester having 2 or more and 10 or less carbon atoms in the alkyl group, and a (meth) acrylic acid alkyl ester having 4 or more and 8 or less carbon atoms in the alkyl group. It is more preferable to contain at least one of n-butyl acrylate and 2-ethylhexyl acrylate. The styrene resin and the (meth) acrylic acid ester resin preferably contain the same type of (meth) acrylic acid ester as a polymerization component from the viewpoint of forming pressure-responsive particles that easily undergo a phase transition due to pressure.
スチレン系樹脂の重合成分全体に占める(メタ)アクリル酸エステルの質量割合は、加圧されていない状態で圧力応答性粒子が流動化することを抑制する観点から、40質量%以下が好ましく、30質量%以下がより好ましく、25質量%以下が更に好ましく、圧力によって相転移しやすい圧力応答性粒子を形成する観点から、5質量%以上が好ましく、10質量%以上がより好ましく、15質量%以上が更に好ましい。ここでの(メタ)アクリル酸エステルとしては、(メタ)アクリル酸アルキルエステルが好ましく、アルキル基の炭素数が2個以上10個以下である(メタ)アクリル酸アルキルエステルがより好ましく、アルキル基の炭素数が4個以上8個以下である(メタ)アクリル酸アルキルエステルが更に好ましい。 The mass ratio of the (meth) acrylic acid ester to the total polymerized components of the styrene resin is preferably 40% by mass or less, preferably 30% by mass or less, from the viewpoint of suppressing the fluidization of the pressure-responsive particles in the unpressurized state. More preferably, it is 5% by mass or less, more preferably 25% by mass or less, and from the viewpoint of forming pressure-responsive particles that are easily phase-shifted by pressure, 5% by mass or more is more preferable, 10% by mass or more is more preferable, and 15% by mass or more. Is more preferable. As the (meth) acrylic acid ester here, a (meth) acrylic acid alkyl ester is preferable, and a (meth) acrylic acid alkyl ester having an alkyl group having 2 or more and 10 or less carbon atoms is more preferable, and the alkyl group has an alkyl group. A (meth) acrylic acid alkyl ester having 4 or more and 8 or less carbon atoms is more preferable.
スチレン系樹脂は重合成分としてアクリル酸n−ブチル及びアクリル酸2−エチルヘキシルの少なくとも一方を含むことが特に好ましく、スチレン系樹脂の重合成分全体に占めるアクリル酸n−ブチル及びアクリル酸2−エチルヘキシルの合計量は、加圧されていない状態で圧力応答性粒子が流動化することを抑制する観点から、40質量%以下が好ましく、30質量%以下がより好ましく、25質量%以下が更に好ましく、圧力によって相転移しやすい圧力応答性粒子を形成する観点から、5質量%以上が好ましく、10質量%以上がより好ましく、15質量%以上が更に好ましい。 The styrene resin preferably contains at least one of n-butyl acrylate and 2-ethylhexyl acrylate as the polymerization component, and the total of n-butyl acrylate and 2-ethylhexyl acrylate in the entire polymerization component of the styrene resin. The amount is preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 25% by mass or less, depending on the pressure, from the viewpoint of suppressing the fluidization of the pressure-responsive particles in the unpressurized state. From the viewpoint of forming pressure-responsive particles that easily undergo a phase transition, 5% by mass or more is preferable, 10% by mass or more is more preferable, and 15% by mass or more is further preferable.
スチレン系樹脂の重量平均分子量は、加圧されていない状態で圧力応答性粒子が流動化することを抑制する観点から、3000以上が好ましく、4000以上がより好ましく、5000以上が更に好ましく、圧力によって相転移しやすい圧力応答性粒子を形成する観点から、60000以下が好ましく、55000以下がより好ましく、50000以下が更に好ましい。 The weight average molecular weight of the styrene resin is preferably 3000 or more, more preferably 4000 or more, further preferably 5000 or more, depending on the pressure, from the viewpoint of suppressing the fluidization of pressure-responsive particles in a non-pressurized state. From the viewpoint of forming pressure-responsive particles that easily undergo a phase transition, 60,000 or less is preferable, 55,000 or less is more preferable, and 50,000 or less is further preferable.
本開示において樹脂の重量平均分子量は、ゲルパーミエーションクロマトグラフィ(GPC)により測定する。GPCによる分子量測定は、GPC装置として東ソー製HLC−8120GPCを用い、カラムとして東ソー製TSKgel SuperHM−M(15cm)を用い、溶媒としてテトラヒドロフランを用いて行う。樹脂の重量平均分子量は、単分散ポリスチレン標準試料により作成した分子量校正曲線を使用して算出する。 In the present disclosure, the weight average molecular weight of the resin is measured by gel permeation chromatography (GPC). The molecular weight measurement by GPC is performed by using HLC-8120GPC manufactured by Tosoh as a GPC device, TSKgel SuperHM-M (15 cm) manufactured by Tosoh as a column, and tetrahydrofuran as a solvent. The weight average molecular weight of the resin is calculated using a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample.
スチレン系樹脂のガラス転移温度は、加圧されていない状態で圧力応答性粒子が流動化することを抑制する観点から、30℃以上であることが好ましく、40℃以上であることがより好ましく、50℃以上であることが更に好ましく、圧力によって相転移しやすい圧力応答性粒子を形成する観点から、110℃以下であることが好ましく、100℃以下であることがより好ましく、90℃以下であることが更に好ましい。 The glass transition temperature of the styrene resin is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, from the viewpoint of suppressing the fluidization of pressure-responsive particles in a non-pressurized state. The temperature is more preferably 50 ° C. or higher, and from the viewpoint of forming pressure-responsive particles that easily undergo a phase transition due to pressure, the temperature is preferably 110 ° C. or lower, more preferably 100 ° C. or lower, and 90 ° C. or lower. Is even more preferable.
本開示において、樹脂のガラス転移温度は、示差走査熱量測定(Differential Scanning Calorimetry、DSC)を行って得た示差走査熱量曲線(DSC曲線)から求める。より具体的には、JIS K7121:1987「プラスチックの転移温度測定方法」のガラス転移温度の求め方に記載の「補外ガラス転移開始温度」に従って求める。 In the present disclosure, the glass transition temperature of the resin is obtained from the differential scanning calorimetry (DSC curve) obtained by performing differential scanning calorimetry (DSC). More specifically, it is obtained according to the "external glass transition start temperature" described in the method for determining the glass transition temperature of JIS K7121: 1987 "Method for measuring the transition temperature of plastics".
樹脂のガラス転移温度は、重合成分の種類及び重合割合によって制御できる。ガラス転移温度は、主鎖に含まれるメチレン基、エチレン基、オキシエチレン基等の柔軟な単位の密度が高いほど低く、主鎖に含まれる芳香環、シクロヘキサン環等の剛直な単位の密度が高いほど高い傾向がある。また、ガラス転移温度は、側鎖における脂肪族基の密度が高いほど低い傾向がある。 The glass transition temperature of the resin can be controlled by the type of polymerization component and the polymerization ratio. The glass transition temperature is lower as the density of flexible units such as methylene group, ethylene group and oxyethylene group contained in the main chain is higher, and the density of rigid units such as aromatic ring and cyclohexane ring contained in the main chain is higher. Tends to be high. In addition, the glass transition temperature tends to be lower as the density of aliphatic groups in the side chain increases.
本実施形態において圧力応答性母粒子全体に占めるスチレン系樹脂の質量割合は、加圧されていない状態で圧力応答性粒子が流動化することを抑制する観点から、55質量%以上が好ましく、60質量%以上がより好ましく、65質量%以上が更に好ましく、圧力によって相転移しやすい圧力応答性粒子を形成する観点から、80質量%以下が好ましく、75質量%以下がより好ましく、70質量%以下が更に好ましい。 In the present embodiment, the mass ratio of the styrene-based resin to the total pressure-responsive mother particles is preferably 55% by mass or more, preferably 60% by mass or more, from the viewpoint of suppressing the fluidization of the pressure-responsive particles in the unpressurized state. Mass% or more is more preferable, 65% by mass or more is further preferable, and from the viewpoint of forming pressure-responsive particles that easily undergo a phase transition due to pressure, 80% by mass or less is preferable, 75% by mass or less is more preferable, and 70% by mass or less. Is more preferable.
−(メタ)アクリル酸エステル系樹脂−
本実施形態に係る圧力応答性粒子を構成する圧力応答性母粒子は、少なくとも2種の(メタ)アクリル酸エステルを重合成分に含み、重合成分全体に占める(メタ)アクリル酸エステルの質量割合が90質量%以上である(メタ)アクリル酸エステル系樹脂を含有する。
-(Meta) acrylic acid ester resin-
The pressure-responsive mother particles constituting the pressure-responsive particles according to the present embodiment contain at least two types of (meth) acrylic acid esters in the polymerization component, and the mass ratio of the (meth) acrylic acid ester to the total polymerization component is Contains 90% by mass or more of (meth) acrylic acid ester resin.
(メタ)アクリル酸エステル系樹脂の重合成分全体に占める(メタ)アクリル酸エステルの質量割合は、90質量%以上であり、95質量%以上がより好ましく、98質量%以上が更に好ましく、100質量%が更に好ましい。 The mass ratio of the (meth) acrylic acid ester to the total polymerization component of the (meth) acrylic acid ester resin is 90% by mass or more, more preferably 95% by mass or more, further preferably 98% by mass or more, and 100% by mass. % Is more preferable.
(メタ)アクリル酸エステルとしては、(メタ)アクリル酸アルキルエステル、(メタ)アクリル酸カルボキシ置換アルキルエステル、(メタ)アクリル酸ヒドロキシ置換アルキルエステル、(メタ)アクリル酸アルコキシ置換アルキルエステル、ジ(メタ)アクリル酸エステル等が挙げられる。 Examples of the (meth) acrylic acid ester include (meth) acrylic acid alkyl ester, (meth) acrylic acid carboxy-substituted alkyl ester, (meth) acrylic acid hydroxy-substituted alkyl ester, (meth) acrylic acid alkoxy-substituted alkyl ester, and di (meth). ) Acrylic acid ester and the like can be mentioned.
(メタ)アクリル酸アルキルエステルとしては、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸n−ブチル、(メタ)メタクリル酸イソブチル、(メタ)アクリル酸n−ヘキシル、(メタ)アクリル酸2−エチルヘキシル、(メタ)アクリル酸ラウリル、(メタ)アクリル酸ステアリル、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸ジシクロペンタニル、(メタ)アクリル酸イソボルニル等が挙げられる。
(メタ)アクリル酸カルボキシ置換アルキルエステルとしては、(メタ)アクリル酸2−カルボキシエチル等が挙げられる。
(メタ)アクリル酸ヒドロキシ置換アルキルエステルとしては、(メタ)アクリル酸2−ヒドロキシエチル、(メタ)アクリル酸2−ヒドロキシプロピル、(メタ)アクリル酸3−ヒドロキシプロピル、(メタ)アクリル酸2−ヒドロキシブチル、(メタ)アクリル酸3−ヒドロキシブチル、(メタ)アクリル酸4−ヒドロキシブチル等が挙げられる。
(メタ)アクリル酸アルコキシ置換アルキルエステルとしては、(メタ)アクリル酸2−メトキシエチル等が挙げられる。
ジ(メタ)アクリル酸エステルとしては、エチレングリコールジ(メタ)アクリラート、ジエチレングリコールジ(メタ)アクリラート、トリエチレングリコールジ(メタ)アクリラート、ブタンジオールジ(メタ)アクリラート、ペンタンジオールジ(メタ)アクリラート、ヘキサンジオールジ(メタ)アクリラート、ノナンジオールジ(メタ)アクリラート、デカンジオールジ(メタ)アクリラート等が挙げられる。
Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, n-butyl (meth) acrylic acid, and (meth). Isobutyl methacrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclo (meth) acrylate Examples thereof include pentanyl and isobornyl (meth) acrylate.
Examples of the (meth) acrylic acid carboxy-substituted alkyl ester include 2-carboxyethyl (meth) acrylic acid.
Examples of the (meth) acrylic acid hydroxy-substituted alkyl ester include (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 3-hydroxypropyl, and (meth) acrylic acid 2-hydroxy. Examples thereof include butyl, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
Examples of the (meth) acrylic acid alkoxy-substituted alkyl ester include 2-methoxyethyl (meth) acrylic acid.
Examples of the di (meth) acrylic acid ester include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, and pentanediol di (meth) acrylate. Examples thereof include hexanediol di (meth) acrylate, nonanediol di (meth) acrylate, and decanediol di (meth) acrylate.
(メタ)アクリル酸エステルとしては、(メタ)アクリル酸2−(ジエチルアミノ)エチル、(メタ)アクリル酸ベンジル、メトキシポリエチレングリコール(メタ)アクリラート等も挙げられる。 Examples of the (meth) acrylic acid ester include 2- (diethylamino) ethyl (diethylamino) ethyl (meth) acrylate, benzyl (meth) acrylate, and methoxypolyethylene glycol (meth) acrylate.
(メタ)アクリル酸エステルは、1種を単独で使用してもよいし、2種以上を併用してもよい。 One type of (meth) acrylic acid ester may be used alone, or two or more types may be used in combination.
(メタ)アクリル酸エステルとしては、圧力によって相転移しやすく且つ接着性に優れる圧力応答性粒子を形成する観点から、(メタ)アクリル酸アルキルエステルが好ましく、アルキル基の炭素数が2個以上10個以下である(メタ)アクリル酸アルキルエステルがより好ましく、アルキル基の炭素数が4個以上8個以下である(メタ)アクリル酸アルキルエステルが更に好ましく、アクリル酸n−ブチル及びアクリル酸2−エチルヘキシルが特に好ましい。スチレン系樹脂と(メタ)アクリル酸エステル系樹脂とは、圧力によって相転移しやすい圧力応答性粒子を形成する観点から、同種の(メタ)アクリル酸エステルを重合成分として含むことが好ましい。 As the (meth) acrylic acid ester, a (meth) acrylic acid alkyl ester is preferable from the viewpoint of forming pressure-responsive particles that are easily phase-shifted by pressure and have excellent adhesiveness, and the alkyl group has 2 or more carbon atoms and is 10 or more. The number of (meth) acrylic acid alkyl esters is more preferable, and the number of (meth) acrylic acid alkyl esters having 4 or more and 8 or less carbon atoms of the alkyl group is more preferable, and n-butyl acrylate and 2-acrylic acid 2-. Ethylhexyl is particularly preferred. The styrene resin and the (meth) acrylic acid ester resin preferably contain the same type of (meth) acrylic acid ester as a polymerization component from the viewpoint of forming pressure-responsive particles that easily undergo a phase transition due to pressure.
(メタ)アクリル酸エステル系樹脂の重合成分全体に占める(メタ)アクリル酸アルキルエステルの質量割合は、圧力によって相転移しやすく且つ接着性に優れる圧力応答性粒子を形成する観点から、90質量%以上が好ましく、95質量%以上がより好ましく、98質量%以上が更に好ましく、100質量%が更に好ましい。ここでの(メタ)アクリル酸アルキルエステルとしては、アルキル基の炭素数が2個以上10個以下である(メタ)アクリル酸アルキルエステルが好ましく、アルキル基の炭素数が4個以上8個以下である(メタ)アクリル酸アルキルエステルがより好ましい。 The mass ratio of the (meth) acrylic acid alkyl ester to the total polymerization component of the (meth) acrylic acid ester-based resin is 90% by mass from the viewpoint of forming pressure-responsive particles that are easily phase-transferred by pressure and have excellent adhesiveness. The above is preferable, 95% by mass or more is more preferable, 98% by mass or more is further preferable, and 100% by mass is further preferable. As the (meth) acrylic acid alkyl ester here, a (meth) acrylic acid alkyl ester having an alkyl group having 2 or more and 10 or less carbon atoms is preferable, and the alkyl group has 4 or more and 8 or less carbon atoms. Certain (meth) acrylic acid alkyl esters are more preferred.
(メタ)アクリル酸エステル系樹脂に重合成分として含まれる少なくとも2種の(メタ)アクリル酸エステルのうち最も質量割合の多い2種の質量比は、圧力によって相転移しやすく且つ接着性に優れる圧力応答性粒子を形成する観点から、80:20〜20:80であることが好ましく、70:30〜30:70であることがより好ましく、60:40〜40:60であることが更に好ましい。 The mass ratio of the two types having the largest mass ratio among at least two types of (meth) acrylic acid esters contained as a polymerization component in the (meth) acrylic acid ester-based resin is a pressure that easily undergoes a phase transition due to pressure and has excellent adhesiveness. From the viewpoint of forming responsive particles, it is preferably 80:20 to 20:80, more preferably 70:30 to 30:70, and even more preferably 60:40 to 40:60.
(メタ)アクリル酸エステル系樹脂に重合成分として含まれる少なくとも2種の(メタ)アクリル酸エステルのうち最も質量割合の多い2種は(メタ)アクリル酸アルキルエステルであることが好ましい。ここでの(メタ)アクリル酸アルキルエステルとしては、アルキル基の炭素数が2個以上10個以下である(メタ)アクリル酸アルキルエステルが好ましく、アルキル基の炭素数が4個以上8個以下である(メタ)アクリル酸アルキルエステルがより好ましい。 Of the at least two (meth) acrylic acid esters contained as a polymerization component in the (meth) acrylic acid ester-based resin, the two having the largest mass ratio are preferably (meth) acrylic acid alkyl esters. As the (meth) acrylic acid alkyl ester here, a (meth) acrylic acid alkyl ester having an alkyl group having 2 or more and 10 or less carbon atoms is preferable, and the alkyl group has 4 or more and 8 or less carbon atoms. Certain (meth) acrylic acid alkyl esters are more preferred.
(メタ)アクリル酸エステル系樹脂に重合成分として含まれる少なくとも2種の(メタ)アクリル酸エステルのうち最も質量割合の多い2種が(メタ)アクリル酸アルキルエステルである場合、当該2種の(メタ)アクリル酸アルキルエステルのアルキル基の炭素数の差は、圧力によって転移しやすく且つ接着性に優れる圧力応答性粒子を形成する観点から、1個以上4個以下であることが好ましく、2個以上4個以下であることがより好ましく、3個又は4個であることが更に好ましい。 When the two types having the largest mass ratio among at least two types of (meth) acrylic acid esters contained as a polymerization component in the (meth) acrylic acid ester-based resin are (meth) acrylic acid alkyl esters, the two types (meth) The difference in the number of carbon atoms of the alkyl group of the (meth) acrylic acid alkyl ester is preferably 1 or more and 4 or less, preferably 2 or less, from the viewpoint of forming pressure-responsive particles that are easily transferred by pressure and have excellent adhesiveness. The number is more preferably 4 or less, and further preferably 3 or 4.
(メタ)アクリル酸エステル系樹脂は、圧力によって相転移しやすく且つ接着性に優れる圧力応答性粒子を形成する観点から、重合成分としてアクリル酸n−ブチル及びアクリル酸2−エチルヘキシルを含むことが好ましく、(メタ)アクリル酸エステル系樹脂に重合成分として含まれる少なくとも2種の(メタ)アクリル酸エステルのうち最も質量割合の多い2種がアクリル酸n−ブチルとアクリル酸2−エチルヘキシルとであることが特に好ましい。(メタ)アクリル酸エステル系樹脂の重合成分全体に占めるアクリル酸n−ブチル及びアクリル酸2−エチルヘキシルの合計量は、90質量%以上が好ましく、95質量%以上がより好ましく、98質量%以上が更に好ましく、100質量%が更に好ましい。 The (meth) acrylic acid ester resin preferably contains n-butyl acrylate and 2-ethylhexyl acrylate as polymerization components from the viewpoint of forming pressure-responsive particles that are easily phase-shifted by pressure and have excellent adhesiveness. Of the at least two (meth) acrylic acid esters contained as a polymerization component in the (meth) acrylic acid ester resin, the two having the largest mass ratio are n-butyl acrylate and 2-ethylhexyl acrylate. Is particularly preferable. The total amount of n-butyl acrylate and 2-ethylhexyl acrylate in the total polymerization component of the (meth) acrylic acid ester resin is preferably 90% by mass or more, more preferably 95% by mass or more, and 98% by mass or more. More preferably, 100% by mass is further preferable.
(メタ)アクリル酸エステル系樹脂は、(メタ)アクリル酸エステル以外のビニルモノマーを重合成分に含んでいてもよい。(メタ)アクリル酸エステル以外のビニルモノマーとしては、例えば、(メタ)アクリル酸;スチレン;スチレン以外のスチレン系モノマー;(メタ)アクリロニトリル;ビニルメチルエーテル、ビニルイソブチルエーテル等のビニルエーテル;ビニルメチルケトン、ビニルエチルケトン、ビニルイソプロペニルケトン等のビニルケトン;イソプレン、ブテン、ブタジエン等のオレフィン;が挙げられる。これらビニルモノマーは、1種を単独で使用してもよいし、2種以上を併用してもよい。 The (meth) acrylic acid ester-based resin may contain a vinyl monomer other than the (meth) acrylic acid ester as a polymerization component. Examples of vinyl monomers other than (meth) acrylic acid esters include (meth) acrylic acid; styrene; styrene-based monomers other than styrene; (meth) acrylonitrile; vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; vinyl methyl ketone, Vinyl ketones such as vinyl ethyl ketone and vinyl isopropenyl ketone; olefins such as isoprene, butene and butadiene; can be mentioned. These vinyl monomers may be used alone or in combination of two or more.
(メタ)アクリル酸エステル系樹脂が(メタ)アクリル酸エステル以外のビニルモノマーを重合成分に含む場合、(メタ)アクリル酸エステル以外のビニルモノマーとしては、アクリル酸及びメタクリル酸の少なくとも一方が好ましく、アクリル酸がより好ましい。 When the (meth) acrylic acid ester resin contains a vinyl monomer other than the (meth) acrylic acid ester as a polymerization component, at least one of acrylic acid and methacrylic acid is preferable as the vinyl monomer other than the (meth) acrylic acid ester. Acrylic acid is more preferred.
(メタ)アクリル酸エステル系樹脂の重量平均分子量は、加圧されていない状態で圧力応答性粒子が流動化することを抑制する観点から、5万以上が好ましく、10万以上がより好ましく、12万以上が更に好ましく、15万以上が更に好ましく、圧力によって相転移しやすい圧力応答性粒子を形成する観点から、25万以下が好ましく、22万以下がより好ましく、20万以下が更に好ましい。 The weight average molecular weight of the (meth) acrylic acid ester resin is preferably 50,000 or more, more preferably 100,000 or more, and more preferably 100,000 or more, from the viewpoint of suppressing the fluidization of pressure-responsive particles in a non-pressurized state. It is more preferably 10,000 or more, further preferably 150,000 or more, and further preferably 250,000 or less, more preferably 220,000 or less, still more preferably 200,000 or less, from the viewpoint of forming pressure-responsive particles that easily undergo a phase transition due to pressure.
(メタ)アクリル酸エステル系樹脂のガラス転移温度は、圧力によって相転移しやすい圧力応答性粒子を形成する観点から、10℃以下であることが好ましく、0℃以下であることがより好ましく、−10℃以下であることが更に好ましく、加圧されていない状態で圧力応答性粒子が流動化することを抑制する観点から、−90℃以上であることが好ましく、−80℃以上であることがより好ましく、−70℃以上であることが更に好ましい。 The glass transition temperature of the (meth) acrylic acid ester resin is preferably 10 ° C. or lower, more preferably 0 ° C. or lower, from the viewpoint of forming pressure-responsive particles that easily undergo a phase transition with pressure. It is more preferably 10 ° C. or lower, and preferably −90 ° C. or higher, preferably −80 ° C. or higher, from the viewpoint of suppressing the fluidization of pressure-responsive particles in a non-pressurized state. More preferably, it is more preferably −70 ° C. or higher.
本実施形態において圧力応答性母粒子全体に占める(メタ)アクリル酸エステル系樹脂の質量割合は、圧力によって相転移しやすい圧力応答性粒子を形成する観点から、20質量%以上が好ましく、25質量%以上がより好ましく、30質量%以上が更に好ましく、加圧されていない状態で圧力応答性粒子が流動化することを抑制する観点から、45質量%以下が好ましく、40質量%以下がより好ましく、35質量%以下が更に好ましい。 In the present embodiment, the mass ratio of the (meth) acrylic acid ester-based resin to the entire pressure-responsive mother particles is preferably 20% by mass or more, preferably 25% by mass, from the viewpoint of forming pressure-responsive particles that easily undergo a phase transition due to pressure. % Or more is more preferable, 30% by mass or more is further preferable, and from the viewpoint of suppressing fluidization of pressure-responsive particles in a non-pressurized state, 45% by mass or less is preferable, and 40% by mass or less is more preferable. , 35% by mass or less is more preferable.
本実施形態において圧力応答性母粒子に含まれるスチレン系樹脂と(メタ)アクリル酸エステル系樹脂の合計量は、圧力応答性母粒子全体に対して、70質量%以上が好ましく、80質量%以上がより好ましく、90質量%以上が更に好ましく、95質量%以上が更に好ましく、100質量%が更に好ましい。 In the present embodiment, the total amount of the styrene resin and the (meth) acrylic acid ester resin contained in the pressure-responsive mother particles is preferably 70% by mass or more, preferably 80% by mass or more, based on the entire pressure-responsive mother particles. Is more preferable, 90% by mass or more is further preferable, 95% by mass or more is further preferable, and 100% by mass is further preferable.
−その他の樹脂−
圧力応答性母粒子は、例えば、ポリスチレン;エポキシ樹脂、ポリエステル樹脂、ポリウレタン樹脂、ポリアミド樹脂、セルロース樹脂、ポリエーテル樹脂、変性ロジン等の非ビニル系樹脂;などを含有していてもよい。これらの樹脂は、1種を単独で用いてもよいし、2種以上を併用してもよい。
-Other resins-
The pressure-responsive mother particles may contain, for example, polystyrene; a non-vinyl resin such as an epoxy resin, a polyester resin, a polyurethane resin, a polyamide resin, a cellulose resin, a polyether resin, or a modified rosin; One of these resins may be used alone, or two or more of these resins may be used in combination.
−各種の添加剤−
圧力応答性母粒子は、必要に応じて、着色剤(例えば、顔料、染料)、離型剤(例えば、炭化水素系ワックス;カルナバワックス、ライスワックス、キャンデリラワックス等の天然ワックス;モンタンワックス等の合成又は鉱物・石油系ワックス;脂肪酸エステル、モンタン酸エステル等のエステル系ワックス)、帯電制御剤などを含有していてもよい。
-Various additives-
The pressure-responsive mother particles are, if necessary, a colorant (for example, a pigment, a dye), a mold release agent (for example, a hydrocarbon wax; a natural wax such as carnauba wax, rice wax, and candelilla wax; Synthetic or mineral / petroleum wax; ester wax such as fatty acid ester and montanic acid ester), charge control agent and the like may be contained.
本実施形態に係る圧力応答性粒子を透明な圧力応答性粒子とする場合は、圧力応答性母粒子中の着色剤量は圧力応答性母粒子全体に対して1.0質量%以下であることが好ましく、圧力応答性粒子の透明性を高める観点からは少ないほど好ましい。 When the pressure-responsive particles according to the present embodiment are transparent pressure-responsive particles, the amount of the colorant in the pressure-responsive mother particles is 1.0% by mass or less with respect to the entire pressure-responsive mother particles. Is preferable, and the smaller the number, the better, from the viewpoint of increasing the transparency of the pressure-responsive particles.
−圧力応答性母粒子の構造−
圧力応答性母粒子の内部構造は海島構造であることが好ましく、海島構造としては、スチレン系樹脂を含む海相と、当該海相に分散した(メタ)アクリル酸エステル系樹脂を含む島相とを有する海島構造が好ましい。海相に含まれるスチレン系樹脂の具体的形態は、先述のとおりである。島相に含まれる(メタ)アクリル酸エステル系樹脂の具体的形態は、先述のとおりである。海相に(メタ)アクリル酸エステル系樹脂を含まない島相が分散していてもよい。
-Structure of pressure-responsive mother particles-
The internal structure of the pressure-responsive mother particles is preferably a sea-island structure, and the sea-island structure includes a sea phase containing a styrene resin and an island phase containing a (meth) acrylic acid ester-based resin dispersed in the sea phase. A sea-island structure having is preferable. The specific form of the styrene resin contained in the sea phase is as described above. The specific form of the (meth) acrylic acid ester resin contained in the island phase is as described above. An island phase that does not contain a (meth) acrylic acid ester resin may be dispersed in the sea phase.
圧力応答性母粒子が海島構造を有する場合、島相の平均径は、200nm以上500nm以下が好ましい。島相の平均径が500nm以下であると、圧力によって圧力応答性母粒子が相転移しやすく、島相の平均径が200nm以上であると、圧力応答性母粒子に求められる機械的強度(例えば、現像器内で攪拌された際に変形しにくい強度)に優れる。これらの観点から、島相の平均径は、220nm以上450nm以下がより好ましく、250nm以上400nm以下が更に好ましい。 When the pressure-responsive mother particle has a sea-island structure, the average diameter of the island phase is preferably 200 nm or more and 500 nm or less. When the mean diameter of the island phase is 500 nm or less, the pressure-responsive mother particles are likely to undergo a phase transition due to pressure, and when the mean diameter of the island phase is 200 nm or more, the mechanical strength required for the pressure-responsive mother particles (for example). , Strength that does not easily deform when stirred in the developer) is excellent. From these viewpoints, the average diameter of the island phase is more preferably 220 nm or more and 450 nm or less, and further preferably 250 nm or more and 400 nm or less.
海島構造の島相の平均径を上記範囲に制御する方法としては、例えば、後述する圧力応答性母粒子の製造方法において、スチレン系樹脂の量に対する(メタ)アクリル酸エステル系樹脂の量を増減する、凝集した樹脂粒子を融合・合一する工程において高温に維持する時間を増減する、等が挙げられる。 As a method of controlling the mean diameter of the island phase of the sea-island structure within the above range, for example, in the method for producing pressure-responsive mother particles described later, the amount of (meth) acrylic acid ester-based resin is increased or decreased with respect to the amount of styrene-based resin. In the process of fusing and coalescing the agglomerated resin particles, the time for maintaining the high temperature is increased or decreased.
海島構造の確認、及び島相の平均径の測定は、次の方法により行う。
圧力応答性粒子をエポキシ樹脂に包埋し、ダイヤモンドナイフ等で切片を作製し、作製した切片をデシケータ内で四酸化オスミウム又は四酸化ルテニウムを用いて染色する。染色された切片を走査型電子顕微鏡(SEM)にて観察する。海島構造の海相と島相とは、四酸化オスミウム又は四酸化ルテニウムによる樹脂の染色度合いに起因する濃淡で区別され、これを利用して海島構造の有無を確認する。SEM画像から100個の島相を無作為に選択し、各島相の長径を計測し、長径100個の平均値を平均径とする。
The sea-island structure is confirmed and the average diameter of the island fauna is measured by the following method.
The pressure-responsive particles are embedded in an epoxy resin, sections are prepared with a diamond knife or the like, and the prepared sections are stained with osmium tetroxide or ruthenium tetroxide in a desiccator. The stained section is observed with 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 using this. 100 island phases are randomly selected from the SEM image, the major axis of each island phase is measured, and the average value of 100 major axes is taken as the average diameter.
圧力応答性母粒子は、単層構造の圧力応答性母粒子であってもよいし、コア部とコア部を被覆するシェル層とを有するコア・シェル構造の圧力応答性母粒子であってもよい。加圧されていない状態で圧力応答性粒子が流動化することを抑制する観点から、圧力応答性母粒子はコア・シェル構造であることが好ましい。 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 having a core portion and a shell layer covering the core portion. Good. From the viewpoint of suppressing the fluidization of the pressure-responsive particles in the unpressurized state, the pressure-responsive mother particles preferably have a core-shell structure.
圧力応答性母粒子がコア・シェル構造を有する場合、圧力によって相転移しやすい観点から、コア部がスチレン系樹脂及び(メタ)アクリル酸エステル系樹脂を含有することが好ましい。さらに、加圧されていない状態で圧力応答性粒子が流動化することを抑制する観点から、シェル層がスチレン系樹脂を含有することが好ましい。スチレン系樹脂の具体的形態は、先述のとおりである。(メタ)アクリル酸エステル系樹脂の具体的形態は、先述のとおりである。 When the pressure-responsive mother particles have a core-shell structure, the core portion preferably contains a styrene resin and a (meth) acrylic acid ester resin from the viewpoint of facilitating a phase transition due to pressure. Further, from the viewpoint of suppressing the fluidization of the pressure-responsive particles in the unpressurized state, it is preferable that the shell layer contains a styrene resin. The specific form of the styrene resin is as described above. The specific form of the (meth) acrylic acid ester resin is as described above.
圧力応答性母粒子がコア・シェル構造を有する場合、コア部がスチレン系樹脂を含む海相と、海相に分散した(メタ)アクリル酸エステル系樹脂を含む島相とを有することが好ましい。島相の平均径は、先述の範囲であることが好ましい。さらに、コア部が上記構成であることに加えて、シェル層がスチレン系樹脂を含有することが好ましい。この場合、コア部の海相とシェル層とが連続した構造となり、圧力によって圧力応答性母粒子が相転移しやすい。コア部の海相及びシェル層に含まれるスチレン系樹脂の具体的形態は、先述のとおりである。コア部の島相に含まれる(メタ)アクリル酸エステル系樹脂の具体的形態は、先述のとおりである。 When the pressure-responsive mother particles have a core-shell structure, it is preferable that the core portion has a sea phase containing a styrene resin and an island phase containing a (meth) acrylic acid ester resin dispersed in the sea phase. The average diameter of the island fauna is preferably in the above range. Further, in addition to the core portion having the above-mentioned structure, it is preferable that the shell layer contains a styrene resin. In this case, the sea phase of the core portion and the shell layer have a continuous structure, and the pressure-responsive mother particles are likely to undergo a phase transition due to pressure. The specific form of the styrene-based resin contained in the sea phase of the core portion and the shell layer is as described above. The specific form of the (meth) acrylic acid ester-based resin contained in the island phase of the core portion is as described above.
シェル層に含まれる樹脂としては、ポリスチレン;エポキシ樹脂、ポリエステル樹脂、ポリウレタン樹脂、ポリアミド樹脂、セルロース樹脂、ポリエーテル樹脂、変性ロジン等の非ビニル系樹脂;なども挙げられる。これらの樹脂は、1種を単独で用いてもよいし、2種以上を併用してもよい。 Examples of the resin contained in the shell layer include polystyrene; non-vinyl resin such as epoxy resin, polyester resin, polyurethane resin, polyamide resin, cellulose resin, polyether resin, and modified rosin. One of these resins may be used alone, or two or more of these resins may be used in combination.
シェル層の平均厚は、圧力応答性母粒子の変形抑制の観点から、120nm以上が好ましく、130nm以上がより好ましく、140nm以上が更に好ましく、圧力によって圧力応答性母粒子が相転移しやすい観点から、550nm以下が好ましく、500nm以下がより好ましく、400nm以下が更に好ましい。 The average thickness of the shell layer is preferably 120 nm or more, more preferably 130 nm or more, further preferably 140 nm or more, from the viewpoint of suppressing deformation of the pressure-responsive mother particles, and from the viewpoint that the pressure-responsive mother particles are likely to undergo a phase transition due to pressure. It is preferably 550 nm or less, more preferably 500 nm or less, and even more preferably 400 nm or less.
シェル層の平均厚は、次の方法により測定する。
圧力応答性粒子をエポキシ樹脂に包埋し、ダイヤモンドナイフ等で切片を作製し、作製した切片をデシケータ内で四酸化オスミウム又は四酸化ルテニウムを用いて染色する。染色された切片を走査型電子顕微鏡(SEM)にて観察する。SEM画像から10個の圧力応答性母粒子断面を無作為に選択し、圧力応答性母粒子1個につきシェル層の厚さを20か所計測して平均値を算出し、圧力応答性母粒子10個の平均値を平均厚とする。
The average thickness of the shell layer is measured by the following method.
The pressure-responsive particles are embedded in an epoxy resin, sections are prepared with a diamond knife or the like, and the prepared sections are stained with osmium tetroxide or ruthenium tetroxide in a desiccator. The stained section is observed with a scanning electron microscope (SEM). Ten cross sections of pressure-responsive mother particles were randomly selected from the SEM image, and the thickness of the shell layer was measured at 20 points for each pressure-responsive mother particle to calculate the average value, and the pressure-responsive mother particles were calculated. The average value of 10 particles is taken as the average thickness.
圧力応答性母粒子の体積平均粒径(D50v)は、圧力応答性母粒子の取り扱いの容易さの観点から、4μm以上が好ましく、5μm以上がより好ましく、6μm以上が更に好ましく、圧力によって圧力応答性母粒子全体が相転移しやすい観点から、12μm以下が好ましく、10μm以下がより好ましく、9μm以下が更に好ましい。 The volume average particle diameter (D50v) of the pressure-responsive mother particles is preferably 4 μm or more, more preferably 5 μm or more, further preferably 6 μm or more, and pressure-responsive depending on the pressure, from the viewpoint of ease of handling of the pressure-responsive mother particles. From the viewpoint that the entire sex mother particle is easily undergoing a phase transition, it is preferably 12 μm or less, more preferably 10 μm or less, and further preferably 9 μm or less.
圧力応答性母粒子の体積平均粒径(D50v)は、コールターマルチサイザーII(ベックマン・コールター社製)及びアパーチャー径100μmのアパーチャーを用いて測定する。アルキルベンゼンスルホン酸ナトリウム5質量%水溶液2mLに圧力応答性母粒子を0.5mg以上50mg以下加え分散させ、次いで、電解液(ISOTON−II、ベックマン・コールター社製)100mL以上150mL以下と混合し、超音波分散機で1分間分散処理を行い、得られた分散液を試料とする。試料中の粒径2μm以上60μm以下の粒子50000個の粒径を測定する。小径側から起算した体積基準の粒度分布において累積50%となる粒径を体積平均粒径(D50v)とする。 The volume average particle diameter (D50v) of the pressure-responsive mother particles is measured using a Coulter Multisizer II (manufactured by Beckman Coulter) and an aperture having an aperture diameter of 100 μm. Pressure-responsive mother particles were added to 2 mL of a 5 mass% aqueous solution of sodium alkylbenzene sulfonate (0.5 mg or more and 50 mg or less) to disperse them, and then mixed with an electrolytic solution (ISOTON-II, manufactured by Beckman Coulter) of 100 mL or more and 150 mL or less. Disperse with a sonic disperser for 1 minute, and use the obtained dispersion as a sample. The particle size of 50,000 particles having a particle size of 2 μm or more and 60 μm or less in the sample is measured. The volume average particle size (D50v) is defined as the particle size that is cumulatively 50% in the volume-based particle size distribution calculated from the small diameter side.
[外添剤]
外添剤としては、例えば、無機粒子が挙げられる。無機粒子として、SiO2、TiO2、Al2O3、CuO、ZnO、SnO2、CeO2、Fe2O3、MgO、BaO、CaO、K2O、Na2O、ZrO2、CaO・SiO2、K2O・(TiO2)n、Al2O3・2SiO2、CaCO3、MgCO3、BaSO4、MgSO4等が挙げられる。
[External agent]
Examples of the external additive include inorganic particles. As inorganic particles, SiO 2 , TiO 2 , Al 2 O 3 , CuO, ZnO, SnO 2 , CeO 2 , Fe 2 O 3 , MgO, BaO, CaO, K 2 O, Na 2 O, ZrO 2 , CaO · SiO 2, K 2 O · (TiO 2) n, Al 2 O 3 · 2SiO 2, CaCO 3, MgCO 3, BaSO 4, MgSO 4 , and the like.
外添剤としての無機粒子の表面は、疎水化処理が施されていることがよい。疎水化処理は、例えば、疎水化処理剤に無機粒子を浸漬する等して行う。疎水化処理剤は特に制限されないが、例えば、シラン系カップリング剤、シリコーンオイル、チタネート系カップリング剤、アルミニウム系カップリング剤等が挙げられる。これらは1種単独で使用してもよいし、2種以上を併用してもよい。疎水化処理剤の量は、例えば、無機粒子100質量部に対して、1質量部以上10質量部以下である。 The surface of the inorganic particles as an external additive should be hydrophobized. The hydrophobizing treatment is performed, for example, by immersing the inorganic particles in the hydrophobizing agent. The hydrophobizing agent is not particularly limited, and examples thereof include a silane-based coupling agent, a silicone oil, a titanate-based coupling agent, and an aluminum-based coupling agent. These may be used alone 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.
外添剤としては、樹脂粒子(ポリスチレン、ポリメチルメタクリレート、メラミン樹脂等の樹脂粒子)、クリーニング活剤(例えば、ステアリン酸亜鉛に代表される高級脂肪酸の金属塩、フッ素系高分子量体の粒子)等も挙げられる。 Examples of the external additive include resin particles (resin particles such as polystyrene, polymethylmethacrylate, and melamine resin), cleaning activators (for example, metal salts of higher fatty acids typified by zinc stearate, particles of fluoropolymers). And so on.
外添剤の外添量は、圧力応答性母粒子に対して、0.01質量%以上5質量%以下が好ましく、0.01質量%以上2.0質量%以下がより好ましい。 The amount of the external additive added is preferably 0.01% by mass or more and 5% by mass or less, and more preferably 0.01% by mass or more and 2.0% by mass or less with respect to the pressure-responsive mother particles.
[圧力応答性粒子の特性]
本実施形態に係る圧力応答性粒子は、少なくとも2つのガラス転移温度を有するところ、ガラス転移温度の1つはスチレン系樹脂のガラス転移温度と推測され、もう1つは(メタ)アクリル酸エステル系樹脂のガラス転移温度と推測される。
[Characteristics of pressure-responsive particles]
When the pressure-responsive particles according to the present embodiment have at least two glass transition temperatures, one of the glass transition temperatures is presumed to be the glass transition temperature of the styrene resin, and the other is the (meth) acrylic acid ester-based. It is presumed to be the glass transition temperature of the resin.
本実施形態に係る圧力応答性粒子は、3つ以上のガラス転移温度を有していてもよいが、ガラス転移温度の個数は2個であることが好ましい。ガラス転移温度の個数が2個である形態としては、圧力応答性粒子に含まれる樹脂がスチレン系樹脂と(メタ)アクリル酸エステル系樹脂のみである形態;スチレン系樹脂及び(メタ)アクリル酸エステル系樹脂ではないその他の樹脂の含有量が少ない形態(例えば、その他の樹脂の含有量が圧力応答性粒子全体に対して5質量%以下である形態);である。 The pressure-responsive particles according to the present embodiment may have three or more glass transition temperatures, but the number of glass transition temperatures is preferably two. The form in which the number of glass transition temperatures is two is that the resin contained in the pressure-responsive particles is only a styrene resin and a (meth) acrylic acid ester resin; a styrene resin and a (meth) acrylic acid ester. A form in which the content of other resins other than the styrene resin is low (for example, a form in which the content of the other resin is 5% by mass or less with respect to the total pressure-responsive particles);
本実施形態に係る圧力応答性粒子は、少なくとも2つのガラス転移温度を有し、最も低いガラス転移温度と最も高いガラス転移温度との差が30℃以上である。最も低いガラス転移温度と最も高いガラス転移温度との差は、圧力によって圧力応答性粒子が相転移しやすい観点から、より好ましくは40℃以上であり、更に好ましくは50℃以上であり、更に好ましくは60℃以上である。最も低いガラス転移温度と最も高いガラス転移温度との差は、その上限が、例えば、140℃以下であり、130℃以下であり、120℃以下である。 The pressure-responsive particles according to the present embodiment have at least two glass transition temperatures, and the difference between the lowest glass transition temperature and the highest glass transition temperature is 30 ° C. or more. The difference between the lowest glass transition temperature and the highest glass transition temperature is more preferably 40 ° C. or higher, still more preferably 50 ° C. or higher, still more preferably 50 ° C. or higher, from the viewpoint that pressure-responsive particles are likely to undergo a phase transition due to pressure. Is 60 ° C. or higher. The upper limit of the difference between the lowest glass transition temperature and the highest glass transition temperature is, for example, 140 ° C. or lower, 130 ° C. or lower, and 120 ° C. or lower.
本実施形態に係る圧力応答性粒子が示す最も低いガラス転移温度は、圧力によって圧力応答性粒子が相転移しやすい観点から、10℃以下であることが好ましく、0℃以下であることがより好ましく、−10℃以下であることが更に好ましく、加圧されていない状態で圧力応答性粒子が流動化することを抑制する観点から、−90℃以上であることが好ましく、−80℃以上であることがより好ましく、−70℃以上であることが更に好ましい。 The lowest glass transition temperature exhibited by the pressure-responsive particles according to the present embodiment is preferably 10 ° C. or lower, more preferably 0 ° C. or lower, from the viewpoint that the pressure-responsive particles are likely to undergo a phase transition due to pressure. , −10 ° C. or lower, and preferably −90 ° C. or higher, preferably −80 ° C. or higher, from the viewpoint of suppressing the fluidization of pressure-responsive particles in a non-pressurized state. More preferably, it is more preferably −70 ° C. or higher.
本実施形態に係る圧力応答性粒子が示す最も高いガラス転移温度は、加圧されていない状態で圧力応答性粒子が流動化することを抑制する観点から、30℃以上であることが好ましく、40℃以上であることがより好ましく、50℃以上であることが更に好ましく、圧力によって圧力応答性粒子が相転移しやすい観点から、70℃以下であることが好ましく、65℃以下であることがより好ましく、60℃以下であることが更に好ましい。 The highest glass transition temperature exhibited by the pressure-responsive particles according to the present embodiment is preferably 30 ° C. or higher, preferably 40 ° C. or higher, from the viewpoint of suppressing the fluidization of the pressure-responsive particles in the unpressurized state. The temperature is more preferably 70 ° C. or higher, more preferably 50 ° C. or higher, and from the viewpoint that pressure-responsive particles are likely to undergo a phase transition due to pressure, the temperature is preferably 70 ° C. or lower, more preferably 65 ° C. or lower. It is preferably 60 ° C. or lower, and more preferably 60 ° C. or lower.
本開示において、圧力応答性粒子のガラス転移温度は、示差走査熱量測定(Differential Scanning Calorimetry、DSC)を行って得た示差走査熱量曲線(DSC曲線)から求める。より具体的には、JIS K7121:1987「プラスチックの転移温度測定方法」のガラス転移温度の求め方に記載の「補外ガラス転移開始温度」に従って求める。 In the present disclosure, the glass transition temperature of pressure-responsive particles is determined from a differential scanning calorimetry (DSC curve) obtained by performing differential scanning calorimetry (DSC). More specifically, it is obtained according to the "external glass transition start temperature" described in the method for determining the glass transition temperature of JIS K7121: 1987 "Method for measuring the transition temperature of plastics".
本実施形態に係る圧力応答性粒子は、圧力によって相転移する圧力応答性粒子であり、下記の式1を満たす。
式1・・・10℃≦T1−T2
式1において、T1は、圧力1MPa下に粘度10000Pa・sを示す温度であり、T2は、圧力10MPa下に粘度10000Pa・sを示す温度である。
The pressure-responsive particles according to the present embodiment are pressure-responsive particles that undergo a phase transition due to pressure, and satisfy the following formula 1.
Equation 1 ... 10 ° C. ≤ T1-T2
In the formula 1, T1 is a temperature showing a viscosity of 10000 Pa · s under a pressure of 1 MPa, and T2 is a temperature showing a viscosity of 10000 Pa · s under a pressure of 10 MPa.
温度差(T1−T2)は、圧力によって圧力応答性粒子が相転移しやすい観点から、10℃以上であり、15℃以上が好ましく、20℃以上がより好ましく、加圧されていない状態で圧力応答性粒子が流動化することを抑制する観点から、120℃以下が好ましく、100℃以下がより好ましく、80℃以下が更に好ましい。 The temperature difference (T1-T2) is 10 ° C. or higher, preferably 15 ° C. or higher, more preferably 20 ° C. or higher, and the pressure in a non-pressurized state from the viewpoint that pressure-responsive particles are easily phase-translated by pressure. From the viewpoint of suppressing the fluidization of the responsive particles, 120 ° C. or lower is preferable, 100 ° C. or lower is more preferable, and 80 ° C. or lower is further preferable.
温度T1の値は、140℃以下が好ましく、130℃以下がより好ましく、120℃以下が更に好ましく、115℃以下が更に好ましい。温度T1の下限は、80℃以上が好ましく、85℃以上がより好ましい。
温度T2の値は、40℃以上が好ましく、50℃以上がより好ましく、60℃以上が更に好ましい。温度T2の上限は、85℃以下が好ましい。
The value of the temperature T1 is preferably 140 ° C. or lower, more preferably 130 ° C. or lower, further preferably 120 ° C. or lower, still more preferably 115 ° C. or lower. The lower limit of the temperature T1 is preferably 80 ° C. or higher, more preferably 85 ° C. or higher.
The value of the temperature T2 is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, and even more preferably 60 ° C. or higher. The upper limit of the temperature T2 is preferably 85 ° C. or lower.
圧力応答性粒子が圧力によって相転移しやすいことを示す指標として、圧力1MPa下に粘度10000Pa・sを示す温度T1と、圧力4MPa下に粘度10000Pa・sを示す温度T3との温度差(T1−T3)が挙げられ、温度差(T1−T3)は5℃以上であることが好ましい。本実施形態に係る圧力応答性粒子は、圧力によって相転移しやすい観点から、温度差(T1−T3)が5℃以上であることが好ましく、10℃以上であることがより好ましい。
温度差(T1−T3)は、一般的に25℃以下である。
As an index showing that pressure-responsive particles are likely to undergo a phase transition due to pressure, the temperature difference (T1-) between the temperature T1 having a viscosity of 10000 Pa · s under a pressure of 1 MPa and the temperature T3 having a viscosity of 10000 Pa · s under a pressure of 4 MPa (T1- T3) is mentioned, and the temperature difference (T1-T3) is preferably 5 ° C. or higher. The pressure-responsive particles according to the present embodiment preferably have a temperature difference (T1-T3) of 5 ° C. or higher, more preferably 10 ° C. or higher, from the viewpoint of easy phase transition due to pressure.
The temperature difference (T1-T3) is generally 25 ° C. or lower.
本実施形態に係る圧力応答性粒子は、温度差(T1−T3)が5℃以上となる観点から、圧力4MPa下に粘度10000Pa・sを示す温度T3が90℃以下であることが好ましく、85℃以下であることがより好ましく、80℃以下であることが更に好ましい。温度T3の下限は、60℃以上が好ましい。 The pressure-responsive particles according to the present embodiment preferably have a temperature T3 of 90 ° C. or lower, which exhibits a viscosity of 10000 Pa · s under a pressure of 4 MPa, from the viewpoint that the temperature difference (T1-T3) is 5 ° C. or higher. It is more preferably ° C. or lower, and even more preferably 80 ° C. or lower. The lower limit of the temperature T3 is preferably 60 ° C. or higher.
温度T1、温度T2及び温度T3を求める方法は、次のとおりである。
圧力応答性粒子を圧縮してペレット状の試料を作製する。ペレット状の試料をフローテスター(島津製作所製、CFT−500)にセットして、印加圧力を1MPaに固定して、1MPaにおける温度に対する粘度を測定する。得られた粘度のグラフから、印加圧力1MPaにおいて粘度が104Pa・sになるときの温度T1を決定する。印加圧力1MPaを10MPaとする以外は、温度T1に係る方法と同様にして、温度T2を決定する。印加圧力1MPaを4MPaとする以外は、温度T1に係る方法と同様にして、温度T3を決定する。温度T1と温度T2から温度差(T1−T2)を算出する。温度T1と温度T3から温度差(T1−T3)を算出する。
The method for obtaining the temperature T1, the temperature T2 and the temperature T3 is as follows.
The pressure-responsive particles are compressed to prepare a pellet-shaped sample. A pellet-shaped sample is set in a flow tester (CFT-500 manufactured by Shimadzu Corporation), the applied pressure is fixed at 1 MPa, and the viscosity with respect to the temperature at 1 MPa is measured. From the graph of the resulting viscosity, at an applied pressure 1MPa to determine the temperature T1 at which becomes 10 4 Pa · s. The temperature T2 is determined in the same manner as the method related to the temperature T1 except that the applied pressure of 1 MPa is 10 MPa. The temperature T3 is determined in the same manner as the method related to the temperature T1 except that the applied pressure of 1 MPa is 4 MPa. The temperature difference (T1-T2) is calculated from the temperature T1 and the temperature T2. The temperature difference (T1-T3) is calculated from the temperature T1 and the temperature T3.
[圧力応答性粒子の製造方法]
本実施形態に係る圧力応答性粒子は、圧力応答性母粒子を製造後、圧力応答性母粒子に対して、外添剤を外添することで得られる。
[Manufacturing method of pressure-responsive particles]
The pressure-responsive particles according to the present embodiment can be obtained by externally adding an external additive to the pressure-responsive mother particles after producing the pressure-responsive mother particles.
圧力応答性母粒子は、乾式製法(例えば、混練粉砕法等)、湿式製法(例えば、凝集合一法、懸濁重合法、溶解懸濁法等)のいずれにより製造してもよい。これらの製法に特に制限はなく、公知の製法が採用される。これらの中でも、凝集合一法により圧力応答性母粒子を得ることがよい。 The pressure-responsive mother particles may be produced by any of a dry production method (for example, a kneading and pulverizing method) and a wet production method (for example, an agglomeration coalescence method, a suspension polymerization method, a dissolution suspension method, etc.). There are no particular restrictions on these manufacturing methods, and known manufacturing methods are adopted. Among these, it is preferable to obtain pressure-responsive mother particles by the aggregation and coalescence method.
圧力応答性母粒子を凝集合一法により製造する場合、例えば、
スチレン系樹脂を含むスチレン系樹脂粒子が分散したスチレン系樹脂粒子分散液を準備する工程(スチレン系樹脂粒子分散液準備工程)と、
スチレン系樹脂粒子分散液中で(メタ)アクリル酸エステル系樹脂を重合し、スチレン系樹脂及び(メタ)アクリル酸エステル系樹脂を含有する複合樹脂粒子を形成する工程(複合樹脂粒子形成工程)と、
複合樹脂粒子が分散した複合樹脂粒子分散液中で複合樹脂粒子を凝集させ、凝集粒子を形成する工程(凝集粒子形成工程)と、
凝集粒子が分散した凝集粒子分散液を加熱し、凝集粒子を融合・合一して、圧力応答性母粒子を形成する工程(融合・合一工程)と、を経て、圧力応答性母粒子を製造する。
When the pressure-responsive mother particles are produced by the aggregation and coalescence method, for example,
A step of preparing a styrene-based resin particle dispersion liquid in which styrene-based resin particles containing a styrene-based resin are dispersed (styrene-based resin particle dispersion liquid preparation step) and
A step of polymerizing a (meth) acrylic acid ester resin in a styrene resin particle dispersion to form composite resin particles containing the styrene resin and the (meth) acrylic acid ester resin (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 agglomerated particles (aggregated particle forming step).
The pressure-responsive mother particles are formed through a step of heating the agglomerated particle dispersion liquid in which the agglomerated particles are dispersed and fusing and coalescing the agglomerated particles to form a pressure-responsive mother particle (fusion and coalescence step). To manufacture.
以下、各工程の詳細について説明する。
以下の説明では、着色剤及び離型剤を含まない圧力応答性母粒子を得る方法について説明する。着色剤、離型剤、その他添加剤は、必要に応じて用いてもよい。圧力応答性母粒子に着色剤及び離型剤を含有させる場合は、複合樹脂粒子分散液と着色剤粒子分散液と離型剤粒子分散液とを混合した後、融合・合一工程を行う。着色剤粒子分散液及び離型剤粒子分散液は、例えば、材料を混合した後、公知の分散機を用いて分散処理を行うことで作製できる。
The details of each step will be described below.
In the following description, a method for obtaining pressure-responsive mother particles containing no colorant and release agent will be described. Colorants, mold release agents, and other additives may be used as needed. When the pressure-responsive mother particles contain a colorant and a mold release agent, the composite resin particle dispersion liquid, the colorant particle dispersion liquid, and the release agent particle dispersion liquid are mixed, and then the fusion / coalescence step is performed. The colorant particle dispersion and the release agent particle dispersion can be produced, for example, by mixing the materials and then performing a dispersion treatment using a known disperser.
−スチレン系樹脂粒子分散液準備工程−
スチレン系樹脂粒子分散液は、例えば、界面活性剤によりスチレン系樹脂粒子を分散媒中に分散させた分散液である。
-Styrene-based resin particle dispersion preparation process-
The styrene-based resin particle dispersion liquid is, for example, a dispersion liquid in which styrene-based resin particles are dispersed in a dispersion medium with a surfactant.
分散媒としては、例えば、水、アルコール類などの水系媒体が挙げられる。これらは、1種を単独で使用してもよいし、2種以上を併用してもよい。 Examples of the dispersion medium include water-based media such as water and alcohols. These may be used alone or in combination of two or more.
界面活性剤としては、例えば、硫酸エステル塩系、スルホン酸塩系、リン酸エステル系、せっけん系等のアニオン界面活性剤;アミン塩型、4級アンモニウム塩型等のカチオン界面活性剤;ポリエチレングリコール系、アルキルフェノールエチレンオキサイド付加物系、多価アルコール系等の非イオン系界面活性剤等が挙げられる。非イオン系界面活性剤は、アニオン界面活性剤又はカチオン界面活性剤と併用してもよい。これらの中でも、アニオン界面活性剤が好ましい。界面活性剤は、1種単独で使用してもよいし、2種以上を併用してもよい。 Examples of the surfactant include anionic surfactants such as sulfate ester type, sulfonate type, phosphoric acid ester type and soap type; cationic surfactants such as amine salt type and quaternary ammonium salt type; polyethylene glycol. Examples thereof include nonionic surfactants such as systems, alkylphenol ethylene oxide adducts, and polyhydric alcohols. 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.
スチレン系樹脂粒子を分散媒に分散する方法としては、例えば、スチレン系樹脂と分散媒とを混合し、回転せん断型ホモジナイザーや、メディアを有するボールミル、サンドミル、ダイノミル等を用いて攪拌して分散させる方法が挙げられる。 As a method of dispersing the styrene resin particles in the dispersion medium, for example, the styrene resin and the dispersion medium are mixed and stirred and dispersed using a rotary shear type homogenizer, a ball mill having a medium, a sand mill, a dyno mill, or the like. The method can be mentioned.
スチレン系樹脂粒子を分散媒に分散する別の方法としては、乳化重合法が挙げられる。具体的には、スチレン系樹脂の重合成分と連鎖移動剤又は重合開始剤とを混合した後、界面活性剤を含有する水系媒体をさらに混合し、攪拌して乳化液を作製し、乳化液中でスチレン系樹脂を重合する。この際、連鎖移動剤としてドデカンチオールを用いることが好ましい。 As another method of dispersing the styrene resin particles in the dispersion medium, an emulsion polymerization method can be mentioned. Specifically, after mixing the polymerization component of the styrene resin with the chain transfer agent or the polymerization initiator, an aqueous medium containing a surfactant is further mixed and stirred to prepare an emulsion, which is contained in the emulsion. Polymerize the styrene resin in. At this time, it is preferable to use dodecanethiol as the chain transfer agent.
スチレン系樹脂粒子分散液中に分散するスチレン系樹脂粒子の体積平均粒径は、100nm以上250nm以下が好ましく、120nm以上220nm以下がより好ましく、150nm以上200nm以下が更に好ましい。
樹脂粒子分散液に含まれる樹脂粒子の体積平均粒径は、レーザ回折式粒度分布測定装置(例えば、堀場製作所製LA−700)にて粒径を測定し、小径側から起算した体積基準の粒度分布において累積50%となる粒径を体積平均粒径(D50v)とする。
The volume average particle size of the styrene resin particles dispersed in the styrene resin particle dispersion is preferably 100 nm or more and 250 nm or less, more preferably 120 nm or more and 220 nm or less, and further preferably 150 nm or more and 200 nm or less.
The volume average particle size of the resin particles contained in the resin particle dispersion is measured by a laser diffraction type particle size distribution measuring device (for example, LA-700 manufactured by Horiba Seisakusho), and the particle size is based on the volume calculated from the small diameter side. The particle size that is cumulatively 50% in the distribution is defined as the volume average particle size (D50v).
スチレン系樹脂粒子分散液に含まれるスチレン系樹脂粒子の含有量は、30質量%以上60質量%以下が好ましく、40質量%以上50質量%以下がより好ましい。 The content of the styrene-based resin particles contained in the styrene-based resin particle dispersion is preferably 30% by mass or more and 60% by mass or less, and more preferably 40% by mass or more and 50% by mass or less.
−複合樹脂粒子形成工程−
スチレン系樹脂粒子分散液と(メタ)アクリル酸エステル系樹脂の重合成分とを混合し、スチレン系樹脂粒子分散液中で(メタ)アクリル酸エステル系樹脂を重合し、スチレン系樹脂及び(メタ)アクリル酸エステル系樹脂を含有する複合樹脂粒子を形成する。
-Composite resin particle forming process-
The styrene resin particle dispersion liquid and the polymer component of the (meth) acrylic acid ester resin are mixed, and the (meth) acrylic acid ester resin is polymerized in the styrene resin particle dispersion liquid to form the styrene resin and the (meth) resin. Form composite resin particles containing an acrylic acid ester resin.
複合樹脂粒子は、スチレン系樹脂と(メタ)アクリル酸エステル系樹脂とがミクロ相分離の状態で含まれる樹脂粒子であることが好ましい。当該樹脂粒子は、例えば、下記の方法で製造することができる。 The composite resin particles are preferably resin particles containing a styrene resin and a (meth) acrylic acid ester resin in a microphase-separated state. The resin particles can be produced, for example, by the following method.
スチレン系樹脂粒子分散液に、(メタ)アクリル酸エステル系樹脂の重合成分(少なくとも2種の(メタ)アクリル酸エステルを含むモノマー群)を添加し、必要に応じて水系媒体を添加する。次いで、分散液をゆっくりと攪拌しながら、分散液の温度をスチレン系樹脂のガラス転移温度以上(例えばスチレン系樹脂のガラス転移温度より10℃から30℃高い温度)に加熱する。次いで、温度を保ちながら、重合開始剤を含有する水系媒体をゆっくりと滴下し、さらに1時間以上15時間以下の範囲で長時間攪拌を継続する。この際、重合開始剤として過硫酸アンモニウムを用いることが好ましい。 A polymerization component of the (meth) acrylic acid ester-based resin (monomer group containing at least two types of (meth) acrylic acid ester) is added to the styrene-based resin particle dispersion, and an aqueous medium is added as necessary. 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 resin (for example, a temperature 10 ° C to 30 ° C higher than the glass transition temperature of the styrene resin). Then, while maintaining the temperature, the aqueous medium containing the polymerization initiator is slowly added dropwise, and stirring is continued for a long time in the range of 1 hour or more and 15 hours or less. At this time, it is preferable to use ammonium persulfate as the polymerization initiator.
詳細な機序は必ずしも明らかではないが、上記の方法を採用した場合、スチレン系樹脂粒子中にモノマーと重合開始剤とが含浸し、スチレン系樹脂粒子の内部で(メタ)アクリル酸エステルが重合すると推測される。これによって、スチレン系樹脂粒子の内部に(メタ)アクリル酸エステル系樹脂が含まれており、粒子内部においてスチレン系樹脂と(メタ)アクリル酸エステル系樹脂とがミクロ相分離の状態を形成している複合樹脂粒子が得られると推測される。 Although the detailed mechanism is not always clear, when the above method is adopted, the monomer and the polymerization initiator are impregnated in the styrene resin particles, and the (meth) acrylic acid ester is polymerized inside the styrene resin particles. It is presumed that. As a result, the (meth) acrylic acid ester-based resin is contained inside the styrene-based resin particles, and the styrene-based resin and the (meth) acrylic acid ester-based resin form a microphase-separated state inside the particles. It is presumed that the composite resin particles are obtained.
上記の複合樹脂粒子の製造中又は製造後に、複合樹脂粒子が分散している分散液にスチレン系樹脂の重合成分(すなわち、スチレン及びその他のビニルモノマー)を添加し、重合反応を継続してもよい。これにより、粒子内部にスチレン系樹脂と(メタ)アクリル酸エステル系樹脂とがミクロ相分離の状態を形成し、且つ、粒子表面にスチレン系樹脂が付着した複合樹脂粒子が得られると推測される。粒子表面にスチレン系樹脂が付着した複合樹脂粒子を用いて製造した圧力応答性粒子は、粗粉の発生が比較的少ない。
複合樹脂粒子の表面に付着させるスチレン系樹脂の重合成分であるその他のビニルモノマーは、複合樹脂粒子の内部に有るスチレン系樹脂又は(メタ)アクリル酸エステル系樹脂を構成しているモノマーの少なくとも1種と同種のモノマーを含むことが好ましく、具体的には、アクリル酸n−ブチル及びアクリル酸2−エチルヘキシルの少なくとも一方を含むことが好ましい。
Even if the polymerization component of the styrene resin (that is, styrene and other vinyl monomers) is added to the dispersion liquid in which the composite resin particles are dispersed during or after the production of the composite resin particles, and the polymerization reaction is continued. Good. As a result, it is presumed that composite resin particles in which the styrene resin and the (meth) acrylic acid ester resin form a microphase-separated state inside the particles and the styrene resin adheres to the particle surface can be obtained. .. Pressure-responsive particles produced using composite resin particles in which a styrene-based resin is adhered to the particle surface generate relatively little coarse powder.
The other vinyl monomer, which is a polymerization component of the styrene-based resin attached to the surface of the composite resin particles, is at least one of the monomers constituting the styrene-based resin or the (meth) acrylic acid ester-based resin inside the composite resin particles. It is preferable to contain the same kind of monomer as the seed, and specifically, it is preferable to contain at least one of n-butyl acrylate and 2-ethylhexyl acrylate.
複合樹脂粒子分散液中に分散する複合樹脂粒子の体積平均粒径は、140nm以上300nm以下が好ましく、150nm以上280nm以下がより好ましく、160nm以上250nm以下が更に好ましい。 The volume average particle diameter of the composite resin particles dispersed in the composite resin particle dispersion is preferably 140 nm or more and 300 nm or less, more preferably 150 nm or more and 280 nm or less, and further preferably 160 nm or more and 250 nm or less.
複合樹脂粒子分散液に含まれる複合樹脂粒子の含有量は、20質量%以上50質量%以下が好ましく、30質量%以上40質量%以下がより好ましい。 The content of the composite resin particles contained in the composite resin particle dispersion is preferably 20% by mass or more and 50% by mass or less, and more preferably 30% by mass or more and 40% by mass or less.
−凝集粒子形成工程−
複合樹脂粒子分散液中で複合樹脂粒子を凝集させ、目的とする圧力応答性母粒子の径に近い径を持つ凝集粒子を形成する。
-Agglomerated particle formation process-
The composite resin particles are agglomerated in the composite resin particle dispersion to form agglomerated particles having a diameter close to the diameter of the target pressure-responsive mother particles.
具体的には、例えば、複合樹脂粒子分散液に凝集剤を添加すると共に、複合樹脂粒子分散液のpHを酸性(例えばpH2以上5以下)に調整し、必要に応じて分散安定剤を添加した後、スチレン系樹脂のガラス転移温度に近い温度(具体的には、例えば、スチレン系樹脂のガラス転移温度−30℃以上ガラス転移温度−10℃以下)に加熱し、複合樹脂粒子を凝集させて、凝集粒子を形成する。 Specifically, for example, a flocculant was added to the composite resin particle dispersion, the pH of the composite resin particle dispersion was adjusted to acidic (for example, pH 2 or more and 5 or less), and a dispersion stabilizer was added as necessary. After that, the composite resin particles are agglomerated by heating to a temperature close to the glass transition temperature of the styrene resin (specifically, for example, the glass transition temperature of the styrene resin is -30 ° C or higher and the glass transition temperature is -10 ° C or lower). , Form agglomerated particles.
凝集粒子形成工程においては、複合樹脂粒子分散液を回転せん断型ホモジナイザーで攪拌下、室温(例えば25℃)で凝集剤を添加し、複合樹脂粒子分散液のpHを酸性(例えばpH2以上5以下)に調整し、必要に応じて分散安定剤を添加した後に、加熱を行ってもよい。 In the agglomerated particle forming step, the composite resin particle dispersion is stirred with a rotary shear type homogenizer, a flocculant is added at room temperature (for example, 25 ° C.), and the pH of the composite resin particle dispersion is acidic (for example, pH 2 or more and 5 or less). If necessary, a dispersion stabilizer may be added, and then heating may be performed.
凝集剤としては、例えば、複合樹脂粒子分散液に含まれる界面活性剤と逆極性の界面活性剤、無機金属塩、2価以上の金属錯体が挙げられる。凝集剤として金属錯体を用いた場合には、界面活性剤の使用量が低減され、帯電特性が向上する。
凝集剤と共に、該凝集剤の金属イオンと錯体もしくは類似の結合を形成する添加剤を必要に応じて用いてもよい。この添加剤としては、キレート剤が好適に用いられる。
Examples of the flocculant include a surfactant having a polarity opposite to that of the surfactant contained in the composite resin particle dispersion, an inorganic metal salt, and a divalent or higher valent metal complex. When a metal complex is used as the flocculant, 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 flocculant may be used together with the flocculant, if necessary. As this additive, a chelating agent is preferably used.
無機金属塩としては、例えば、塩化カルシウム、硝酸カルシウム、塩化バリウム、塩化マグネシウム、塩化亜鉛、塩化アルミニウム、硫酸アルミニウム等の金属塩;ポリ塩化アルミニウム、ポリ水酸化アルミニウム、多硫化カルシウム等の無機金属塩重合体;などが挙げられる。
キレート剤としては、水溶性のキレート剤を用いてもよい。キレート剤としては、例えば、酒石酸、クエン酸、グルコン酸等のオキシカルボン酸;イミノ二酸酢(IDA)、ニトリロ三酢酸(NTA)、エチレンジアミン四酢酸(EDTA)等のアミノカルボン酸;などが挙げられる。
キレート剤の添加量は、樹脂粒子100質量部に対して0.01質量部以上5.0質量部以下が好ましく、0.1質量部以上3.0質量部未満がより好ましい。
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; and inorganic metal salts such as polyaluminum chloride, polyaluminum hydroxide and calcium polysulfide. Polymers; and the like.
As the chelating agent, a water-soluble chelating agent may be used. Examples of the chelating agent include oxycarboxylic acids such as tartaric acid, citric acid and gluconic acid; aminocarboxylic acids such as iminodioic acid vinegar (IDA), nitrilotriacetic acid (NTA) and ethylenediaminetetraacetic acid (EDTA); Be done.
The amount of the chelating agent added is preferably 0.01 parts by mass or more and 5.0 parts by mass or less, and more preferably 0.1 parts by mass or more and less than 3.0 parts by mass with respect to 100 parts by mass of the resin particles.
−融合・合一工程−
次に、凝集粒子が分散された凝集粒子分散液を、例えば、スチレン系樹脂のガラス転移温度以上(例えばスチレン系樹脂のガラス転移温度より10℃から30℃高い温度)に加熱して、凝集粒子を融合・合一し、圧力応答性母粒子を形成する。
-Fusion / unification process-
Next, the agglomerated particle dispersion liquid in which the agglomerated particles are dispersed is heated to, for example, a temperature equal to or higher than the glass transition temperature of the styrene resin (for example, a temperature 10 ° C. to 30 ° C. higher than the glass transition temperature of the styrene resin) to obtain the agglomerated particles. Are fused and united to form a pressure-responsive mother particle.
以上の工程を経て得られた圧力応答性母粒子は、通常、スチレン系樹脂を含む海相と、当該海相に分散した(メタ)アクリル酸エステル系樹脂を含む島相とを有する海島構造を有する。複合樹脂粒子においてはスチレン系樹脂と(メタ)アクリル酸エステル系樹脂とがミクロ相分離の状態であったところ、融合・合一工程において、スチレン系樹脂が互いに集まって海相になり、(メタ)アクリル酸エステル系樹脂が互いに集まって島相になるものと推測される。 The pressure-responsive mother particles obtained through the above steps usually have a sea-island structure having a sea phase containing a styrene resin and an island phase containing a (meth) acrylic acid ester-based resin dispersed in the sea phase. Have. In the composite resin particles, the styrene resin and the (meth) acrylic acid ester resin were in a microphase-separated state, but in the fusion / union step, the styrene resins gathered together to form a sea phase (meth). ) It is presumed that the acrylic acid ester resins gather together to form an island phase.
海島構造の島相の平均径は、例えば、複合樹脂粒子形成工程において使用するスチレン系樹脂粒子分散液の量又は少なくとも2種の(メタ)アクリル酸エステルの量を増減すること、融合・合一工程において高温に維持する時間を増減すること、等によって制御できる。 The average diameter of the island phase of the sea-island structure is, for example, increasing or decreasing the amount of the styrene-based resin particle dispersion liquid used in the composite resin particle forming step or the amount of at least two (meth) acrylic acid esters, fusion and coalescence. It can be controlled by increasing or decreasing the time for maintaining the high temperature in the process.
コア・シェル構造の圧力応答性母粒子は、例えば、
凝集粒子分散液を得た後、凝集粒子分散液とスチレン系樹脂粒子分散液とをさらに混合し、凝集粒子の表面にさらにスチレン系樹脂粒子を付着するように凝集して、第2凝集粒子を形成する工程と、
第2凝集粒子が分散された第2凝集粒子分散液に対して加熱をし、第2凝集粒子を融合・合一して、コア・シェル構造の圧力応答性母粒子を形成する工程と、
を経て製造する。
上記工程を経て得られるコア・シェル構造の圧力応答性母粒子は、スチレン系樹脂を含むシェル層を有する。スチレン系樹脂粒子分散液の代わりに他の種類の樹脂粒子が分散した樹脂粒子分散液を用いて、他の種類の樹脂を含むシェル層を形成してもよい。
Pressure-responsive mother particles of core-shell structure are, for example,
After obtaining the agglomerated particle dispersion, the agglomerated particle dispersion and the styrene resin particle dispersion are further mixed and aggregated so that the styrene resin particles are further adhered to the surface of the agglomerated particles to form the second agglomerated particles. The process of forming and
A step of heating the second agglomerated particle dispersion liquid in which the second agglomerated particles are dispersed to fuse and coalesce the second agglomerated particles to form a pressure-responsive mother particle having a core-shell structure.
Manufactured via.
The pressure-responsive mother particles having a core-shell structure obtained through the above steps have a shell layer containing a styrene resin. Instead of the styrene-based resin particle dispersion liquid, a resin particle dispersion liquid in which other types of resin particles are dispersed may be used to form a shell layer containing another type of resin.
融合・合一工程終了後、溶液中に形成された圧力応答性母粒子に、公知の洗浄工程、固液分離工程、及び乾燥工程を施して乾燥した状態の圧力応答性母粒子を得る。洗浄工程は、帯電性の観点から、イオン交換水による置換洗浄を充分に施すことがよい。固液分離工程は、生産性の観点から、吸引濾過、加圧濾過等を施すことがよい。乾燥工程は、生産性の観点から、凍結乾燥、気流乾燥、流動乾燥、振動型流動乾燥等を施すことがよい。 After completion of the fusion / coalescence step, the pressure-responsive mother particles formed in the solution are subjected to a known washing step, solid-liquid separation step, and drying step to obtain a dried pressure-responsive mother particles. In the cleaning step, from the viewpoint of chargeability, it is preferable to sufficiently perform replacement cleaning with ion-exchanged water. In the solid-liquid separation step, suction filtration, pressure filtration and the like may be performed from the viewpoint of productivity. From the viewpoint of productivity, the drying step may be freeze-dried, air-flow-dried, fluid-dried, vibrating fluid-dried or the like.
そして、本実施形態に係る圧力応答性粒子は、例えば、得られた乾燥状態の圧力応答性母粒子に、外添剤を添加し、混合することにより製造される。混合は、例えばVブレンダー、ヘンシェルミキサー、レーディゲミキサー等によって行うことがよい。さらに、必要に応じて、振動篩分機、風力篩分機等を使って圧力応答性粒子の粗大粒子を取り除いてもよい。 The pressure-responsive particles according to the present embodiment are produced, for example, by adding an external additive to the obtained dry pressure-responsive mother particles and mixing them. The mixing may be carried out by, for example, a V blender, a Henschel mixer, a Ladyge mixer or the like. Further, if necessary, coarse particles of pressure-responsive particles may be removed by using a vibration sieving machine, a wind sieving machine, or the like.
<カートリッジ>
本実施形態に係るカートリッジは、本実施形態に係る圧力応答性粒子を収容し、印刷物の製造装置に着脱されるカートリッジである。カートリッジが印刷物の製造装置に装着されたとき、カートリッジと、印刷物の製造装置が有する、圧力応答性粒子を記録媒体上に配置する配置手段とが供給管で接続される。
カートリッジから配置手段に圧力応答性粒子が供給され、カートリッジ内に収容されている圧力応答性粒子が少なくなったら、そのカートリッジが交換される。
<Cartridge>
The cartridge according to the present embodiment is a cartridge that contains the pressure-responsive particles according to the present embodiment and is attached to and detached from the printed matter manufacturing apparatus. When the cartridge is mounted on the printed matter manufacturing apparatus, the cartridge and the arrangement means for arranging the pressure-responsive particles on the recording medium, which the printed matter manufacturing apparatus has, are connected by a supply pipe.
When the pressure-responsive particles are supplied from the cartridge to the placement means and the pressure-responsive particles contained in the cartridge are reduced, the cartridge is replaced.
<印刷物の製造装置、印刷物の製造方法、印刷物>
本実施形態に係る印刷物の製造装置は、本実施形態に係る圧力応答性粒子を収容し、前記圧力応答性粒子を記録媒体上に配置する配置手段と、前記記録媒体を折り重ねて圧着する、又は、前記記録媒体と別の記録媒体とを重ねて圧着する圧着手段と、を含む。
<Printed matter manufacturing equipment, printed matter manufacturing method, printed matter>
The printed matter manufacturing apparatus according to the present embodiment accommodates the pressure-responsive particles according to the present embodiment, and folds and crimps the recording medium with an arrangement means for arranging the pressure-responsive particles on the recording medium. Alternatively, the crimping means for superimposing and crimping the recording medium and another recording medium is included.
配置手段は、例えば、圧力応答性粒子を記録媒体上に付与する付与装置を備え、さらに、記録媒体上に付与された圧力応答性粒子を記録媒体上に固定する固定装置を備えてもよい。 The arranging means may include, for example, an applying device for applying pressure-responsive particles on the recording medium, and further may include a fixing device for fixing the pressure-responsive particles applied on the recording medium on the recording medium.
圧着手段は、例えば、圧力応答性粒子が配置された記録媒体を折り重ねる折り装置、又は、圧力応答性粒子が配置された記録媒体と別の記録媒体とを重ねる重ね装置と、重なった記録媒体を加圧する加圧装置と、を備える。 The crimping means includes, for example, a folding device for folding a recording medium on which pressure-responsive particles are arranged, or a stacking device for stacking a recording medium on which pressure-responsive particles are arranged and another recording medium, and an overlapping recording medium. It is provided with a pressurizing device for pressurizing.
圧着手段が備える加圧装置は、圧力応答性粒子が配置された記録媒体に圧力を印加する。これによって、記録媒体上において圧力応答性粒子が流動化し接着性を発揮する。 The pressurizing device provided by the crimping means applies pressure to a recording medium on which pressure-responsive particles are arranged. As a result, the pressure-responsive particles are fluidized on the recording medium and exhibit adhesiveness.
本実施形態に係る印刷物の製造装置によって、本実施形態に係る印刷物の製造方法が実施される。本実施形態に係る印刷物の製造方法は、本実施形態に係る圧力応答性粒子を用いるとともに、前記圧力応答性粒子を記録媒体上に配置する配置工程と、前記記録媒体を折り重ねて圧着する、又は、前記記録媒体と別の記録媒体とを重ねて圧着する圧着工程と、を含む。 The printed matter manufacturing apparatus according to the present embodiment implements the printed matter manufacturing method according to the present embodiment. The method for producing a printed matter according to the present embodiment uses the pressure-responsive particles according to the present embodiment, arranges the pressure-responsive particles on a recording medium, and folds and crimps the recording medium. Alternatively, the crimping step of superimposing and crimping the recording medium and another recording medium is included.
配置工程は、例えば、圧力応答性粒子を記録媒体上に付与する工程を含み、さらに、記録媒体上に付与された圧力応答性粒子を記録媒体上に固定する工程を含んでもよい。 The arrangement step may include, for example, a step of applying the pressure-responsive particles on the recording medium, and may further include a step of fixing the pressure-responsive particles applied on the recording medium on the recording medium.
圧着工程は、例えば、記録媒体を折り重ねる折り工程又は記録媒体と別の記録媒体とを重ねる重ね工程と、重なった記録媒体を加圧する加圧工程と、を備える。 The crimping step includes, for example, a folding step of folding the recording medium, a stacking step of stacking the recording medium and another recording medium, and a pressurizing step of pressurizing the overlapping recording media.
圧力応答性粒子は、記録媒体の全面に配置されてもよく、記録媒体の一部に配置されてもよい。圧力応答性粒子は、記録媒体上に1層又は複数層配置される。圧力応答性粒子の層は、記録媒体の面方向に連続した層であってもよいし、記録媒体の面方向に不連続な層であってもよい。圧力応答性粒子の層は、圧力応答性粒子が粒子のまま並んだ層であってもよく、隣接する圧力応答性粒子どうしが融合して並んだ層であってもよい。 The pressure-responsive particles may be arranged on the entire surface of the recording medium or may be arranged on a part of the recording medium. The pressure-responsive particles are arranged in one or more layers on the recording medium. The layer of the pressure-responsive particles may be a layer continuous in the plane direction of the recording medium or a layer discontinuous in the plane direction of the recording medium. The layer of the pressure-responsive particles may be a layer in which the pressure-responsive particles are arranged as particles, or may be a layer in which adjacent pressure-responsive particles are fused and arranged.
記録媒体上の圧力応答性粒子(好ましくは透明な圧力応答性粒子)の量は、配置された領域において、例えば、0.5g/m2以上50g/m2以下であり、1g/m2以上40g/m2以下であり、1.5g/m2以上30g/m2以下である。記録媒体上の圧力応答性粒子(好ましくは透明な圧力応答性粒子)の層厚は、例えば、0.2μm以上25μm以下であり、0.4μm以上20μm以下であり、0.6μm以上15μm以下である。 The amount of pressure-responsive particles (preferably transparent pressure-responsive particles) on the recording medium is, for example, 0.5 g / m 2 or more and 50 g / m 2 or less and 1 g / m 2 or more in the arranged region. It is 40 g / m 2 or less, and 1.5 g / m 2 or more and 30 g / m 2 or less. The layer thickness of the pressure-responsive particles (preferably transparent pressure-responsive particles) on the recording medium is, for example, 0.2 μm or more and 25 μm or less, 0.4 μm or more and 20 μm or less, and 0.6 μm or more and 15 μm or less. is there.
本実施形態に係る印刷物の製造装置に適用する記録媒体としては、例えば、紙、紙の表面を樹脂等でコーティングしたコート紙、布、不織布、樹脂フィルム、樹脂シートなどが挙げられる。記録媒体は、片面又は両面に画像を有していてもよい。 Examples of the recording medium applied to the printed matter manufacturing apparatus according to the present embodiment include paper, coated paper in which the surface of the paper is coated with resin or the like, cloth, non-woven fabric, resin film, resin sheet, and the like. The recording medium may have an image on one side or both sides.
以下、本実施形態に係る印刷物の製造装置の一例を示すが、本実施形態はこれに限定されるわけではない。 Hereinafter, an example of a printed matter manufacturing apparatus according to the present embodiment will be shown, but the present embodiment is not limited to this.
図1は、本実施形態に係る印刷物の製造装置の一例を示す概略構成図である。図1に示す印刷物の製造装置は、配置手段100と、配置手段100の下流に配置された圧着手段200とを備える。矢印は、記録媒体の搬送方向を示す。 FIG. 1 is a schematic configuration diagram showing an example of a printed matter manufacturing apparatus according to the present embodiment. The printed matter manufacturing apparatus shown in FIG. 1 includes an arrangement means 100 and a crimping means 200 arranged downstream of the arrangement means 100. The arrow indicates the transport direction of the recording medium.
配置手段100は、本実施形態に係る圧力応答性粒子を用いて、圧力応答性粒子を記録媒体P上に配置する装置である。記録媒体Pには、片面又は両面に予め画像が形成されている。 The arranging means 100 is an apparatus for arranging the pressure responsive particles on the recording medium P by using the pressure responsive particles according to the present embodiment. An image is formed in advance on one side or both sides of the recording medium P.
配置手段100は、付与装置110と、付与装置110の下流に配置された固定装置120とを備えている。 The arranging means 100 includes a granting device 110 and a fixing device 120 arranged downstream of the granting device 110.
付与装置110は、圧力応答性粒子Mを記録媒体P上に付与する。付与装置110が採用する付与方法としては、例えば、スプレー法、バーコート法、ダイコート法、ナイフコート法、ロールコート法、リバースロールコート法、グラビアコート法、スクリーン印刷法、インクジェット法、ラミネート法、電子写真法などが挙げられる。付与方法に応じて、圧力応答性粒子Mを分散媒に分散させ液体組成物を調製し、液体組成物を付与装置110に適用してもよい。 The applying device 110 applies the pressure-responsive particles M onto the recording medium P. Examples of the applying method adopted by the applying device 110 include a spray method, a bar coating method, a die coating method, a knife coating method, a roll coating method, a reverse roll coating method, a gravure coating method, a screen printing method, an inkjet method, and a laminating method. Examples include electrophotographic method. Depending on the application method, the pressure-responsive particles M may be dispersed in a dispersion medium to prepare a liquid composition, and the liquid composition may be applied to the application device 110.
付与装置110によって圧力応答性粒子Mが付与された記録媒体Pは固定装置120へ搬送される。 The recording medium P to which the pressure-responsive particles M are attached by the applying device 110 is conveyed to the fixing device 120.
固定装置120は、例えば、加熱源を備え、通過する記録媒体P上の圧力応答性粒子Mを加熱し、圧力応答性粒子Mを記録媒体P上に固定させる加熱装置;一対の加圧部材(ロール/ロール、ベルト/ロール)を備え、通過する記録媒体Pを加圧し、圧力応答性粒子Mを記録媒体P上に固定させる加圧装置;内部に加熱源を備える一対の加圧部材(ロール/ロール、ベルト/ロール)を備え、通過する記録媒体Pを加圧及び加熱し、圧力応答性粒子Mを記録媒体P上に固定させる加圧加熱装置;などである。 The fixing device 120 includes, for example, a heating device that includes a heating source, heats the pressure-responsive particles M on the passing recording medium P, and fixes the pressure-responsive particles M on the recording medium P; a pair of pressurizing members ( A pressurizing device provided with a roll / roll, a belt / roll, pressurizing a passing recording medium P, and fixing pressure-responsive particles M on the recording medium P; a pair of pressurizing members (rolls) having a heating source inside. / Roll, belt / roll), a pressure heating device that pressurizes and heats the passing recording medium P, and fixes the pressure-responsive particles M on the recording medium P; and the like.
固定装置120が加熱源を有する場合、固定装置120によって加熱された際の記録媒体Pの表面温度は、10℃以上80℃以下が好ましく、20℃以上60℃以下がより好ましく、30℃以上50℃以下が更に好ましい。 When the fixing device 120 has a heating source, the surface temperature of the recording medium P when heated by the fixing device 120 is preferably 10 ° C. or higher and 80 ° C. or lower, more preferably 20 ° C. or higher and 60 ° C. or lower, and 30 ° C. or higher and 50 ° C. or higher. ° C or lower is more preferable.
固定装置120が加圧部材を有する場合、加圧部材が記録媒体Pに印加する圧力は、加圧装置230が記録媒体P2に印加する圧力に比較して低圧でよい。 When the fixing device 120 has a pressurizing member, the pressure applied by the pressurizing member to the recording medium P may be lower than the pressure applied by the pressurizing device 230 to the recording medium P2.
記録媒体Pは、配置手段100を通過することによって、画像上に圧力応答性粒子Mが付与された記録媒体P1になる。記録媒体P1は、圧着手段200に向けて搬送される。 By passing through the arrangement means 100, the recording medium P becomes the recording medium P1 to which the pressure-responsive particles M are added on the image. The recording medium P1 is conveyed toward the crimping means 200.
本実施形態に係る印刷物の製造装置において、配置手段100と圧着手段200とは、近接している形態でもよく、離隔している形態でもよい。配置手段100と圧着手段200とが離隔している場合、配置手段100と圧着手段200とは、例えば、記録媒体P1を搬送する搬送手段(例えばベルトコンベア)によって繋がれる。 In the printed matter manufacturing apparatus according to the present embodiment, the arranging means 100 and the crimping means 200 may be in close proximity to each other or may be separated from each other. When the arrangement means 100 and the crimping means 200 are separated from each other, the arrangement means 100 and the crimping means 200 are connected by, for example, a conveying means (for example, a belt conveyor) that conveys the recording medium P1.
圧着手段200は、折り装置220と加圧装置230とを備え、記録媒体P1を折り重ねて圧着する手段である。 The crimping means 200 includes a folding device 220 and a pressurizing device 230, and is a means for folding and crimping the recording medium P1.
折り装置220は、当該装置を通過する記録媒体P1を折り重ね、折り重なった記録媒体P2を作製する。記録媒体P2の折り重なり方は、例えば、二つ折り、三つ折り、四つ折りであり、記録媒体P2の一部のみが折り重なっている形態でもよい。記録媒体P2は、対向する2つの面の少なくとも一方の面の少なくとも一部に、圧力応答性粒子Mが配置された状態である。 The folding device 220 folds the recording medium P1 that passes through the device to produce the folded recording medium P2. The folding method of the recording medium P2 is, for example, two-fold, three-fold, or four-fold, and a form in which only a part of the recording medium P2 is folded may be used. The recording medium P2 is in a state in which the pressure-responsive particles M are arranged on at least a part of at least one of the two opposing surfaces.
折り装置220は、記録媒体P2に圧力を印加する一対の加圧部材(例えば、ロール/ロール、ベルト/ロール)を有していてもよい。折り装置220の加圧部材が記録媒体P2に印加する圧力は、加圧装置230が記録媒体P2に印加する圧力に比較して低圧でよい。 The folding device 220 may have a pair of pressure members (for example, roll / roll, belt / roll) that apply pressure to the recording medium P2. The pressure applied to the recording medium P2 by the pressurizing member of the folding device 220 may be lower than the pressure applied to the recording medium P2 by the pressurizing device 230.
圧着手段200は、折り装置220の代わりに、記録媒体P1と別の記録媒体とを重ねる重ね装置を備えていてもよい。記録媒体P1と別の記録媒体との重なりの形態は、例えば、記録媒体P1上に別の記録媒体が1枚重なっている形態、記録媒体P1上の複数個所に別の記録媒体が1枚ずつそれぞれ重なっている形態などである。別の記録媒体は、片面又は両面に予め画像が形成されている記録媒体でもよく、画像が形成されていない記録媒体でもよく、予め作製しておいた圧着印刷物でもよい。 The crimping means 200 may include a stacking device for stacking the recording medium P1 and another recording medium instead of the folding device 220. The overlapping form of the recording medium P1 and another recording medium is, for example, a form in which one other recording medium is overlapped on the recording medium P1, and another recording medium is placed at a plurality of locations on the recording medium P1. These are overlapping forms. The other recording medium may be a recording medium in which an image is formed in advance on one side or both sides, a recording medium in which an image is not formed, or a pressure-bonded printed matter prepared in advance.
折り装置220(又は重ね装置)を出た記録媒体P2は、加圧装置230に向けて搬送される。 The recording medium P2 exiting the folding device 220 (or the stacking device) is conveyed toward the pressurizing device 230.
加圧装置230は、一対の加圧部材(則ち、加圧ロール231及び232)を備える。加圧ロール231と加圧ロール232とは互いの外周面で接触し且つ押し合い、通過する記録媒体P2に圧力を印加する。加圧装置230が備える一対の加圧部材は、加圧ロールと加圧ロールの組合せに限られず、加圧ロールと加圧ベルトの組合せ、加圧ベルトと加圧ベルトの組合せでもよい。 The pressurizing device 230 includes a pair of pressurizing members (that is, pressurizing rolls 231 and 232). The pressure roll 231 and the pressure roll 232 come into contact with each other and press each other on their outer peripheral surfaces, and apply pressure to the passing recording medium P2. The pair of pressurizing members included in the pressurizing device 230 is not limited to the combination of the pressurizing roll and the pressurizing roll, but may be a combination of the pressurizing roll and the pressurizing belt, or a combination of the pressurizing belt and the pressurizing belt.
加圧装置230を通過する記録媒体P2に圧力が印加されると、記録媒体P2上において圧力応答性粒子Mが圧力によって流動化し接着性を発揮する。 When pressure is applied to the recording medium P2 passing through the pressurizing device 230, the pressure-responsive particles M are fluidized by the pressure on the recording medium P2 to exhibit adhesiveness.
加圧装置230は内部に、記録媒体P2を加熱するための加熱源(例えばハロゲンヒータ)を有していても、有していなくてもよい。なお、加圧装置230が内部に加熱源を有しないことは、加圧装置230が備えるモーター等の発熱により、加圧装置230内の温度が環境温度以上になることを除外しない。 The pressurizing device 230 may or may not have a heating source (for example, a halogen heater) for heating the recording medium P2 inside. The fact that the pressurizing device 230 does not have a heating source inside does not exclude that the temperature inside the pressurizing device 230 becomes equal to or higher than the ambient temperature due to heat generated by the motor or the like included in the pressurizing device 230.
記録媒体P2が加圧装置230を通過することによって、折り重なった面どうしが流動化した圧力応答性粒子Mによって接着され、圧着印刷物P3が作製される。圧着印刷物P3は、対向する2つの面どうしが、一部又は全部、接着されている。 When the recording medium P2 passes through the pressurizing device 230, the folded surfaces are adhered to each other by the fluidized pressure-responsive particles M, and the crimped printed matter P3 is produced. In the pressure-bonded printed matter P3, two facing surfaces are partially or wholly adhered to each other.
完成した圧着印刷物P3は、加圧装置230から搬出される。 The completed crimped printed matter P3 is carried out from the pressurizing device 230.
圧着印刷物P3の第一の形態は、折り重なった記録媒体が、対向する面において、圧力応答性粒子Mによって接着されてなる、圧着印刷物である。本形態の圧着印刷物P3は、折り装置220を備える印刷物の製造装置によって製造される。 The first form of the crimped printed matter P3 is a crimped printed matter in which the folded recording medium is adhered by the pressure-responsive particles M on the facing surfaces. The crimped printed matter P3 of this embodiment is manufactured by a printed matter manufacturing apparatus including a folding device 220.
圧着印刷物P3の第二の形態は、重なった複数の記録媒体が、対向する面において、圧力応答性粒子Mによって接着されてなる、圧着印刷物である。本形態の圧着印刷物P3は、重ね装置を備える圧着印刷物の製造装置によって製造される。 A second form of the crimped printed matter P3 is a crimped printed matter in which a plurality of overlapping recording media are adhered to each other by pressure-responsive particles M on opposite surfaces. The crimped printed matter P3 of this embodiment is manufactured by a crimped printed matter manufacturing apparatus including a stacking device.
本実施形態に係る印刷物の製造装置は、記録媒体P2を折り装置220(又は重ね装置)から加圧装置230へ連続して搬送する形態の装置に限定されない。本実施形態に係る印刷物の製造装置は、折り装置220(又は重ね装置)を出た記録媒体P2を貯留し、記録媒体P2の貯留量が予め定められた量に達した後、記録媒体P2を加圧装置230に搬送する形態の装置でもよい。 The printed matter manufacturing apparatus according to the present embodiment is not limited to the apparatus in which the recording medium P2 is continuously conveyed from the folding device 220 (or the stacking device) to the pressurizing device 230. The printed matter manufacturing apparatus according to the present embodiment stores the recording medium P2 that has exited the folding device 220 (or the stacking device), and after the storage amount of the recording medium P2 reaches a predetermined amount, the recording medium P2 is stored. The device may be in the form of being conveyed to the pressurizing device 230.
本実施形態に係る印刷物の製造装置において、折り装置220(又は重ね装置)と圧着加圧装置230とは、近接している形態でもよく、離隔している形態でもよい。折り装置220(又は重ね装置)と圧着加圧装置230とが離隔している場合、折り装置220(又は重ね装置)と圧着加圧装置230とは、例えば、記録媒体P2を搬送する搬送手段(例えばベルトコンベア)によって繋がれる。 In the printed matter manufacturing apparatus according to the present embodiment, the folding apparatus 220 (or the stacking apparatus) and the crimping pressurizing apparatus 230 may be in close proximity to each other or may be separated from each other. When the folding device 220 (or the stacking device) and the crimping pressurizing device 230 are separated from each other, the folding device 220 (or the stacking device) and the crimping pressurizing device 230 are, for example, a transport means for transporting the recording medium P2. For example, they are connected by a belt conveyor).
本実施形態に係る印刷物の製造装置は、記録媒体を予め定められた寸法に裁断する裁断手段を備えていてもよい。裁断手段は、例えば、配置手段100と圧着手段200との間に配置され、記録媒体P1の一部であって圧力応答性粒子Mが配置されていない領域を切り落とす裁断手段;折り装置220と加圧装置230との間に配置され、記録媒体P2の一部であって圧力応答性粒子Mが配置されていない領域を切り落とす裁断手段;圧着手段200の下流に配置され、圧着印刷物P3の一部であって圧力応答性粒子Mによって接着されていない領域を切り落とす裁断手段;などである。 The printed matter manufacturing apparatus according to the present embodiment may include a cutting means for cutting the recording medium to a predetermined size. The cutting means is arranged, for example, between the arranging means 100 and the crimping means 200, and cuts off a region which is a part of the recording medium P1 and where the pressure-responsive particles M are not arranged; the folding device 220 and the addition. Cutting means arranged between the pressure device 230 and a part of the recording medium P2 where the pressure-responsive particles M are not arranged; a cutting means arranged downstream of the crimping means 200 and a part of the crimping printed matter P3. A cutting means for cutting off a region that is not adhered by the pressure-responsive particles M; and the like.
本実施形態に係る印刷物の製造装置は、枚葉式の装置に限定されない。本実施形態に係る印刷物の製造装置は、長尺の記録媒体に対して配置工程及び圧着工程を行って長尺の圧着印刷物を形成した後、長尺の圧着印刷物を予め定められた寸法に裁断する様式の装置であってもよい。 The printed matter manufacturing apparatus according to the present embodiment is not limited to the sheet-fed type apparatus. The printed matter manufacturing apparatus according to the present embodiment performs an arrangement step and a crimping step on a long recording medium to form a long crimped printed matter, and then cuts the long crimped printed matter to a predetermined size. It may be a device in the style of
本実施形態に係る印刷物の製造装置は、色材を用いて記録媒体上に有色画像を形成する有色画像形成手段をさらに含んでもよい。有色画像形成手段は、例えば、色材として有色のインクを用いてインクジェット方式により記録媒体上に有色インク画像を形成する手段、有色の静電荷像現像剤を用いて電子写真方式により記録媒体上に有色画像を形成する手段等が挙げられる。 The printed matter manufacturing apparatus according to the present embodiment may further include a colored image forming means for forming a colored image on a recording medium using a coloring material. The colored image forming means is, for example, a means for forming a colored ink image on a recording medium by an inkjet method using a colored ink as a coloring material, or a means for forming a colored ink image on a recording medium by an electrophotographic method using a colored electrostatic charge image developer. Means for forming a colored image and the like can be mentioned.
上記構成の製造装置によって、本実施形態に係る印刷物の製造方法であって、色材を用いて記録媒体上に有色画像を形成する有色画像形成工程をさらに含む製造方法が実施される。有色画像形成工程は、具体的には、例えば、色材として有色のインクを用いてインクジェット方式により記録媒体上に有色インク画像を形成する工程、有色の静電荷像現像剤を用いて電子写真方式により記録媒体上に有色画像を形成する工程等が挙げられる。 With the manufacturing apparatus having the above configuration, the manufacturing method according to the present embodiment, further including a colored image forming step of forming a colored image on a recording medium using a coloring material, is carried out. Specifically, the colored image forming step is, for example, a step of forming a colored ink image on a recording medium by an inkjet method using a colored ink as a coloring material, and an electrophotographic method using a colored electrostatic charge image developer. Examples thereof include a step of forming a colored image on a recording medium.
<印刷物製造用シート、印刷物製造用シートの製造方法>
本実施形態に係る印刷物製造用シートは、基材と、前記基材上に配置された圧力応答性粒子と、を有する。本実施形態に係る印刷物製造用シートは、本実施形態に係る圧力応答性粒子を用いて製造される。基材上の圧力応答性粒子は、基材上に配置される前の粒子形状を保っていてもよく、保っていなくてもよい。
<Printed matter manufacturing sheet, manufacturing method of printed matter manufacturing sheet>
The printed matter manufacturing sheet according to the present embodiment has a base material and pressure-responsive particles arranged on the base material. The printed matter manufacturing sheet according to the present embodiment is manufactured by using the pressure-responsive particles according to the present embodiment. The pressure-responsive particles on the substrate may or may not retain their particle shape prior to being placed on the substrate.
本実施形態に係る印刷物製造用シートは、例えば、記録媒体に記録された情報を秘匿したい場合に記録媒体に重ねて接着されるマスキングシート;記録媒体どうしを重ねて接着する際に、記録媒体上に接着剤層を設けるために使用される剥離シート;などに適用される。 The printed matter manufacturing sheet according to the present embodiment is, for example, a masking sheet that is adhered to the recording medium when it is desired to conceal the information recorded on the recording medium; when the recording media are adhered to each other on the recording medium. It is applied to a release sheet used for providing an adhesive layer on the surface; and the like.
本実施形態に係る印刷物製造用シートに適用する基材としては、例えば、紙、紙の表面を樹脂等でコーティングしたコート紙、布、不織布、樹脂フィルム、樹脂シートなどが挙げられる。基材には、片面又は両面に画像が形成されていてもよい。 Examples of the base material applied to the printed matter manufacturing sheet according to the present embodiment include paper, coated paper in which the surface of the paper is coated with resin or the like, cloth, non-woven fabric, resin film, resin sheet, and the like. An image may be formed on one side or both sides of the base material.
本実施形態に係る印刷物製造用シートにおいて、圧力応答性粒子は、基材の全面に配置されていてもよく、基材の一部に配置されていてもよい。圧力応答性粒子は、基材上に1層又は複数層配置されている。圧力応答性粒子の層は、基材の面方向に連続した層であってもよいし、基材の面方向に不連続な層であってもよい。圧力応答性粒子の層は、圧力応答性粒子が粒子のまま並んだ層であってもよく、隣接する圧力応答性粒子どうしが融合して並んだ層であってもよい。 In the printed matter manufacturing sheet according to the present embodiment, the pressure-responsive particles may be arranged on the entire surface of the base material or may be arranged on a part of the base material. The pressure-responsive particles are arranged in one 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 base material or a layer discontinuous in the plane direction of the base material. The layer of the pressure-responsive particles may be a layer in which the pressure-responsive particles are arranged as particles, or may be a layer in which adjacent pressure-responsive particles are fused and arranged.
基材上の圧力応答性粒子の量は、配置された領域において、例えば、0.5g/m2以上50g/m2以下であり、1g/m2以上40g/m2以下であり、1.5g/m2以上30g/m2以下である。基材上の圧力応答性粒子の層厚は、例えば、0.2μm以上25μm以下であり、0.4μm以上20μm以下であり、0.6μm以上15μm以下である。 The amount of pressure-responsive particles on the substrate is, for example, 0.5 g / m 2 or more and 50 g / m 2 or less, 1 g / m 2 or more and 40 g / m 2 or less, in the arranged region. It is 5 g / m 2 or more and 30 g / m 2 or less. The layer thickness of the pressure-responsive particles on the substrate is, for example, 0.2 μm or more and 25 μm or less, 0.4 μm or more and 20 μm or less, and 0.6 μm or more and 15 μm or less.
本実施形態に係る印刷物製造用シートは、例えば、本実施形態に係る圧力応答性粒子を用いるとともに、前記圧力応答性粒子を基材上に配置する配置工程を含む製造方法によって製造される。 The printed matter manufacturing sheet according to the present embodiment is manufactured by, for example, a manufacturing method including the pressure-responsive particles according to the present embodiment and an arrangement step of arranging the pressure-responsive particles on a substrate.
配置工程は、例えば、圧力応答性粒子を基材上に付与する付与工程を含み、さらに、基材上に付与された圧力応答性粒子を基材上に固定する固定工程を含んでもよい。 The arranging step may include, for example, an application step of applying the pressure-responsive particles on the substrate, and may further include a fixing step of fixing the pressure-responsive particles applied on the substrate on the substrate.
付与工程は、例えば、スプレー法、バーコート法、ダイコート法、ナイフコート法、ロールコート法、リバースロールコート法、グラビアコート法、スクリーン印刷法、インクジェット法、ラミネート法、電子写真法などの付与方法により実現される。付与工程の付与方法に応じて、圧力応答性粒子を分散媒に分散させ液体組成物を調製し、液体組成物を付与工程に適用してもよい。 The applying process includes, for example, a spray method, a bar coating method, a die coating method, a knife coating method, a roll coating method, a reverse roll coating method, a gravure coating method, a screen printing method, an inkjet method, a laminating method, an electrophotographic method, and the like. Is realized by. Depending on the method of applying the application step, pressure-responsive particles may be dispersed in a dispersion medium to prepare a liquid composition, and the liquid composition may be applied to the application step.
固定工程は、例えば、基材上の圧力応答性粒子を加熱源で加熱し、圧力応答性粒子を基材上に固定する加熱工程;圧力応答性粒子が付与された基材を一対の加圧部材(ロール/ロール、ベルト/ロール)にて加圧し、圧力応答性粒子を基材上に固定する加圧工程;圧力応答性粒子が付与された基材を、内部に加熱源を備える一対の加圧部材(ロール/ロール、ベルト/ロール)にて加圧及び加熱し、圧力応答性粒子を基材上に固定する加圧加熱工程;などである。 The fixing step is, for example, a heating step of heating the pressure-responsive particles on the substrate with a heating source and fixing the pressure-responsive particles on the substrate; a pair of pressurization of the substrate to which the pressure-responsive particles are applied. Pressurization step of pressurizing with a member (roll / roll, belt / roll) and fixing pressure-responsive particles on a base material; a pair of base materials to which pressure-responsive particles are applied, having a heating source inside. A pressure heating step of pressurizing and heating with a pressure member (roll / roll, belt / roll) to fix pressure-responsive particles on a substrate; and the like.
<電子写真方式による印刷物の製造>
本実施形態に係る圧力応答性粒子を電子写真方式に適用する実施形態例を説明する。電子写真方式においては、圧力応答性粒子はトナーとして使用される。
<Manufacturing printed matter by electrophotographic method>
An example of an embodiment in which the pressure-responsive particles according to the present embodiment are applied to the electrophotographic method will be described. In electrophotographic schemes, pressure responsive particles are used as toner.
[静電荷像現像剤]
本実施形態に係る静電荷像現像剤は、本実施形態に係る圧力応答性粒子を少なくとも含むものである。本実施形態に係る静電荷像現像剤は、本実施形態に係る圧力応答性粒子のみを含む一成分現像剤であってもよいし、本実施形態に係る圧力応答性粒子とキャリアとを混合した二成分現像剤であってもよい。
[Static charge image developer]
The electrostatic charge image developer according to the present embodiment contains at least the pressure-responsive particles according to the present embodiment. The electrostatic charge 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 the pressure-responsive particles according to the present embodiment and carriers are mixed. It may be a two-component developer.
キャリアとしては、特に制限はなく、公知のキャリアが挙げられる。キャリアとしては、例えば、磁性粉からなる芯材の表面に樹脂を被覆した被覆キャリア;マトリックス樹脂中に磁性粉が分散して配合された磁性粉分散型キャリア;多孔質の磁性粉に樹脂を含浸させた樹脂含浸型キャリア;等が挙げられる。磁性粉分散型キャリア、樹脂含浸型キャリアは、当該キャリアの構成粒子を芯材とし、この表面を樹脂で被覆したキャリアであってもよい。 The carrier is not particularly limited, and examples thereof include known carriers. As the carrier, for example, a coating carrier in which the surface of a core material made of magnetic powder is coated with a resin; a magnetic powder dispersion type carrier in which the magnetic powder is dispersed in a matrix resin; and a porous magnetic powder is impregnated with the resin. Resin-impregnated carrier; etc. The magnetic powder dispersion type carrier and the resin impregnation type carrier may be carriers in which the constituent particles of the carrier are used as a core material and the surface thereof is coated with a resin.
磁性粉としては、例えば、鉄、ニッケル、コバルト等の磁性金属;フェライト、マグネタイト等の磁性酸化物;などが挙げられる。 Examples of the magnetic powder include magnetic metals such as iron, nickel and cobalt; magnetic oxides such as ferrite and magnetite; and the like.
被覆用の樹脂及びマトリックス樹脂としては、例えば、ポリエチレン、ポリプロピレン、ポリスチレン、ポリビニルアセテート、ポリビニルアルコール、ポリビニルブチラール、ポリ塩化ビニル、ポリビニルエーテル、ポリビニルケトン、塩化ビニル−酢酸ビニル共重合体、スチレン−アクリル酸エステル共重合体、オルガノシロキサン結合を含んで構成されるストレートシリコーン樹脂又はその変性品、フッ素樹脂、ポリエステル、ポリカーボネート、フェノール樹脂、エポキシ樹脂等が挙げられる。被覆用の樹脂及びマトリックス樹脂には、導電性粒子等、その他添加剤を含ませてもよい。導電性粒子としては、金、銀、銅等の金属、カーボンブラック、酸化チタン、酸化亜鉛、酸化スズ、硫酸バリウム、ホウ酸アルミニウム、チタン酸カリウム等の粒子が挙げられる。 Examples of the coating resin and matrix resin include polyethylene, polypropylene, polystyrene, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl ether, polyvinyl ketone, vinyl chloride-vinyl acetate copolymer, and styrene-acrylic acid. Examples thereof include an ester copolymer, a straight silicone resin containing an organosiloxane bond or a modified product thereof, a fluororesin, a polyester, a polypropylene, 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, and particles such as carbon black, titanium oxide, zinc oxide, tin oxide, barium sulfate, aluminum borate and potassium titanate.
芯材の表面を樹脂で被覆するには、被覆用の樹脂、及び各種添加剤(必要に応じて使用する)を適当な溶媒に溶解した被覆層形成用溶液により被覆する方法等が挙げられる。溶媒としては、特に限定されるものではなく、使用する樹脂の種類や、塗布適性等を勘案して選択すればよい。
具体的な樹脂被覆方法としては、芯材を被覆層形成用溶液中に浸漬する浸漬法;被覆層形成用溶液を芯材表面に噴霧するスプレー法;芯材を流動エアーにより浮遊させた状態で被覆層形成用溶液を噴霧する流動床法;ニーダーコーター中でキャリアの芯材と被覆層形成用溶液とを混合し、その後に溶剤を除去するニーダーコーター法;等が挙げられる。
Examples of coating the surface of the core material with a resin include a method of coating with a coating resin and a coating layer forming solution in which various additives (used if necessary) are dissolved in an appropriate solvent. The solvent is not particularly limited, and may be selected in consideration of the type of resin used, coating suitability, and the like.
Specific resin coating methods include a dipping method in which the core material is immersed in a coating layer forming solution; a spray method in which the coating layer forming solution is sprayed onto the core material surface; and the core material is suspended by flowing air. Examples thereof include a fluidized bed method in which a coating layer forming solution is sprayed; a kneader coater method in which a carrier core material and a coating layer forming solution are mixed in a kneader coater, and then the solvent is removed.
二成分現像剤における圧力応答性粒子とキャリアとの混合比(質量比)は、圧力応答性粒子:キャリア=1:100乃至30:100が好ましく、3:100乃至20:100がより好ましい。 The mixing ratio (mass ratio) of the pressure-responsive particles and the carriers in the two-component developer is preferably pressure-responsive particles: carriers = 1: 100 to 30: 100, and more preferably 3: 100 to 20: 100.
[印刷物の製造装置、印刷物の製造方法]
電子写真方式を適用した印刷物の製造装置は、本実施形態に係る圧力応答性粒子を含む現像剤を収容し、前記圧力応答性粒子を電子写真方式により記録媒体上に配置する配置手段と、前記記録媒体を折り重ねて圧着する、又は、前記記録媒体と別の記録媒体とを重ねて圧着する圧着手段と、を含む。
[Printed matter manufacturing equipment, printed matter manufacturing method]
The printed matter manufacturing apparatus to which the electrophotographic method is applied includes an arrangement means for accommodating the developer containing the pressure-responsive particles according to the present embodiment and arranging the pressure-responsive particles on a recording medium by the electrophotographic method, and the above-mentioned It includes a crimping means for folding and crimping a recording medium, or stacking and crimping the recording medium and another recording medium.
本実施形態に係る印刷物の製造装置によって、電子写真方式による印刷物の製造方法が実施される。本実施形態に係る印刷物の製造方法は、本実施形態に係る圧力応答性粒子を含む現像剤を用いて、前記圧力応答性粒子を電子写真方式により記録媒体上に配置する配置工程と、前記記録媒体を折り重ねて圧着する、又は、前記記録媒体と別の記録媒体とを重ねて圧着する圧着工程と、を含む。 The printed matter manufacturing apparatus according to the present embodiment implements a printed matter manufacturing method by an electrophotographic method. The method for producing a printed matter according to the present embodiment includes an arrangement step of arranging the pressure-responsive particles on a recording medium by an electrophotographic method using a developer containing the pressure-responsive particles according to the present embodiment, and the recording. It includes a crimping step of folding and crimping a medium, or stacking and crimping the recording medium and another recording medium.
本実施形態に係る印刷物の製造装置が含む前記配置手段は、例えば、
感光体と、
前記感光体の表面を帯電する帯電手段と、
帯電した前記感光体の表面に静電荷像を形成する静電荷像形成手段と、
本実施形態に係る静電荷像現像剤を収容し、前記静電荷像現像剤により、前記感光体の表面に形成された静電荷像を圧力応答性粒子付与部として現像する現像手段と、
前記感光体の表面に形成された圧力応答性粒子付与部を記録媒体の表面に転写する転写手段と、
を備える。
前記配置手段は、記録媒体の表面に転写された圧力応答性粒子付与部を固定する固定手段をさらに備えることが好ましい。
The arrangement means included in the printed matter manufacturing apparatus according to the present embodiment is, for example,
Photoreceptor and
A charging means for charging the surface of the photoconductor and
An electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged photoconductor, and
A developing means that accommodates the electrostatic charge image developer according to the present embodiment and develops the electrostatic charge image formed on the surface of the photoconductor as a pressure-responsive particle imparting portion by the electrostatic charge image developer.
A transfer means for transferring the pressure-responsive particle-imparting portion formed on the surface of the photoconductor to the surface of the recording medium, and
To be equipped.
It is preferable that the arrangement means further includes a fixing means for fixing the pressure-responsive particle-imparting portion transferred to the surface of the recording medium.
本実施形態に係る印刷物の製造方法が含む前記配置工程は、例えば、
感光体の表面を帯電する帯電工程と、
帯電した前記感光体の表面に静電荷像を形成する静電荷像形成工程と、
本実施形態に係る静電荷像現像剤により、前記感光体の表面に形成された静電荷像を圧力応答性粒子付与部として現像する現像工程と、
前記感光体の表面に形成された圧力応答性粒子付与部を記録媒体の表面に転写する転写工程と、
を含む。
前記配置工程は、記録媒体の表面に転写された圧力応答性粒子付与部を固定する固定工程をさらに含むことが好ましい。
The arrangement step included in the method for producing a printed matter according to the present embodiment is, for example,
The charging process that charges the surface of the photoconductor,
A static charge image forming step of forming an electrostatic charge image on the surface of the charged photoconductor, and
A developing step of developing an electrostatic charge image formed on the surface of the photoconductor as a pressure-responsive particle-imparting portion by using the electrostatic charge image developer according to the present embodiment.
A transfer step of transferring the pressure-responsive particle-imparting portion formed on the surface of the photoconductor to the surface of the recording medium, and
including.
It is preferable that the arrangement step further includes a fixing step of fixing the pressure-responsive particle-imparting portion transferred to the surface of the recording medium.
前記配置手段は、例えば、感光体の表面に形成された圧力応答性粒子付与部を直接記録媒体に転写する直接転写方式の装置;感光体の表面に形成された圧力応答性粒子付与部を中間転写体の表面に一次転写し、中間転写体の表面に転写された圧力応答性粒子付与部を記録媒体の表面に二次転写する中間転写方式の装置;圧力応答性粒子付与部の転写後、帯電前の感光体の表面をクリーニングするクリーニング手段を備えた装置;圧力応答性粒子付与部の転写後、帯電前に感光体の表面に除電光を照射して除電する除電手段を備える装置;などの装置である。前記配置手段が中間転写方式の装置の場合、転写手段は、例えば、表面に圧力応答性粒子付与部が転写される中間転写体と、感光体の表面に形成された圧力応答性粒子付与部を中間転写体の表面に一次転写する一次転写手段と、中間転写体の表面に転写された圧力応答性粒子付与部を記録媒体の表面に二次転写する二次転写手段と、を有する。 The arrangement means is, for example, a direct transfer type device that directly transfers the pressure-responsive particle-imparting portion formed on the surface of the photoconductor to a recording medium; the pressure-responsive particle-imparting portion formed on the surface of the photoconductor is intermediate. An intermediate transfer type device that first transfers to the surface of the transfer body and secondarily transfers the pressure-responsive particle-imparting portion transferred to the surface of the intermediate transfer body to the surface of the recording medium; after the transfer of the pressure-responsive particle-imparting portion, A device equipped with a cleaning means for cleaning the surface of the photoconductor before charging; a device provided with a static elimination means for irradiating the surface of the photoconductor with static elimination light after transfer of the pressure-responsive particle-imparting portion and before charging; It is a device of. When the arrangement means is an intermediate transfer type apparatus, the transfer means includes, for example, an intermediate transfer body in which the pressure-responsive particle-imparting portion is transferred to the surface and a pressure-responsive particle-imparting portion formed on the surface of the photoconductor. It has a primary transfer means for primary transfer to the surface of the intermediate transfer body, and a secondary transfer means for secondary transfer of the pressure-responsive particle-imparting portion transferred to the surface of the intermediate transfer body to the surface of the recording medium.
前記配置手段は、現像手段を含む部分が、前記配置手段に着脱するカートリッジ構造(いわゆるプロセスカートリッジ)であってもよい。プロセスカートリッジとしては、例えば、本実施形態に係る静電荷像現像剤を収容し、現像手段を備えるプロセスカートリッジが好適に用いられる。 The arrangement means may have a cartridge structure (so-called process cartridge) in which a portion including the developing means is attached to and detached from the arrangement means. As the process cartridge, for example, a process cartridge containing the electrostatic charge image developer according to the present embodiment and provided with developing means is preferably used.
本実施形態に係る印刷物の製造装置が含む圧着手段は、本実施形態に係る圧力応答性粒子が配置された記録媒体に圧力を印加する。これによって、記録媒体上において本実施形態に係る圧力応答性粒子が流動化し接着性を発揮する。本実施形態に係る圧力応答性粒子を流動化させる目的で圧着手段が記録媒体に印加する圧力は、3MPa以上300MPa以下が好ましく、10MPa以上200MPa以下がより好ましく、30MPa以上150MPa以下が更に好ましい。 The crimping means included in the printed matter manufacturing apparatus according to the present embodiment applies pressure to the recording medium on which the pressure-responsive particles according to the present embodiment are arranged. As a result, the pressure-responsive particles according to the present embodiment flow on the recording medium and exhibit adhesiveness. The pressure applied to the recording medium by the pressure-bonding means for the purpose of fluidizing the pressure-responsive particles according to the present embodiment is preferably 3 MPa or more and 300 MPa or less, more preferably 10 MPa or more and 200 MPa or less, and further preferably 30 MPa or more and 150 MPa or less.
本実施形態に係る圧力応答性粒子は、記録媒体の全面に配置されてもよく、記録媒体の一部に配置されてもよい。本実施形態に係る圧力応答性粒子は、記録媒体上に1層又は複数層配置される。本実施形態に係る圧力応答性粒子の層は、記録媒体の面方向に連続した層であってもよいし、記録媒体の面方向に不連続な層であってもよい。本実施形態に係る圧力応答性粒子の層は、圧力応答性粒子が粒子のまま並んだ層であってもよく、隣接する圧力応答性粒子どうしが融合して並んだ層であってもよい。 The pressure-responsive particles according to the present embodiment may be arranged on the entire surface of the recording medium or may be arranged on a part of the recording medium. The pressure-responsive particles according to the present embodiment are arranged in one layer or a plurality of layers on a recording medium. The layer of the pressure-responsive particles according to the present embodiment may be a layer continuous in the plane direction of the recording medium or a layer discontinuous in the plane direction of the recording medium. The layer of the pressure-responsive particles according to the present embodiment may be a layer in which the pressure-responsive particles are arranged as they are, or may be a layer in which adjacent pressure-responsive particles are fused and arranged.
記録媒体上の本実施形態に係る圧力応答性粒子(好ましくは透明な圧力応答性粒子)の量は、配置された領域において、例えば、0.5g/m2以上50g/m2以下であり、1g/m2以上40g/m2以下であり、1.5g/m2以上30g/m2以下である。記録媒体上の本実施形態に係る圧力応答性粒子(好ましくは透明な圧力応答性粒子)の層厚は、例えば、0.2μm以上25μm以下であり、0.4μm以上20μm以下であり、0.6μm以上15μm以下である。 The amount of pressure-responsive particles (preferably transparent pressure-responsive particles) according to the present embodiment on the recording medium is, for example, 0.5 g / m 2 or more and 50 g / m 2 or less in the arranged region. It is 1 g / m 2 or more and 40 g / m 2 or less, and 1.5 g / m 2 or more and 30 g / m 2 or less. The layer thickness of the pressure-responsive particles (preferably transparent pressure-responsive particles) according to the present embodiment on the recording medium is, for example, 0.2 μm or more and 25 μm or less, 0.4 μm or more and 20 μm or less, and 0. It is 6 μm or more and 15 μm or less.
本実施形態に係る印刷物の製造装置に適用する記録媒体としては、例えば、紙、紙の表面を樹脂等でコーティングしたコート紙、布、不織布、樹脂フィルム、樹脂シートなどが挙げられる。記録媒体は、片面又は両面に画像を有していてもよい。 Examples of the recording medium applied to the printed matter manufacturing apparatus according to the present embodiment include paper, coated paper in which the surface of the paper is coated with resin or the like, cloth, non-woven fabric, resin film, resin sheet, and the like. The recording medium may have an image on one side or both sides.
以下、電子写真方式を適用した本実施形態に係る印刷物の製造装置の一例を示すが、本実施形態はこれに限定されるわけではない。 Hereinafter, an example of a printed matter manufacturing apparatus according to the present embodiment to which the electrophotographic method is applied will be shown, but the present embodiment is not limited to this.
図2は、本実施形態に係る印刷物の製造装置の一例を示す概略構成図である。図2に示す印刷物の製造装置は、配置手段100と、配置手段100の下流に配置された圧着手段200とを備える。矢印は、感光体の回転方向又は記録媒体の搬送方向を示す。 FIG. 2 is a schematic configuration diagram showing an example of a printed matter manufacturing apparatus according to the present embodiment. The printed matter manufacturing apparatus shown in FIG. 2 includes an arrangement means 100 and a crimping means 200 arranged downstream of the arrangement means 100. The arrow indicates the rotation direction of the photoconductor or the transport direction of the recording medium.
配置手段100は、本実施形態に係る圧力応答性粒子を含む現像剤を用いて、本実施形態に係る圧力応答性粒子を電子写真方式により記録媒体P上に配置する直接転写方式の装置である。記録媒体Pには、片面又は両面に予め画像が形成されている。 The arranging means 100 is a direct transfer type apparatus for arranging the pressure responsive particles according to the present embodiment on the recording medium P by an electrophotographic method using a developer containing the pressure responsive particles according to the present embodiment. .. An image is formed in advance on one side or both sides of the recording medium P.
配置手段100は、感光体101を有している。感光体101の周囲には、感光体101の表面を帯電させる帯電ロール(帯電手段の一例)102、帯電した感光体101の表面をレーザ光線によって露光して静電荷像を形成する露光装置(静電荷像形成手段の一例)103、静電荷像に圧力応答性粒子を供給して静電荷像を現像する現像装置(現像手段の一例)104、現像した圧力応答性粒子付与部を記録媒体P上に転写する転写ロール(転写手段の一例)105、及び転写後に感光体101の表面に残存する圧力応答性粒子を除去する感光体クリーニング装置(クリーニング手段の一例)106が順に配置されている。 The arranging means 100 has a photoconductor 101. Around the photoconductor 101, a charging roll (an example of charging means) 102 that charges the surface of the photoconductor 101, and an exposure apparatus (static) that exposes the surface of the charged photoconductor 101 with a laser beam to form a static charge image. Example of charge image forming means) 103, a developing device (an example of developing means) 104 that supplies pressure-responsive particles to an electrostatic charge image to develop an electrostatic charge image, and a developed pressure-responsive particle imparting portion on a recording medium P. A transfer roll (an example of a transfer means) 105 to be transferred to, and a photoconductor cleaning device (an example of a cleaning means) 106 for removing pressure-responsive particles remaining on the surface of the photoconductor 101 after transfer are arranged in this order.
配置手段100が本実施形態に係る圧力応答性粒子を記録媒体P上に配置する動作について説明する。
まず、帯電ロール102によって感光体101の表面が帯電される。帯電した感光体101の表面に、図示しない制御部から送られてくる画像データに従って、露光装置103がレーザ光線を照射する。それにより、本実施形態に係る圧力応答性粒子の配置パターンの静電荷像が感光体101の表面に形成される。
The operation of the arranging means 100 arranging the pressure-responsive particles according to the present embodiment on the recording medium P will be described.
First, the surface of the photoconductor 101 is charged by the charging roll 102. The exposure device 103 irradiates the surface of the charged photoconductor 101 with a laser beam according to image data sent from a control unit (not shown). As a result, an electrostatic charge image of the arrangement pattern of the pressure-responsive particles according to the present embodiment is formed on the surface of the photoconductor 101.
感光体101上に形成された静電荷像は、感光体101の走行に従って現像位置まで回転する。そして、現像位置で、感光体101上の静電荷像が、現像装置104によって現像され圧力応答性粒子付与部になる。 The electrostatic charge image formed on the photoconductor 101 rotates to the developing position as the photoconductor 101 travels. Then, at the developing position, the electrostatic charge image on the photoconductor 101 is developed by the developing device 104 to become a pressure-responsive particle imparting portion.
現像装置104内には、少なくとも本実施形態に係る圧力応答性粒子とキャリアとを含む現像剤が収容されている。本実施形態に係る圧力応答性粒子は、現像装置104の内部でキャリアとともに攪拌されることで摩擦帯電し、現像剤ロール上に保持されている。感光体101の表面が現像装置104を通過していくことにより、感光体101表面の静電荷像に圧力応答性粒子が静電的に付着し、静電荷像が圧力応答性粒子によって現像される。圧力応答性粒子付与部が形成された感光体101は、引き続き走行し、感光体101上の圧力応答性粒子付与部が転写位置へ搬送される。 The developing apparatus 104 contains at least a developing agent containing pressure-responsive particles and carriers according to the present embodiment. The pressure-responsive particles according to the present embodiment are triboelectrically charged by being stirred together with the carrier inside the developing apparatus 104 and are held on the developing agent roll. As the surface of the photoconductor 101 passes through the developing device 104, the pressure-responsive particles are electrostatically attached to the electrostatic charge image on the surface of the photoconductor 101, and the electrostatic charge image is developed by the pressure-responsive particles. .. The photoconductor 101 on which the pressure-responsive particle-imparting portion is formed continues to run, and the pressure-responsive particle-imparting portion on the photoconductor 101 is conveyed to the transfer position.
感光体101上の圧力応答性粒子付与部が転写位置へ搬送されると、転写ロール105に転写バイアスが印加され、感光体101から転写ロール105に向う静電気力が圧力応答性粒子付与部に作用し、感光体101上の圧力応答性粒子付与部が記録媒体P上に転写される。 When the pressure-responsive particle-imparting portion on the photoconductor 101 is conveyed to the transfer position, a transfer bias is applied to the transfer roll 105, and an electrostatic force from the photoconductor 101 toward the transfer roll 105 acts on the pressure-responsive particle-imparting portion. Then, the pressure-responsive particle-imparting portion on the photoconductor 101 is transferred onto the recording medium P.
感光体101上に残留した圧力応答性粒子は感光体クリーニング装置106で除去されて回収される。感光体クリーニング装置106は、例えば、クリーニングブレード、クリーニングブラシ等である。感光体クリーニング装置106は、感光体の表面に残留した本実施形態に係る圧力応答性粒子が圧力により流動化して感光体の表面に膜状に付着する現象を抑制する観点から、クリーニングブラシであることが好ましい。 The pressure-responsive particles remaining on the photoconductor 101 are removed by the photoconductor cleaning device 106 and recovered. The photoconductor cleaning device 106 is, for example, a cleaning blade, a cleaning brush, or the like. The photoconductor cleaning device 106 is a cleaning brush from the viewpoint of suppressing the phenomenon that the pressure-responsive particles according to the present embodiment remaining on the surface of the photoconductor are fluidized by pressure and adhere to the surface of the photoconductor in the form of a film. Is preferable.
圧力応答性粒子付与部が転写された記録媒体Pは固定装置(固定手段の一例)107へと搬送される。固定装置107は、例えば、一対の固定部材(ロール/ロール、ベルト/ロール)である。配置手段100は、固定装置107を備えていなくてもよいが、記録媒体Pから本実施形態に係る圧力応答性粒子が脱落することを抑制する観点から、固定装置107を備えていることが好ましい。固定装置107が記録媒体Pに印加する圧力は、加圧装置230が記録媒体P2に印加する圧力に比較して低圧でよく、具体的には、0.2MPa以上1MPa以下が好ましい。 The recording medium P on which the pressure-responsive particle-imparting portion is transferred is conveyed to a fixing device (an example of fixing means) 107. The fixing device 107 is, for example, a pair of fixing members (roll / roll, belt / roll). The arranging means 100 may not be provided with the fixing device 107, but is preferably provided with the fixing device 107 from the viewpoint of suppressing the pressure-responsive particles according to the present embodiment from falling off from 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, it is preferably 0.2 MPa or more and 1 MPa or less.
固定装置107は内部に、記録媒体Pを加熱するための加熱源(例えばハロゲンヒータ)を有していても、有していなくてもよい。固定装置107が内部に加熱源を有する場合、加熱源によって加熱された際の記録媒体Pの表面温度は、150℃以上220℃以下が好ましく、155℃以上210℃以下がより好ましく、160℃以上200℃以下が更に好ましい。なお、固定装置107が内部に加熱源を有しないことは、配置手段100が備えるモーター等の発熱により、固定装置107内の温度が環境温度以上になることを除外しない。 The fixing device 107 may or may not have a heating source (for example, a halogen heater) for heating the recording medium P inside. When the fixing device 107 has a heating source inside, the surface temperature of the recording medium P when heated by the heating source is preferably 150 ° C. or higher and 220 ° C. or lower, more preferably 155 ° C. or higher and 210 ° C. or lower, and 160 ° C. or higher. More preferably 200 ° C. or lower. The fact that the fixing device 107 does not have a heating source inside does not exclude that the temperature inside the fixing device 107 becomes equal to or higher than the environmental temperature due to the heat generated by the motor or the like included in the arrangement means 100.
記録媒体Pは、配置手段100を通過することによって、画像上に本実施形態に係る圧力応答性粒子が付与された記録媒体P1になる。記録媒体P1は、圧着手段200に向けて搬送される。 By passing through the arrangement means 100, the recording medium P becomes the recording medium P1 to which the pressure-responsive particles according to the present embodiment are imparted on the image. The recording medium P1 is conveyed toward the crimping means 200.
本実施形態に係る印刷物の製造装置において、配置手段100と圧着手段200とは、近接している形態でもよく、離隔している形態でもよい。配置手段100と圧着手段200とが離隔している場合、配置手段100と圧着手段200とは、例えば、記録媒体P1を搬送する搬送手段(例えばベルトコンベア)によって繋がれる。 In the printed matter manufacturing apparatus according to the present embodiment, the arranging means 100 and the crimping means 200 may be in close proximity to each other or may be separated from each other. When the arrangement means 100 and the crimping means 200 are separated from each other, the arrangement means 100 and the crimping means 200 are connected by, for example, a conveying means (for example, a belt conveyor) that conveys the recording medium P1.
圧着手段200は、折り装置220と加圧装置230とを備え、記録媒体P1を折り重ねて圧着する手段である。 The crimping means 200 includes a folding device 220 and a pressurizing device 230, and is a means for folding and crimping the recording medium P1.
折り装置220は、当該装置を通過する記録媒体P1を折り重ね、折り重なった記録媒体P2を作製する。記録媒体P2の折り重なり方は、例えば、二つ折り、三つ折り、四つ折りであり、記録媒体P2の一部のみが折り重なっている形態でもよい。記録媒体P2は、対向する2つの面の少なくとも一方の面の少なくとも一部に、本実施形態に係る圧力応答性粒子が配置された状態である。 The folding device 220 folds the recording medium P1 that passes through the device to produce the folded recording medium P2. The folding method of the recording medium P2 is, for example, two-fold, three-fold, or four-fold, and a form in which only a part of the recording medium P2 is folded may be used. The recording medium P2 is in a state in which the pressure-responsive particles according to the present embodiment are arranged on at least a part of at least one of the two opposing surfaces.
折り装置220は、記録媒体P2に圧力を印加する一対の加圧部材(例えば、ロール/ロール、ベルト/ロール)を有していてもよい。折り装置220の加圧部材が記録媒体P2に印加する圧力は、加圧装置230が記録媒体P2に印加する圧力に比較して低圧でよく、具体的には、1MPa以上10MPa以下が好ましい。 The folding device 220 may have a pair of pressure members (for example, roll / roll, belt / roll) that apply pressure to the recording medium P2. The pressure applied to the recording medium P2 by the pressurizing member of the folding device 220 may be lower than the pressure applied to the recording medium P2 by the pressurizing device 230, and specifically, it is preferably 1 MPa or more and 10 MPa or less.
圧着手段200は、折り装置220の代わりに、記録媒体P1と別の記録媒体とを重ねる重ね装置を備えていてもよい。記録媒体P1と別の記録媒体との重なりの形態は、例えば、記録媒体P1上に別の記録媒体が1枚重なっている形態、記録媒体P1上の複数個所に別の記録媒体が1枚ずつそれぞれ重なっている形態などである。別の記録媒体は、片面又は両面に予め画像が形成されている記録媒体でもよく、画像が形成されていない記録媒体でもよく、予め作製しておいた圧着印刷物でもよい。 The crimping means 200 may include a stacking device for stacking the recording medium P1 and another recording medium instead of the folding device 220. The overlapping form of the recording medium P1 and another recording medium is, for example, a form in which one other recording medium is overlapped on the recording medium P1, and another recording medium is placed at a plurality of locations on the recording medium P1. These are overlapping forms. The other recording medium may be a recording medium in which an image is formed in advance on one side or both sides, a recording medium in which an image is not formed, or a pressure-bonded printed matter prepared in advance.
折り装置220(又は重ね装置)を出た記録媒体P2は、加圧装置230に向けて搬送される。 The recording medium P2 exiting the folding device 220 (or the stacking device) is conveyed toward the pressurizing device 230.
加圧装置230は、一対の加圧部材(則ち、加圧ロール231及び232)を備える。加圧ロール231と加圧ロール232とは互いの外周面で接触し且つ押し合い、通過する記録媒体P2に圧力を印加する。加圧装置230が備える一対の加圧部材は、加圧ロールと加圧ロールの組合せに限られず、加圧ロールと加圧ベルトの組合せ、加圧ベルトと加圧ベルトの組合せでもよい。 The pressurizing device 230 includes a pair of pressurizing members (that is, pressurizing rolls 231 and 232). The pressure roll 231 and the pressure roll 232 come into contact with each other and press each other on their outer peripheral surfaces, and apply pressure to the passing recording medium P2. The pair of pressurizing members included in the pressurizing device 230 is not limited to the combination of the pressurizing roll and the pressurizing roll, but may be a combination of the pressurizing roll and the pressurizing belt, or a combination of the pressurizing belt and the pressurizing belt.
加圧装置230を通過する記録媒体P2に圧力が印加されると、記録媒体P2上において本実施形態に係る圧力応答性粒子が圧力によって流動化し接着性を発揮する。加圧装置230が記録媒体P2に印加する圧力は、3MPa以上300MPa以下が好ましく、10MPa以上200MPa以下がより好ましく、30MPa以上150MPa以下が更に好ましい。 When pressure is applied to the recording medium P2 passing through the pressurizing device 230, the pressure-responsive particles according to the present embodiment are fluidized by the pressure on the recording medium P2 to exhibit adhesiveness. The pressure applied by the pressurizing device 230 to the recording medium P2 is preferably 3 MPa or more and 300 MPa or less, more preferably 10 MPa or more and 200 MPa or less, and further preferably 30 MPa or more and 150 MPa or less.
加圧装置230は内部に、記録媒体P2を加熱するための加熱源(例えばハロゲンヒータ)を有していても、有していなくてもよい。加圧装置230が内部に加熱源を有する場合、加熱源によって加熱された際の記録媒体P2の表面温度は、30℃以上120℃以下が好ましく、40℃以上100℃以下がより好ましく、50℃以上90℃以下が更に好ましい。なお、加圧装置230が内部に加熱源を有しないことは、加圧装置230が備えるモーター等の発熱により、加圧装置230内の温度が環境温度以上になることを除外しない。 The pressurizing device 230 may or may not have a heating source (for example, a halogen heater) for heating the recording medium P2 inside. When the pressurizing device 230 has a heating source inside, the surface temperature of the recording medium P2 when heated by the heating source is preferably 30 ° C. or higher and 120 ° C. or lower, more preferably 40 ° C. or higher and 100 ° C. or lower, and more preferably 50 ° C. More preferably 90 ° C. or lower. The fact that the pressurizing device 230 does not have a heating source inside does not exclude that the temperature inside the pressurizing device 230 becomes equal to or higher than the ambient temperature due to heat generated by the motor or the like included in the pressurizing device 230.
記録媒体P2が加圧装置230を通過することによって、折り重なった面どうしが流動化した本実施形態に係る圧力応答性粒子によって接着され、圧着印刷物P3が作製される。圧着印刷物P3は、対向する面どうしが、一部又は全部、接着されている。 When the recording medium P2 passes through the pressurizing device 230, the folded surfaces are adhered to each other by the fluidized pressure-responsive particles according to the present embodiment, and the crimped printed matter P3 is produced. In the pressure-bonded printed matter P3, the facing surfaces are partially or wholly adhered to each other.
完成した圧着印刷物P3は、加圧装置230から搬出される。 The completed crimped printed matter P3 is carried out from the pressurizing device 230.
圧着印刷物P3の第一の形態は、折り重なった記録媒体が、対向する面において、本実施形態に係る圧力応答性粒子によって接着されてなる、圧着印刷物である。本形態の圧着印刷物P3は、折り装置220を備える印刷物の製造装置によって製造される。 The first form of the crimped printed matter P3 is a crimped printed matter in which the folded recording media are adhered to each other on the facing surfaces by the pressure-responsive particles according to the present embodiment. The crimped printed matter P3 of this embodiment is manufactured by a printed matter manufacturing apparatus including a folding device 220.
圧着印刷物P3の第二の形態は、重なった複数の記録媒体が、対向する面において、本実施形態に係る圧力応答性粒子によって接着されてなる、圧着印刷物である。本形態の圧着印刷物P3は、重ね装置を備える圧着印刷物の製造装置によって製造される。 A second form of the crimped printed matter P3 is a crimped printed matter in which a plurality of overlapping recording media are adhered to each other on facing surfaces by the pressure-responsive particles according to the present embodiment. The crimped printed matter P3 of this embodiment is manufactured by a crimped printed matter manufacturing apparatus including a stacking device.
本実施形態に係る印刷物の製造装置は、記録媒体P2を折り装置220(又は重ね装置)から加圧装置230へ連続して搬送する形態の装置に限定されない。本実施形態に係る印刷物の製造装置は、折り装置220(又は重ね装置)を出た記録媒体P2を貯留し、記録媒体P2の貯留量が予め定められた量に達した後、記録媒体P2を加圧装置230に搬送する形態の装置でもよい。 The printed matter manufacturing apparatus according to the present embodiment is not limited to the apparatus in which the recording medium P2 is continuously conveyed from the folding device 220 (or the stacking device) to the pressurizing device 230. The printed matter manufacturing apparatus according to the present embodiment stores the recording medium P2 that has exited the folding device 220 (or the stacking device), and after the storage amount of the recording medium P2 reaches a predetermined amount, the recording medium P2 is stored. The device may be in the form of being conveyed to the pressurizing device 230.
本実施形態に係る印刷物の製造装置において、折り装置220(又は重ね装置)と圧着加圧装置230とは、近接している形態でもよく、離隔している形態でもよい。折り装置220(又は重ね装置)と圧着加圧装置230とが離隔している場合、折り装置220(又は重ね装置)と圧着加圧装置230とは、例えば、記録媒体P2を搬送する搬送手段(例えばベルトコンベア)によって繋がれる。 In the printed matter manufacturing apparatus according to the present embodiment, the folding apparatus 220 (or the stacking apparatus) and the crimping pressurizing apparatus 230 may be in close proximity to each other or may be separated from each other. When the folding device 220 (or the stacking device) and the crimping pressurizing device 230 are separated from each other, the folding device 220 (or the stacking device) and the crimping pressurizing device 230 are, for example, a transport means for transporting the recording medium P2. For example, they are connected by a belt conveyor).
本実施形態に係る印刷物の製造装置は、記録媒体を予め定められた寸法に裁断する裁断手段を備えていてもよい。裁断手段は、例えば、配置手段100と圧着手段200との間に配置され、記録媒体P1の一部であって本実施形態に係る圧力応答性粒子が配置されていない領域を切り落とす裁断手段;折り装置220と加圧装置230との間に配置され、記録媒体P2の一部であって本実施形態に係る圧力応答性粒子が配置されていない領域を切り落とす裁断手段;圧着手段200の下流に配置され、圧着印刷物P3の一部であって本実施形態に係る圧力応答性粒子によって接着されていない領域を切り落とす裁断手段;などである。 The printed matter manufacturing apparatus according to the present embodiment may include a cutting means for cutting the recording medium to a predetermined size. The cutting means is arranged, for example, between the arranging means 100 and the crimping means 200, and cuts off a portion of the recording medium P1 in which the pressure-responsive particles according to the present embodiment are not arranged; folding. Cutting means arranged between the device 220 and the pressurizing device 230 to cut off a part of the recording medium P2 in which the pressure-responsive particles according to the present embodiment are not arranged; arranged downstream of the crimping means 200. A cutting means for cutting off a region which is a part of the pressure-bonded printed matter P3 and is not adhered by the pressure-responsive particles according to the present embodiment; and the like.
本実施形態に係る印刷物の製造装置は、枚葉式の装置に限定されない。本実施形態に係る印刷物の製造装置は、長尺の記録媒体に対して配置工程及び圧着工程を行って長尺の圧着印刷物を形成した後、長尺の圧着印刷物を予め定められた寸法に裁断する様式の装置であってもよい。 The printed matter manufacturing apparatus according to the present embodiment is not limited to the sheet-fed type apparatus. The printed matter manufacturing apparatus according to the present embodiment performs an arrangement step and a crimping step on a long recording medium to form a long crimped printed matter, and then cuts the long crimped printed matter to a predetermined size. It may be a device in the style of
本実施形態に係る印刷物の製造装置は、有色の静電荷像現像剤を用いて電子写真方式により記録媒体上に有色画像を形成する有色画像形成手段をさらに含んでもよい。有色画像形成手段は、例えば、
感光体と、
前記感光体の表面を帯電する帯電手段と、
帯電した前記感光体の表面に静電荷像を形成する静電荷像形成手段と、
有色の静電荷像現像剤を収容し、有色の静電荷像現像剤により、前記感光体の表面に形成された静電荷像を有色のトナー画像として現像する現像手段と、
前記感光体の表面に形成された有色のトナー画像を記録媒体の表面に転写する転写手段と、
前記記録媒体の表面に転写された有色のトナー画像を熱定着する熱定着手段と、を備える。
The printed matter manufacturing apparatus according to the present embodiment may further include a colored image forming means for forming a colored image on a recording medium by an electrophotographic method using a colored electrostatic charge image developer. The colored image forming means is, for example,
Photoreceptor and
A charging means for charging the surface of the photoconductor and
An electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged photoconductor, and
A developing means that contains a colored electrostatic charge image developer and develops the electrostatic charge image formed on the surface of the photoconductor as a colored toner image by the colored electrostatic charge image developer.
A transfer means for transferring a colored toner image formed on the surface of the photoconductor to the surface of a recording medium, and
A heat fixing means for heat-fixing a colored toner image transferred to the surface of the recording medium is provided.
上記構成の製造装置によって、本実施形態に係る印刷物の製造方法であって、有色の静電荷像現像剤を用いて電子写真方式により記録媒体上に有色画像を形成する有色画像形成工程をさらに含む製造方法が実施される。有色画像形成工程は、具体的には、
感光体の表面を帯電する帯電工程と、
帯電した前記感光体の表面に静電荷像を形成する静電荷像形成工程と、
有色の静電荷像現像剤により、前記感光体の表面に形成された静電荷像を有色のトナー画像として現像する現像工程と、
前記感光体の表面に形成された有色のトナー画像を記録媒体の表面に転写する転写工程と、
前記記録媒体の表面に転写された有色のトナー画像を熱定着する熱定着工程と、を含む。
The method for producing a printed matter according to the present embodiment further includes a colored image forming step of forming a colored image on a recording medium by an electrophotographic method using a colored electrostatic charge image developer by the manufacturing apparatus having the above configuration. The manufacturing method is carried out. Specifically, the colored image forming process is described.
The charging process that charges the surface of the photoconductor,
A static charge image forming step of forming an electrostatic charge image on the surface of the charged photoconductor, and
A developing step of developing an electrostatic charge image formed on the surface of the photoconductor as a colored toner image with a colored electrostatic charge image developer.
A transfer step of transferring a colored toner image formed on the surface of the photoconductor to the surface of a recording medium, and
It includes a heat fixing step of heat fixing a colored toner image transferred to the surface of the recording medium.
本実施形態に係る印刷物の製造装置が含む有色画像形成手段は、例えば、感光体の表面に形成された有色のトナー画像を直接記録媒体に転写する直接転写方式の装置;感光体の表面に形成された有色のトナー画像を中間転写体の表面に一次転写し、中間転写体の表面に転写された有色のトナー画像を記録媒体の表面に二次転写する中間転写方式の装置;有色のトナー画像の転写後、帯電前の感光体の表面をクリーニングするクリーニング手段を備えた装置;有色のトナー画像の転写後、帯電前に感光体の表面に除電光を照射して除電する除電手段を備える装置;などの装置である。有色画像形成手段が中間転写方式の装置の場合、転写手段は、例えば、表面に有色のトナー画像が転写される中間転写体と、感光体の表面に形成された有色のトナー画像を中間転写体の表面に一次転写する一次転写手段と、中間転写体の表面に転写された有色のトナー画像を記録媒体の表面に二次転写する二次転写手段と、を有する。 The colored image forming means included in the printed matter manufacturing apparatus according to the present embodiment is, for example, a direct transfer type apparatus for directly transferring a colored toner image formed on the surface of the photoconductor to a recording medium; formed on the surface of the photoconductor. An intermediate transfer type device that primary transfers the colored toner image 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 the recording medium; colored toner image. A device equipped with a cleaning means for cleaning the surface of the photoconductor after the transfer and before charging; a device provided with a static elimination means for irradiating the surface of the photoconductor with static elimination light after the transfer of a colored toner image and before charging. ; And so on. When the colored image forming means is an intermediate transfer type apparatus, the transfer means transfers, for example, an intermediate transfer body in which a colored toner image is transferred to the surface and a colored toner image formed on the surface of the photoconductor. It has a primary transfer means for primary transfer to the surface of the intermediate transfer body and a secondary transfer means for secondary transfer of a colored toner image transferred to the surface of the intermediate transfer body to the surface of a recording medium.
本実施形態に係る印刷物の製造装置において、本実施形態に係る圧力応答性粒子を含む現像剤の配置手段と有色画像形成手段とが中間転写方式を採用している場合、配置手段と有色画像形成手段とは、中間転写体及び二次転写手段を共有していてもよい。 In the printed matter manufacturing apparatus according to the present embodiment, when the developing agent containing the pressure-responsive particles and the colored image forming means according to the present embodiment employ an intermediate transfer method, the placing means and the colored image forming means. The means may share an intermediate transfer body and a secondary transfer means.
本実施形態に係る印刷物の製造装置において、本実施形態に係る圧力応答性粒子を含む像現像剤の配置手段と有色画像形成手段とは、熱定着手段を共有していてもよい。 In the printed matter manufacturing apparatus according to the present embodiment, the heat fixing means may be shared between the means for arranging the image developer containing the pressure-responsive particles and the means for forming a colored image according to the present embodiment.
以下、有色画像形成手段を備える本実施形態に係る印刷物の製造装置の一例を示すが、本実施形態はこれに限定されるわけではない。以下の説明においては、図に示す主要部を説明し、その他はその説明を省略する。 Hereinafter, an example of a printed matter manufacturing apparatus according to the present embodiment including the colored image forming means will be shown, but the present embodiment is not limited to this. In the following description, the main parts shown in the figure will be described, and the description thereof will be omitted for the others.
図3は、電子写真方式を適用した本実施形態に係る印刷物の製造装置の一例を示す概略構成図である。図3に示す印刷物の製造装置は、記録媒体への本実施形態に係る圧力応答性粒子の配置と有色画像形成とを一括で行う印刷手段300と、印刷手段300の下流に配置された圧着手段200とを備える。 FIG. 3 is a schematic configuration diagram showing an example of a printed matter manufacturing apparatus according to the present embodiment to which the electrophotographic method is applied. The printed matter manufacturing apparatus shown in FIG. 3 includes a printing means 300 for collectively arranging pressure-responsive particles and forming a colored image according to the present embodiment on a recording medium, and a crimping means arranged downstream of the printing means 300. It is equipped with 200.
印刷手段300は、5連タンデム方式且つ中間転写方式の印刷手段である。印刷手段300は、本実施形態に係る圧力応答性粒子(T)を配置するユニット10Tと、イエロー(Y)、マゼンタ(M)、シアン(C)及びブラック(K)の各色画像を形成するユニット10Y、10M、10C及び10Kとを備えている。ユニット10Tが、本実施形態に係る圧力応答性粒子を含む現像剤を用いて記録媒体P上に本実施形態に係る圧力応答性粒子を配置する配置手段である。ユニット10Y、10M、10C及び10Kがそれぞれ、有色トナーを含む現像剤を用いて記録媒体P上に有色画像を形成する手段である。ユニット10T、10Y、10M、10C及び10Kは、電子写真方式を採用している。 The printing means 300 is a 5-series tandem type and intermediate transfer type printing means. The printing means 300 includes a unit 10T for arranging the pressure-responsive particles (T) according to the present embodiment and a unit for forming each color image of yellow (Y), magenta (M), cyan (C), and black (K). It has 10Y, 10M, 10C and 10K. The unit 10T is an arrangement means for arranging the pressure-responsive particles according to the present embodiment on the recording medium P using the developer containing the pressure-responsive particles according to the present embodiment. Units 10Y, 10M, 10C, and 10K are means for forming a colored image on the recording medium P by using a developing agent containing colored toner, respectively. Units 10T, 10Y, 10M, 10C and 10K employ an electrophotographic method.
ユニット10T、10Y、10M、10C及び10Kは、水平方向に互いに離間して並設されている。ユニット10T、10Y、10M、10C、10Kは、印刷手段300に着脱するプロセスカートリッジであってもよい。 The units 10T, 10Y, 10M, 10C and 10K are arranged side by side so as to be separated from each other in the horizontal direction. The units 10T, 10Y, 10M, 10C, and 10K may be process cartridges attached to and detached from the printing means 300.
ユニット10T、10Y、10M、10C及び10Kの下方には、各ユニットを通して中間転写ベルト(中間転写体の一例)20が延設されている。中間転写ベルト20は、中間転写ベルト20の内面に接する、駆動ロール22、支持ロール23、及び対向ロール24に巻きつけて設けられ、ユニット10Tからユニット10Kに向う方向に走行するようになっている。中間転写ベルト20の像保持面側には、駆動ロール22と対向して中間転写体クリーニング装置21が備えられている。 Below the units 10T, 10Y, 10M, 10C and 10K, an intermediate transfer belt (an example of an intermediate transfer body) 20 extends through each unit. The intermediate transfer belt 20 is provided so as to be wound around a drive roll 22, a support roll 23, and an opposing roll 24 that are in contact with the inner surface of the intermediate transfer belt 20, and travel in a direction from the unit 10T toward 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 drive roll 22.
ユニット10T、10Y、10M、10C及び10Kはそれぞれ、現像装置(現像手段の一例)4T、4Y、4M、4C及び4Kを備える。現像装置4T、4Y、4M、4C、4Kのそれぞれには、圧力応答性粒子カートリッジ8Tに収められた本実施形態に係る圧力応答性粒子、又は、トナーカートリッジ8Y、8M、8C、8Kに収められたイエロートナー、マゼンタトナー、シアントナー、ブラックトナーの供給がなされる。 Units 10T, 10Y, 10M, 10C and 10K include developing devices (an example of developing means) 4T, 4Y, 4M, 4C and 4K, respectively. Each of the developing devices 4T, 4Y, 4M, 4C, and 4K is housed in the pressure-responsive particles according to the present embodiment contained in the pressure-responsive particle cartridge 8T, or in the toner cartridges 8Y, 8M, 8C, 8K. Yellow toner, magenta toner, cyan toner, and black toner are supplied.
ユニット10T、10Y、10M、10C及び10Kは、同等の構成及び動作を有しているため、本実施形態に係る圧力応答性粒子を記録媒体上に配置するユニット10Tについて代表して説明する。 Since the units 10T, 10Y, 10M, 10C and 10K have the same configuration and operation, the unit 10T in which the pressure-responsive particles according to the present embodiment are arranged on the recording medium will be described as a representative.
ユニット10Tは、感光体1Tを有している。感光体1Tの周囲には、感光体1Tの表面を帯電させる帯電ロール(帯電手段の一例)2T、帯電した感光体1Tの表面をレーザ光線によって露光して静電荷像を形成する露光装置(静電荷像形成手段の一例)3T、静電荷像に圧力応答性粒子を供給して静電荷像を現像する現像装置(現像手段の一例)4T、現像した圧力応答性粒子付与部を中間転写ベルト20上に転写する一次転写ロール(一次転写手段の一例)5T、及び一次転写後に感光体1Tの表面に残存する圧力応答性粒子を除去する感光体クリーニング装置(クリーニング手段の一例)6Tが順に配置されている。一次転写ロール5Tは、中間転写ベルト20の内側に配置され、感光体1Tに対向した位置に設けられている。 The unit 10T has a photoconductor 1T. Around the photoconductor 1T, a charging roll (an example of charging means) 2T that charges the surface of the photoconductor 1T, and an exposure apparatus (static) that exposes the surface of the charged photoconductor 1T with a laser beam to form a static charge image. Example of charge image forming means) 3T, developing device (example of developing means) 4T that supplies pressure-responsive particles to the electrostatic charge image to develop the electrostatic charge image, and the developed pressure-responsive particle imparting portion is attached to the intermediate transfer belt 20. A primary transfer roll (an example of a primary transfer means) 5T to be transferred onto the photoconductor and a photoconductor cleaning device (an example of a cleaning means) 6T for removing pressure-responsive particles remaining on the surface of the photoconductor 1T after the primary transfer are arranged in order. ing. The primary transfer roll 5T is arranged inside the intermediate transfer belt 20 and is provided at a position facing the photoconductor 1T.
以下、ユニット10Tの動作を例示しながら、記録媒体P上に本実施形態に係る圧力応答性粒子の配置と有色画像形成とを行う動作について説明する。
まず、帯電ロール2Tによって感光体1Tの表面が帯電される。帯電した感光体1Tの表面に、図示しない制御部から送られてくる画像データに従って、露光装置3Tがレーザ光線を照射する。それにより、本実施形態に係る圧力応答性粒子の配置パターンの静電荷像が感光体1Tの表面に形成される。
Hereinafter, the operation of arranging the pressure-responsive particles and forming a colored image according to the present embodiment on the recording medium P will be described while exemplifying the operation of the unit 10T.
First, the surface of the photoconductor 1T is charged by the charging roll 2T. The exposure device 3T irradiates the surface of the charged photoconductor 1T with a laser beam according to image data sent from a control unit (not shown). As a result, an electrostatic charge image of the arrangement pattern of the pressure-responsive particles according to the present embodiment is formed on the surface of the photoconductor 1T.
感光体1T上に形成された静電荷像は、感光体1Tの走行に従って現像位置まで回転する。そして、現像位置で、感光体1T上の静電荷像が、現像装置4Tによって現像され圧力応答性粒子付与部になる。 The electrostatic charge image formed on the photoconductor 1T rotates to the developing position as the photoconductor 1T travels. Then, at the developing position, the electrostatic charge image on the photoconductor 1T is developed by the developing device 4T and becomes a pressure-responsive particle imparting portion.
現像装置4T内には、少なくとも本実施形態に係る圧力応答性粒子とキャリアとを含む現像剤が収容されている。本実施形態に係る圧力応答性粒子は、現像装置4Tの内部でキャリアとともに攪拌されることで摩擦帯電し、現像剤ロール上に保持されている。感光体1Tの表面が現像装置4Tを通過していくことにより、感光体1T表面の静電荷像に圧力応答性粒子が静電的に付着し、静電荷像が圧力応答性粒子によって現像される。圧力応答性粒子付与部が形成された感光体1Tは、引き続き走行し、感光体1T上の圧力応答性粒子付与部が一次転写位置へ搬送される。 The developing apparatus 4T contains at least a developing agent containing pressure-responsive particles and carriers according to the present embodiment. The pressure-responsive particles according to the present embodiment are triboelectrically charged by being stirred together with the carrier inside the developing apparatus 4T and are held on the developing agent roll. As the surface of the photoconductor 1T passes through the developing device 4T, the pressure-responsive particles are electrostatically attached to the electrostatic charge image on the surface of the photoconductor 1T, and the electrostatic charge image is developed by the pressure-responsive particles. .. The photoconductor 1T on which the pressure-responsive particle-imparting portion is formed continues to run, and the pressure-responsive particle-imparting portion on the photoconductor 1T is conveyed to the primary transfer position.
感光体1T上の圧力応答性粒子付与部が一次転写位置へ搬送されると、一次転写ロール5Tに一次転写バイアスが印加され、感光体1Tから一次転写ロール5Tに向う静電気力が圧力応答性粒子付与部に作用し、感光体1T上の圧力応答性粒子付与部が中間転写ベルト20上に転写される。感光体1T上に残留した圧力応答性粒子は感光体クリーニング装置6Tで除去されて回収される。感光体クリーニング装置6Tは、例えば、クリーニングブレード、クリーニングブラシ等であり、クリーニングブラシであることが好ましい。 When the pressure-responsive particle-imparting portion on the photoconductor 1T is conveyed to the primary transfer position, a primary transfer bias is applied to the primary transfer roll 5T, and the electrostatic force from the photoconductor 1T toward the primary transfer roll 5T is the pressure-responsive particles. It acts on the imparting portion, and the pressure-responsive particle imparting portion on the photoconductor 1T is transferred onto the intermediate transfer belt 20. The pressure-responsive particles remaining on the photoconductor 1T are removed by the photoconductor cleaning device 6T and recovered. The photoconductor cleaning device 6T is, for example, a cleaning blade, a cleaning brush, or the like, and is preferably a cleaning brush.
ユニット10Y、10M、10C及び10Kにおいても、ユニット10Tと同様の動作が、有色トナーを含む現像剤を用いて行われる。ユニット10Tにて圧力応答性粒子付与部が転写された中間転写ベルト20が、ユニット10Y、10M、10C、10Kを順次通過し、中間転写ベルト20上に各色のトナー画像が多重転写される。 In units 10Y, 10M, 10C and 10K, the same operation as in unit 10T is performed using a developing agent containing colored toner. The intermediate transfer belt 20 to which the pressure-responsive particle imparting portion is transferred by the unit 10T passes through the units 10Y, 10M, 10C, and 10K in sequence, and the toner images of each color are multiplex-transferred on the intermediate transfer belt 20.
ユニット10T、10Y、10M、10C及び10Kを通して圧力応答性粒子付与部及びトナー画像が多重転写された中間転写ベルト20は、中間転写ベルト20と、中間転写ベルトの内面に接する対向ロール24と、中間転写ベルト20の像保持面側に配置された二次転写ロール(二次転写手段の一例)26とから構成された二次転写部へと至る。一方、記録媒体Pが供給機構を介して二次転写ロール26と中間転写ベルト20とが接触した隙間に給紙され、二次転写バイアスが対向ロール24に印加される。このとき、中間転写ベルト20から記録媒体Pに向う静電気力が圧力応答性粒子付与部及びトナー画像に作用し、中間転写ベルト20上の圧力応答性粒子付与部及びトナー画像が記録媒体P上に転写される。 The intermediate transfer belt 20 in which the pressure-responsive particle imparting portion and the toner image are multiple-transferred through the units 10T, 10Y, 10M, 10C and 10K is intermediate between the intermediate transfer belt 20 and the opposing roll 24 in contact with the inner surface of the intermediate transfer belt. It leads to a secondary transfer unit composed of a secondary transfer roll (an example of the secondary transfer means) 26 arranged on the image holding surface side of the transfer belt 20. On the other hand, the recording medium P is fed to the gap where the secondary transfer roll 26 and the intermediate transfer belt 20 are in contact with each other via the supply mechanism, and the secondary transfer bias is applied to the opposing roll 24. At this time, the electrostatic force from the intermediate transfer belt 20 toward the recording medium P acts on the pressure-responsive particle-imparting portion and the toner image, and the pressure-responsive particle-imparting portion and the toner image on the intermediate transfer belt 20 act on the recording medium P. Transferred.
圧力応答性粒子付与部及びトナー画像が転写された記録媒体Pは熱定着装置(熱定着手段の一例)28へと搬送される。熱定着装置28は、ハロゲンヒータ等の加熱源を備え、記録媒体Pを加熱する。熱定着装置28によって加熱された際の記録媒体Pの表面温度は、150℃以上220℃以下が好ましく、155℃以上210℃以下がより好ましく、160℃以上200℃以下が更に好ましい。熱定着装置28を通過することにより、有色のトナー画像が記録媒体P上へ熱定着される。 The pressure-responsive particle-imparting portion and the recording medium P on which the toner image is transferred are conveyed to a heat fixing device (an example of heat fixing means) 28. The heat fixing device 28 includes a heating 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 ° C. or higher and 220 ° C. or lower, more preferably 155 ° C. or higher and 210 ° C. or lower, and further preferably 160 ° C. or higher and 200 ° C. or lower. By passing through the heat fixing device 28, the colored toner image is heat-fixed on the recording medium P.
熱定着装置28は、記録媒体Pから本実施形態に係る圧力応答性粒子が脱落することを抑制する観点、及び、有色画像の記録媒体Pへの定着性を向上させる観点から、加熱と共に加圧を行う装置であることが好ましく、例えば、内部に加熱源を備える一対の定着部材(ロール/ロール、ベルト/ロール)であってもよい。熱定着装置28が加圧を行う場合、熱定着装置28が記録媒体Pに印加する圧力は、加圧装置230が記録媒体P2に印加する圧力に比較して低圧でよく、具体的には、0.2MPa以上1MPa以下が好ましい。 The heat fixing device 28 pressurizes with heating from the viewpoint of suppressing the pressure-responsive particles according to the present embodiment from falling off from the recording medium P and improving the fixability of the colored image to the recording medium P. It is preferable that the device performs the above, and for example, it may be a pair of fixing members (roll / roll, belt / roll) having a heating source inside. When the heat fixing device 28 pressurizes, the pressure applied by the heat fixing device 28 to the recording medium P may be lower than the pressure applied by the pressurizing device 230 to the recording medium P2. It is preferably 0.2 MPa or more and 1 MPa or less.
記録媒体Pは、印刷手段300を通過することによって、有色画像及び本実施形態に係る圧力応答性粒子が付与された記録媒体P1になる。記録媒体P1は、圧着手段200に向けて搬送される。 By passing through the printing means 300, the recording medium P becomes the recording medium P1 to which the colored image and the pressure-responsive particles according to the present embodiment are attached. The recording medium P1 is conveyed toward the crimping means 200.
図3における圧着手段200の構成は、図2における圧着手段200と同じでよく、圧着手段200については構成及び動作の詳細な説明を省略する。 The configuration of the crimping means 200 in FIG. 3 may be the same as that of the crimping means 200 in FIG. 2, and detailed description of the configuration and operation of the crimping means 200 will be omitted.
本実施形態に係る印刷物の製造装置において、印刷手段300と圧着手段200とは、近接している形態でもよく、離隔している形態でもよい。印刷手段300と圧着手段200とが離隔している場合、印刷手段300と圧着手段200とは、例えば、記録媒体P1を搬送する搬送手段(例えばベルトコンベア)によって繋がれる。 In the printed matter manufacturing apparatus according to the present embodiment, the printing means 300 and the crimping means 200 may be in close proximity to each other or may be separated from each other. When the printing means 300 and the crimping means 200 are separated from each other, the printing means 300 and the crimping means 200 are connected by, for example, a conveying means (for example, a belt conveyor) that conveys the recording medium P1.
本実施形態に係る印刷物の製造装置は、記録媒体を予め定められた寸法に裁断する裁断手段を備えていてもよい。裁断手段は、例えば、印刷手段300と圧着手段200との間に配置され、記録媒体P1の一部であって本実施形態に係る圧力応答性粒子が配置されていない領域を切り落とす裁断手段;折り装置220と加圧装置230との間に配置され、記録媒体P2の一部であって本実施形態に係る圧力応答性粒子が配置されていない領域を切り落とす裁断手段;圧着手段200の下流に配置され、圧着印刷物P3の一部であって本実施形態に係る圧力応答性粒子によって接着されていない領域を切り落とす裁断手段;などである。 The printed matter manufacturing apparatus according to the present embodiment may include a cutting means for cutting the recording medium to a predetermined size. The cutting means is arranged, for example, between the printing means 300 and the crimping means 200, and cuts off a part of the recording medium P1 in which the pressure-responsive particles according to the present embodiment are not arranged; A cutting means arranged between the apparatus 220 and the pressurizing apparatus 230 to cut off a region which is a part of the recording medium P2 and where the pressure-responsive particles according to the present embodiment are not arranged; arranged downstream of the crimping means 200. A cutting means for cutting off a region which is a part of the crimped printed matter P3 and is not adhered by the pressure-responsive particles according to the present embodiment; and the like.
本実施形態に係る印刷物の製造装置は、枚葉式の装置に限定されない。本実施形態に係る印刷物の製造装置は、長尺の記録媒体に対して有色画像形成工程、配置工程及び圧着工程を行って長尺の圧着印刷物を形成した後、長尺の圧着印刷物を予め定められた寸法に裁断する様式の装置であってもよい。 The printed matter manufacturing apparatus according to the present embodiment is not limited to the sheet-fed type apparatus. The printed matter manufacturing apparatus according to the present embodiment performs a colored image forming step, an arrangement step, and a crimping step on a long recording medium to form a long crimped printed matter, and then determines a long crimped printed matter in advance. It may be a device in a style of cutting to the specified dimensions.
[プロセスカートリッジ]
電子写真方式による印刷物の製造装置に適用するプロセスカートリッジを説明する。
本実施形態に係るプロセスカートリッジは、本実施形態に係る静電荷像現像剤を収容し、静電荷像現像剤により、感光体の表面に形成された静電荷像を圧力応答性粒子付与部として現像する現像手段を備え、印刷物の製造装置に着脱されるプロセスカートリッジである。
[Process cartridge]
A process cartridge applied to a printed matter manufacturing apparatus by an electrophotographic method will be described.
The process cartridge according to the present embodiment contains the electrostatic charge image developer according to the present embodiment, and develops the electrostatic charge image formed on the surface of the photoconductor as a pressure-responsive particle imparting portion by the electrostatic charge image developer. It is a process cartridge that is provided with developing means for processing and is attached to and detached from a printed matter manufacturing apparatus.
本実施形態に係るプロセスカートリッジは、現像手段と、必要に応じて、感光体、帯電手段、静電荷像形成手段、転写手段などから選択される少なくとも一つと、を備える構成であってもよい。 The process cartridge according to the present embodiment may have a configuration including a developing means and, if necessary, at least one selected from a photoconductor, a charging means, an electrostatic charge image forming means, a transfer means, and the like.
プロセスカートリッジの実施形態例として、感光体と、感光体の周囲に備えられた帯電ロール(帯電手段の一例)、現像装置(現像手段の一例)及び感光体クリーニング装置(クリーニング手段の一例)とが筐体により一体化されたカートリッジが挙げられる。筐体は、露光のための開口部を有する。筐体は、取り付けレールを有し、取り付けレールを介してプロセスカートリッジが印刷物の製造装置に装着される。 Examples of embodiments of the process cartridge include a photoconductor, a charging roll (an example of charging means), a developing device (an example of a developing means), and a photoconductor cleaning device (an example of a cleaning means) provided around the photoconductor. Examples include cartridges integrated by a housing. The housing has an opening for exposure. The housing has mounting rails through which the process cartridges are mounted in the printed matter manufacturing apparatus.
以下、実施例により発明の実施形態を詳細に説明するが、発明の実施形態は、これら実施例に何ら限定されるものではない。以下の説明において、特に断りのない限り、「部」及び「%」は質量基準である。 Hereinafter, embodiments of the invention will be described in detail with reference to Examples, but the embodiments of the invention are not limited to these Examples. In the following description, unless otherwise specified, "parts" and "%" are based on mass.
<スチレン系樹脂粒子を含む分散液の調製>
[スチレン系樹脂粒子分散液(St1)の調製]
・スチレン :390部
・アクリル酸n−ブチル:100部
・アクリル酸 : 10部
・ドデカンチオール :7.5部
上記の材料を混合し溶解してモノマー溶液を調製した。
アニオン性界面活性剤(ダウ・ケミカル社製、Dowfax2A1)8部をイオン交換水205部に溶解し、前記モノマー溶液を加えて分散し乳化し、乳化液を得た。
アニオン性界面活性剤(ダウ・ケミカル社製、Dowfax2A1)2.2部をイオン交換水462部に溶解し、攪拌機、温度計、還流冷却管及び窒素ガス導入管を備えた重合用フラスコに仕込み、攪拌しながら73℃まで加熱し、保持した。
過硫酸アンモニウム3部をイオン交換水21部に溶解し、前記重合用フラスコに定量ポンプを介して15分間かけて滴下した後、前記乳化液を、定量ポンプを介して160分間かけて滴下した。
次いで、ゆっくりと攪拌を続けながら重合用フラスコを75℃に3時間保持した後、室温に戻した。
これにより、スチレン系樹脂粒子を含み、樹脂粒子の体積平均粒径(D50v)が174nm、GPC(UV検出)による重量平均分子量が49000、ガラス転移温度が54℃、固形分量が42%のスチレン系樹脂粒子分散液(St1)を得た。
<Preparation of dispersion containing styrene resin particles>
[Preparation of styrene-based resin particle dispersion (St1)]
-Styrene: 390 parts-n-Butyl acrylate: 100 parts-Acrylic acid: 10 parts-Dodecanethiol: 7.5 parts The above materials were mixed and dissolved to prepare a monomer solution.
Eight parts of an anionic surfactant (Dowfax2A1 manufactured by Dow Chemical Co., Ltd.) was dissolved in 205 parts of ion-exchanged water, and the monomer solution was added to disperse and emulsify to obtain an emulsion.
2.2 parts of an anionic surfactant (Dowfax2A1 manufactured by Dow Chemical Co., Ltd.) was dissolved in 462 parts of ion-exchanged water and charged into a polymerization flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction tube. It was heated to 73 ° C. with stirring and held.
3 parts of ammonium persulfate was dissolved in 21 parts of ion-exchanged water and added dropwise to the polymerization flask over 15 minutes via a metering pump, and then the emulsion was dropped over 160 minutes via a metering pump.
Then, the polymerization flask was kept at 75 ° C. for 3 hours while continuing to stir slowly, and then returned to room temperature.
As a result, styrene-based resin particles are contained, the volume average particle size (D50v) of the resin particles is 174 nm, the weight average molecular weight by GPC (UV detection) is 49000, the glass transition temperature is 54 ° C., and the solid content is 42%. A resin particle dispersion (St1) was obtained.
スチレン系樹脂粒子分散液(St1)を乾燥してスチレン系樹脂粒子を取り出し、示差走査熱量計(島津製作所製、DSC−60A)にて、温度−100℃から100℃の範囲の熱的挙動を分析したところ、ガラス転移温度が1つ観察された。表1にガラス転移温度を示す。 The styrene resin particle dispersion (St1) is dried to take out the styrene resin particles, and the thermal behavior in the temperature range of -100 ° C to 100 ° C is observed with a differential scanning calorimeter (DSC-60A, manufactured by Shimadzu Corporation). Upon analysis, one glass transition temperature was observed. Table 1 shows the glass transition temperature.
[スチレン系樹脂粒子分散液(St2)〜(St13)の調製]
スチレン系樹脂粒子分散液(St1)の調製と同様にして、但しモノマーを表1に記載の通りに変更して、スチレン系樹脂粒子分散液(St2)〜(St13)を調製した。
[Preparation of Styrene-based Resin Particle Dispersion Liquids (St2) to (St13)]
Styrene-based resin particle dispersions (St2) to (St13) were prepared in the same manner as in the preparation of the styrene-based resin particle dispersion (St1), except that the monomers were changed as shown in Table 1.
スチレン系樹脂粒子分散液(St1)等の組成及び物性を表1に示す。表1においてモノマーは下記の略号で記載する。
スチレン:St、アクリル酸n−ブチル:BA、アクリル酸2−エチルヘキシル:2EHA、アクリル酸エチル:EA、アクリル酸4−ヒドロキシブチル:4HBA、アクリル酸:AA、メタクリル酸:MAA、アクリル酸2−カルボキシエチル:CEA
Table 1 shows the composition and physical properties of the styrene-based resin particle dispersion (St1) and the like. In Table 1, the monomers are listed by the following abbreviations.
Styrene: St, n-butyl acrylate: BA, 2-ethylhexyl acrylate: 2EHA, ethyl acrylate: EA, 4-hydroxybutyl acrylate: 4HBA, acrylate: AA, methacrylic acid: MAA, 2-carboxylate acrylate Ethyl: CEA
<複合樹脂粒子を含む分散液の調製>
[複合樹脂粒子分散液(M1)の調製]
・スチレン系樹脂粒子分散液(St1):1190部(固形分500部)
・アクリル酸2−エチルヘキシル : 250部
・アクリル酸n−ブチル : 250部
・イオン交換水 : 982部
上記の材料を重合用フラスコに仕込み、25℃で1時間攪拌した後、70℃に加熱した。
過硫酸アンモニウム2.5部をイオン交換水75部に溶解し、前記重合用フラスコに定量ポンプを介して60分間かけて滴下した。
次いで、ゆっくりと攪拌を続けながら重合用フラスコを70℃に3時間保持した後、室温に戻した。
これにより、複合樹脂粒子を含み、樹脂粒子の体積平均粒径(D50v)が219nm、GPC(UV検出)による重量平均分子量が219000、固形分量が32%の複合樹脂粒子分散液(M1)を得た。
<Preparation of dispersion containing composite resin particles>
[Preparation of composite resin particle dispersion (M1)]
-Styrene-based resin particle dispersion (St1): 1190 parts (solid content 500 parts)
-2-Ethylhexyl acrylate: 250 parts-n-Butyl acrylate: 250 parts-Ion-exchanged water: 982 parts The above materials were placed in a polymerization flask, stirred at 25 ° C. for 1 hour, and then heated to 70 ° C.
2.5 parts of ammonium persulfate was dissolved in 75 parts of ion-exchanged water and added dropwise to the polymerization flask over 60 minutes via a metering pump.
Then, the polymerization flask was kept at 70 ° C. for 3 hours while continuing to stir slowly, and then returned to room temperature.
As a result, a composite resin particle dispersion (M1) containing composite resin particles, having a volume average particle size (D50v) of 219 nm, a weight average molecular weight of 219000 by GPC (UV detection), and a solid content of 32% is obtained. It was.
複合樹脂粒子分散液(M1)を乾燥して複合樹脂粒子を取り出し、示差走査熱量計(島津製作所製、DSC−60A)にて、温度−150℃から100℃の範囲の熱的挙動を分析したところ、ガラス転移温度が2つ観察された。表2にガラス転移温度を示す。 The composite resin particle dispersion (M1) was dried to take out the composite resin particles, and the thermal behavior in the temperature range of −150 ° C. to 100 ° C. was analyzed with a differential scanning calorimeter (DSC-60A, manufactured by Shimadzu Corporation). However, two glass transition temperatures were observed. Table 2 shows the glass transition temperature.
[複合樹脂粒子分散液(M2)〜(M21)及び(cM1)〜(cM3)の調製]
複合樹脂粒子分散液(M1)の調製と同様にして、但しスチレン系樹脂粒子分散液(St1)を表2に記載の通りに変更して、又は、(メタ)アクリル酸エステル系樹脂の重合成分を表2に記載の通りに変更して、複合樹脂粒子分散液(M2)〜(M21)及び(cM1)〜(cM3)を調製した。
[Preparation of composite resin particle dispersions (M2) to (M21) and (cM1) to (cM3)]
Similar to the preparation of the composite resin particle dispersion (M1), however, the styrene resin particle dispersion (St1) is changed as shown in Table 2, or the polymerized component of the (meth) acrylic acid ester resin. Was changed as shown in Table 2 to prepare composite resin particle dispersions (M2) to (M21) and (cM1) to (cM3).
[複合樹脂粒子分散液(M22)〜(M27)の調製]
複合樹脂粒子分散液(M1)の調製と同様にして、但しアクリル酸2−エチルヘキシル及びアクリル酸n−ブチルの使用量を調節して、複合樹脂粒子分散液(M22)〜(M27)を調製した。
[Preparation of composite resin particle dispersion liquids (M22) to (M27)]
The composite resin particle dispersions (M22) to (M27) were prepared in the same manner as in the preparation of the composite resin particle dispersion (M1), except that the amounts of 2-ethylhexyl acrylate and n-butyl acrylate were adjusted. ..
複合樹脂粒子分散液(M1)等の組成及び物性を表2に示す。表2においてモノマーは下記の略号で記載する。
スチレン:St、アクリル酸n−ブチル:BA、アクリル酸2−エチルヘキシル:2EHA、アクリル酸エチル:EA、アクリル酸4−ヒドロキシブチル:4HBA、アクリル酸:AA、メタクリル酸:MAA、アクリル酸2−カルボキシエチル:CEA、アクリル酸ヘキシル:HA、アクリル酸プロピル:PA
Table 2 shows the composition and physical properties of the composite resin particle dispersion (M1) and the like. In Table 2, the monomers are described by the following abbreviations.
Styrene: St, n-butyl acrylate: BA, 2-ethylhexyl acrylate: 2EHA, ethyl acrylate: EA, 4-hydroxybutyl acrylate: 4HBA, acrylate: AA, methacrylic acid: MAA, 2-carboxylate acrylate Ethyl: CEA, hexyl acrylate: HA, propyl acrylate: PA
[複合樹脂粒子分散液(M28)〜(M30)の調製]
複合樹脂粒子分散液(M1)の調製と同様にして、但し過硫酸アンモニウムの量を表3に記載の通りに変更して、複合樹脂粒子の重量平均分子量が異なる複合樹脂粒子分散液(M28)〜(M30)を調製した。
[Preparation of composite resin particle dispersion liquids (M28) to (M30)]
Similar to the preparation of the composite resin particle dispersion (M1), however, the amount of ammonium persulfate is changed as shown in Table 3, and the composite resin particle dispersions (M28) to which the weight average molecular weights of the composite resin particles are different are different. (M30) was prepared.
複合樹脂粒子分散液(M28)等の組成及び物性を表4に示す。表4においてモノマーは下記の略号で記載する。
スチレン:St、アクリル酸n−ブチル:BA、アクリル酸:AA、アクリル酸2−エチルヘキシル:2EHA
Table 4 shows the composition and physical properties of the composite resin particle dispersion (M28) and the like. In Table 4, the monomers are described by the following abbreviations.
Styrene: St, n-butyl acrylate: BA, acrylic acid: AA, 2-ethylhexyl acrylate: 2EHA
<圧力応答性粒子の調製>
[圧力応答性粒子(1)の調製]
・複合樹脂粒子分散液(M1) :504部
・イオン交換水 :710部
・アニオン性界面活性剤(ダウ・ケミカル社製、Dowfax2A1): 1部
<Preparation of pressure-responsive particles>
[Preparation of pressure-responsive particles (1)]
-Composite resin particle dispersion (M1): 504 parts-Ion-exchanged water: 710 parts-Anionic surfactant (Dowfax2A1 manufactured by Dow Chemical Co., Ltd.): 1 part
温度計及びpH計を備えた反応容器に上記の材料を入れ、温度25℃下に1.0%硝酸水溶液を添加してpHを3.0に調整した後、ホモジナイザー(IKA社製、ウルトラタラックスT50)にて回転数5000rpmで分散しながら、2.0%硫酸アルミニウム水溶液を23部添加した。次いで、反応容器に攪拌機及びマントルヒーターを設置し、温度40℃までは0.2℃/分の昇温速度、40℃を超えてからは0.05℃/分の昇温速度で昇温し、10分ごとにマルチサイザーII(アパーチャー径50μm、ベックマン−コールター社製)にて粒径を測定した。体積平均粒径が5.0μmになったところで温度を保持し、スチレン系樹脂粒子分散液(St1)170部を5分間かけて投入した。投入終了後、50℃に30分間保持した後、1.0%水酸化ナトリウム水溶液を加え、スラリーのpHを6.0に調整した。次いで、5℃ごとにpHを6.0に調整しながら、昇温速度1℃/分で90℃まで昇温し、90℃で保持した。光学顕微鏡と電界放出形走査電子顕微鏡(FE−SEM)にて粒子形状及び表面性を観察したところ、10時間目で粒子の合一が確認されたので、冷却水で容器を30℃まで5分間かけて冷却した。 Put the above materials in a reaction vessel equipped with a thermometer and a pH meter, add a 1.0% aqueous nitric acid solution at a temperature of 25 ° C. to adjust the pH to 3.0, and then homogenizer (Ultrata manufactured by IKA). Twenty-three parts of a 2.0% aqueous aluminum sulfate solution was added while dispersing at a rotation speed of 5000 rpm with Lux T50). Next, a stirrer and a mantle heater are installed in the reaction vessel, and the temperature is raised at a rate of 0.2 ° C./min up to a temperature of 40 ° C. and at a rate of 0.05 ° C./min after exceeding 40 ° C. The particle size was measured every 10 minutes with a multi-sizer II (aperture diameter 50 μm, manufactured by Beckman-Coulter). The temperature was maintained when the volume average particle size reached 5.0 μm, and 170 parts of the styrene resin particle dispersion (St1) was added over 5 minutes. After completion of charging, the mixture was kept at 50 ° C. for 30 minutes, and then a 1.0% aqueous sodium hydroxide solution was added to adjust the pH of the slurry to 6.0. Then, while adjusting the pH to 6.0 every 5 ° C., the temperature was raised to 90 ° C. at a heating rate of 1 ° C./min and maintained at 90 ° C. When the particle shape and surface properties were observed with an optical microscope and a field emission scanning electron microscope (FE-SEM), the coalescence of the particles was confirmed at 10 hours, so the container was cooled to 30 ° C. for 5 minutes. It was cooled over.
冷却後のスラリーを、目開き15μmのナイロンメッシュに通過させ粗大粒子を除去し、メッシュを通過したスラリーをアスピレータで減圧濾過した。濾紙上に残った固形分を手でできるだけ細かく砕いて、固形分量の10倍のイオン交換水(温度30℃)に投入し、30分間攪拌した。次いで、アスピレータで減圧濾過し、濾紙上に残った固形分を手でできるだけ細かく砕いて、固形分量の10倍のイオン交換水(温度30℃)に投入し、30分間攪拌した後、再度アスピレータで減圧濾過し、濾液の電気伝導度を測定した。濾液の電気伝導度が10μS/cm以下になるまでこの操作を繰り返し、固形分を洗浄した。 The cooled slurry was passed through a nylon mesh having an opening of 15 μm to remove coarse particles, and the slurry passed through the mesh was vacuum-filtered with an aspirator. The solid content remaining on the filter paper was crushed as finely as possible by hand, put into ion-exchanged water (temperature 30 ° C.) 10 times the solid content, and stirred for 30 minutes. Next, it is vacuum-filtered with an ejector, the solid content remaining on the filter paper is crushed as finely as possible by hand, put into ion-exchanged water (temperature 30 ° C.) 10 times the solid content, stirred for 30 minutes, and then again with an ejector. The filtrate was filtered under reduced pressure, and the electrical conductivity of the filtrate was measured. This operation was repeated until the electrical conductivity of the filtrate became 10 μS / cm or less, and the solid content was washed.
洗浄された固形分を湿式乾式整粒機(コーミル)で細かく砕き、25℃のオーブン中で36時間真空乾燥して、圧力応答性母粒子(1)を得た。圧力応答性母粒子(1)は、体積平均粒径が8.0μmであった。 The washed solid content was finely crushed with a wet dry granulator (comil) and vacuum dried in an oven at 25 ° C. for 36 hours to obtain pressure-responsive mother particles (1). The pressure-responsive mother particle (1) had a volume average particle diameter of 8.0 μm.
圧力応答性母粒子(1)100部と、疎水性シリカ(日本アエロジル株式会社製、RY50)1.5部とを混合し、サンプルミルを用いて回転速度13000rpmで30秒間混合した。目開き45μmの振動篩で篩分して、圧力応答性粒子(1)を得た。 100 parts of the pressure-responsive mother particle (1) and 1.5 parts of hydrophobic silica (RY50 manufactured by Nippon Aerosil Co., Ltd.) were mixed and mixed for 30 seconds at a rotation speed of 13000 rpm using a sample mill. Pressure-responsive particles (1) were obtained by sieving with a vibrating sieve having a mesh size of 45 μm.
圧力応答性粒子(1)を試料にして、示差走査熱量計(島津製作所製、DSC−60A)にて、温度−150℃から100℃の範囲の熱的挙動を分析したところ、ガラス転移温度が2つ観察された。表5にガラス転移温度を示す。 Using the pressure-responsive particles (1) as a sample, the thermal behavior in the temperature range of -150 ° C to 100 ° C was analyzed with a differential scanning calorimeter (DSC-60A, manufactured by Shimadzu Corporation). Two were observed. Table 5 shows the glass transition temperature.
圧力応答性粒子(1)の温度T1及び温度T2を先述の測定方法によって求めたところ、圧力応答性粒子(1)は式1「10℃≦T1−T2」を満足していた。 When the temperature T1 and the temperature T2 of the pressure-responsive particles (1) were determined by the above-mentioned measuring method, the pressure-responsive particles (1) satisfied the formula 1 “10 ° C. ≦ T1-T2”.
圧力応答性粒子(1)の断面を走査型電子顕微鏡(SEM)にて観察したところ、海島構造が観察された。圧力応答性粒子(1)は、島相が存在するコア部と、島相が存在しないシェル層とを有していた。海相はスチレン系樹脂を含み、島相は(メタ)アクリル酸エステル系樹脂を含んでいた。既述の測定方法にて島相の平均径を求めた。表5に島相の平均径を示す。 When the cross section of the pressure-responsive particles (1) was observed with a scanning electron microscope (SEM), a sea-island structure was observed. The pressure-responsive particles (1) had a core portion in which the island phase was present and a shell layer in which the island phase was not present. The sea phase contained a styrene resin, and the island phase contained a (meth) acrylic acid ester resin. The average diameter of the island phase was determined by the measurement method described above. Table 5 shows the average diameter of the island fauna.
[圧力応答性粒子(2)〜(27)の調製]
圧力応答性粒子(1)の調製と同様にして、但し複合樹脂粒子分散液及びスチレン系樹脂粒子分散液を表5に記載の通りに変更して、圧力応答性粒子(2)〜(27)を調製した。
[Preparation of pressure-responsive particles (2) to (27)]
Similar to the preparation of the pressure responsive particles (1), however, the composite resin particle dispersion and the styrene resin particle dispersion are changed as shown in Table 5, and the pressure responsive particles (2) to (27) are changed. Was prepared.
圧力応答性粒子(2)〜(27)の温度T1及び温度T2を先述の測定方法によって求めたところ、圧力応答性粒子(2)〜(27)はすべて式1「10℃≦T1−T2」を満足していた。 When the temperatures T1 and T2 of the pressure-responsive particles (2) to (27) were determined by the above-mentioned measuring method, all the pressure-responsive particles (2) to (27) were given by Equation 1 "10 ° C.≤T1-T2". Was satisfied.
[圧力応答性粒子(28)〜(30)の調製]
圧力応答性粒子(1)の調製と同様にして、但し複合樹脂粒子分散液を表6に記載の通りに変更して、圧力応答性粒子(28)〜(30)を調製した。
[Preparation of pressure-responsive particles (28) to (30)]
The pressure-responsive particles (28) to (30) were prepared in the same manner as in the preparation of the pressure-responsive particles (1), except that the composite resin particle dispersion was changed as shown in Table 6.
圧力応答性粒子(28)〜(30)の温度T1及び温度T2を先述の測定方法によって求めたところ、圧力応答性粒子(28)〜(30)はすべて式1「10℃≦T1−T2」を満足していた。 When the temperatures T1 and T2 of the pressure-responsive particles (28) to (30) were determined by the above-mentioned measuring method, all the pressure-responsive particles (28) to (30) were given by Equation 1 "10 ° C.≤T1-T2". Was satisfied.
[圧力応答性粒子(31)の調製]
下記の粉砕製法で圧力応答性母粒子を調製した。
複合樹脂粒子分散液(M1)を乾燥して複合樹脂粒子(M31)を得た。複合樹脂粒子(M31)を設定温度100℃のエクストルーダーで熱混錬し、冷却後、粉砕及び分級し、体積平均粒径8.0μmの圧力応答性母粒子(31)を得た。
[Preparation of pressure-responsive particles (31)]
Pressure-responsive mother particles were prepared by the following pulverization method.
The composite resin particle dispersion liquid (M1) was dried to obtain composite resin particles (M31). The composite resin particles (M31) were heat-kneaded with an extruder at a set temperature of 100 ° C., cooled, pulverized and classified to obtain pressure-responsive mother particles (31) having a volume average particle size of 8.0 μm.
圧力応答性母粒子(31)100部と、疎水性シリカ(日本アエロジル株式会社製、RY50)1.5部とを混合し、サンプルミルを用いて回転速度13000rpmで30秒間混合した。目開き45μmの振動篩で篩分して、圧力応答性粒子(31)を得た。 100 parts of the pressure-responsive mother particle (31) and 1.5 parts of hydrophobic silica (RY50 manufactured by Nippon Aerosil Co., Ltd.) were mixed and mixed for 30 seconds at a rotation speed of 13000 rpm using a sample mill. The particles were sieved with a vibrating sieve having a mesh size of 45 μm to obtain pressure-responsive particles (31).
圧力応答性粒子(31)を試料にして、示差走査熱量計(島津製作所製、DSC−60A)にて、温度−150℃から100℃の範囲の熱的挙動を分析したところ、ガラス転移温度が2つ観察された。表6にガラス転移温度を示す。 Using the pressure-responsive particles (31) as a sample, the thermal behavior in the temperature range of -150 ° C to 100 ° C was analyzed with a differential scanning calorimeter (DSC-60A, manufactured by Shimadzu Corporation). Two were observed. Table 6 shows the glass transition temperature.
圧力応答性粒子(31)の温度T1及び温度T2を先述の測定方法によって求めたところ、圧力応答性粒子(31)は式1「10℃≦T1−T2」を満足していた。 When the temperature T1 and the temperature T2 of the pressure-responsive particles (31) were determined by the above-mentioned measuring method, the pressure-responsive particles (31) satisfied the formula 1 “10 ° C. ≦ T1-T2”.
[比較用の圧力応答性粒子(c1)〜(c3)の調製]
圧力応答性粒子(1)の調製と同様にして、但し複合樹脂粒子分散液及びスチレン系樹脂粒子分散液を表5に記載の通りに変更して、圧力応答性粒子(c1)〜(c3)を調製した。
[Preparation of pressure-responsive particles (c1) to (c3) for comparison]
Similar to the preparation of the pressure responsive particles (1), however, the composite resin particle dispersion and the styrene resin particle dispersion are changed as shown in Table 5, and the pressure responsive particles (c1) to (c3) are changed. Was prepared.
[圧力応答性相転移の評価]
圧力応答性粒子が圧力によって相転移しやすいことを示す指標である温度差(T1−T3)を求めた。各圧力応答性粒子を試料にして、フローテスター(島津製作所製、CFT−500)にて、温度T1及び温度T3を測定し、温度差(T1−T3)を算出した。表5及び表6に温度差(T1−T3)を示す。
[Evaluation of pressure-responsive phase transition]
The temperature difference (T1-T3), which is an index indicating that the pressure-responsive particles are likely to undergo a phase transition due to pressure, was determined. Using each pressure-responsive particle as a sample, the temperature T1 and the temperature T3 were measured with a flow tester (CFT-500 manufactured by Shimadzu Corporation), and the temperature difference (T1-T3) was calculated. Tables 5 and 6 show the temperature difference (T1-T3).
[接着性の評価]
記録媒体として富士ゼロックス社製のハガキ用紙V424を用意した。富士ゼロックス(株)製の画像形成装置DocuCentre C7550I並びに富士ゼロックス社製の市販品のイエロートナー、マゼンタトナー、シアントナー及びブラックトナーを用いて、ハガキ用紙の片面に、黒色文字とフルカラー写真画像とが混在した面積密度30%の画像を形成し、画像を定着させた。
ハガキ用紙の画像形成面の全体に、圧力応答性粒子を付与量3g/m2となるように散布し、ベルトロール型固定機を通過させて、ハガキ用紙の画像形成面に圧力応答性粒子を固定させ、圧力応答性粒子の層を形成した。
画像形成面に圧力応答性粒子の層を有するハガキ用紙を、トッパン・フォームズ(株)製のシーラーPRESSLE multiIIを用いて、画像形成面が内側になるように二つ折りにし、二つ折りにしたハガキ用紙に圧力を印加し、内側の画像形成面どうしを圧力90MPaで接着した。
上記の装置及び条件で、画像形成面が内側になるように二つ折りにされ、且つ画像形成面どうしが接着されたハガキを連続して10通作製した。
10通目のハガキを長辺方向に幅15mmで裁断し長方形の試験片を作製して、90度剥離試験を行った。90度剥離試験の剥離速度は20mm/分とし、測定開始後10mmから50mmまでの荷重(N)を0.4mm間隔で採取し、その平均を算出し、さらに試験片3枚の荷重(N)を平均した。剥離に要する荷重(N)を下記のとおり分類した。表5及び表6に結果を示す。
[Evaluation of adhesiveness]
A postcard paper V424 manufactured by Fuji Xerox Co., Ltd. was prepared as a recording medium. Using the image forming device DocuCenter C7550I manufactured by Fuji Xerox Co., Ltd. and commercially available yellow toner, magenta toner, cyan toner and black toner manufactured by Fuji Xerox Co., Ltd., black characters and full-color photographic images can be printed on one side of the postcard paper. An image having a mixed area density of 30% was formed, and the image was fixed.
Pressure-responsive particles are sprayed on the entire image-forming surface of the postcard paper so that the applied amount is 3 g / m 2, and the pressure-responsive particles are passed through a belt roll type fixing machine to spread the pressure-responsive particles on the image-forming surface of the postcard paper. It was immobilized to form a layer of pressure responsive particles.
Postcard paper having a layer of pressure-responsive particles on the image-forming surface is folded in half using a sealer PRESSLE multiII manufactured by Toppan Foams Co., Ltd. so that the image-forming surface is on the inside, and then folded in half. A pressure was applied to the inner image-forming surfaces to bond them at a pressure of 90 MPa.
Under the above equipment and conditions, 10 postcards were continuously produced, which were folded in half so that the image forming surfaces were on the inside and the image forming surfaces were adhered to each other.
The tenth postcard was cut in the long side direction with a width of 15 mm to prepare a rectangular test piece, and a 90-degree peeling test was performed. The peeling speed of the 90-degree peeling test was set to 20 mm / min, and after the start of measurement, loads (N) from 10 mm to 50 mm were collected at 0.4 mm intervals, the average was calculated, and the load (N) of three test pieces was further calculated. Was averaged. The load (N) required for peeling was classified as follows. The results are shown in Tables 5 and 6.
A:0.8N以上
B:0.6N以上、0.8N未満
C:0.4N以上、0.6N未満
D:0.2N以上、0.4N未満
E:0.2N未満
A: 0.8N or more B: 0.6N or more 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
<複合樹脂粒子を含む分散液の調製>
[複合樹脂粒子分散液(M50)の調製]
・スチレン系樹脂粒子分散液(St1):1190部(固形分500部)
・アクリル酸2−エチルヘキシル : 200部
・アクリル酸n−ブチル : 200部
・イオン交換水 :1360部
上記の材料を重合用フラスコに仕込み、25℃で1時間攪拌した後、70℃に加熱した。
過硫酸アンモニウム2.5部をイオン交換水75部に溶解し、前記重合用フラスコに定量ポンプを介して60分間かけて滴下した。
次いで、ゆっくりと攪拌を続けながら重合用フラスコを70℃に2時間保持した後、スチレン85部とアクリル酸n−ブチル15部の混合物を60分間かけて滴下した。滴下後、75℃で3時間保持した後、室温に戻した。
これにより、複合樹脂粒子を含み、樹脂粒子の体積平均粒径(D50v)が223nm、GPC(UV検出)による重量平均分子量が220000、固形分量が32%の複合樹脂粒子分散液(M50)を得た。
<Preparation of dispersion containing composite resin particles>
[Preparation of composite resin particle dispersion (M50)]
-Styrene-based resin particle dispersion (St1): 1190 parts (solid content 500 parts)
-2-Ethylhexyl acrylate: 200 parts-n-Butyl acrylate: 200 parts-Ion-exchanged water: 1360 parts The above materials were placed in a polymerization flask, stirred at 25 ° C. for 1 hour, and then heated to 70 ° C.
2.5 parts of ammonium persulfate was dissolved in 75 parts of ion-exchanged water and added dropwise to the polymerization flask over 60 minutes via a metering pump.
Then, the polymerization flask was held at 70 ° C. for 2 hours with slow stirring, and then a mixture of 85 parts of styrene and 15 parts of n-butyl acrylate was added dropwise over 60 minutes. After the dropping, the mixture was kept at 75 ° C. for 3 hours and then returned to room temperature.
As a result, a composite resin particle dispersion (M50) containing composite resin particles, having a volume average particle size (D50v) of 223 nm, a weight average molecular weight of 220,000 by GPC (UV detection), and a solid content of 32% is obtained. It was.
複合樹脂粒子分散液(M50)を乾燥して複合樹脂粒子を取り出し、示差走査熱量計(島津製作所製、DSC−60A)にて、温度−150℃から100℃の範囲の熱的挙動を分析したところ、ガラス転移温度が2つ観察された。表7にガラス転移温度を示す。 The composite resin particle dispersion (M50) was dried to take out the composite resin particles, and the thermal behavior in the temperature range of −150 ° C. to 100 ° C. was analyzed with a differential scanning calorimeter (DSC-60A, manufactured by Shimadzu Corporation). However, two glass transition temperatures were observed. Table 7 shows the glass transition temperature.
[複合樹脂粒子分散液(M51)〜(M55)の調製]
複合樹脂粒子分散液(M50)の調製と同様にして、但し材料を表7に記載の仕様に変更して、複合樹脂粒子分散液(M51)〜(M55)を調製した。
[Preparation of composite resin particle dispersion liquids (M51) to (M55)]
The composite resin particle dispersions (M51) to (M55) were prepared in the same manner as in the preparation of the composite resin particle dispersions (M50), except that the materials were changed to the specifications shown in Table 7.
複合樹脂粒子分散液(M50)等の組成及び物性を表7に示す。表7においてモノマーは下記の略号で記載する。
スチレン:St、アクリル酸n−ブチル:BA、アクリル酸:AA、アクリル酸2−エチルヘキシル:2EHA
Table 7 shows the composition and physical properties of the composite resin particle dispersion (M50) and the like. In Table 7, the monomers are described by the following abbreviations.
Styrene: St, n-butyl acrylate: BA, acrylic acid: AA, 2-ethylhexyl acrylate: 2EHA
<圧力応答性粒子の調製>
[圧力応答性粒子(50)〜(55)の調製]
圧力応答性粒子(1)の調製と同様にして、但し材料を表8に記載の仕様に変更して、圧力応答性粒子(50)〜(55)を調製した。
<Preparation of pressure-responsive particles>
[Preparation of pressure-responsive particles (50) to (55)]
Pressure-responsive particles (50)-(55) were prepared in the same manner as for the preparation of the pressure-responsive particles (1), except that the material was changed to the specifications shown in Table 8.
圧力応答性粒子(50)〜(55)を試料にして、示差走査熱量計(島津製作所製、DSC−60A)にて、温度−150℃から100℃の範囲の熱的挙動を分析したところ、ガラス転移温度が2つ観察された。表8にガラス転移温度を示す。 Using pressure-responsive particles (50) to (55) as samples, the thermal behavior in the temperature range of -150 ° C to 100 ° C was analyzed with a differential scanning calorimeter (DSC-60A, manufactured by Shimadzu Corporation). Two glass transition temperatures were observed. Table 8 shows the glass transition temperature.
圧力応答性粒子(50)〜(55)の温度T1及び温度T2を先述の測定方法によって求めたところ、圧力応答性粒子(50)〜(55)はすべて式1「10℃≦T1−T2」を満足していた。 When the temperatures T1 and T2 of the pressure-responsive particles (50) to (55) were determined by the above-mentioned measuring method, all the pressure-responsive particles (50) to (55) were given by Equation 1 "10 ° C.≤T1-T2". Was satisfied.
圧力応答性粒子(50)〜(55)の断面を走査型電子顕微鏡(SEM)にて観察したところ、海島構造が観察された。圧力応答性粒子(50)〜(55)は、島相が存在するコア部と、島相が存在しないシェル層とを有していた。海相はスチレン系樹脂を含み、島相は(メタ)アクリル酸エステル系樹脂を含んでいた。既述の測定方法にて島相の平均径を求めた。表8に島相の平均径を示す。 When the cross sections of the pressure-responsive particles (50) to (55) were observed with a scanning electron microscope (SEM), a sea-island structure was observed. The pressure-responsive particles (50) to (55) had a core portion in which the island phase was present and a shell layer in which the island phase was not present. The sea phase contained a styrene resin, and the island phase contained a (meth) acrylic acid ester resin. The average diameter of the island phase was determined by the measurement method described above. Table 8 shows the average diameter of the island fauna.
[圧力応答性相転移の評価]
各圧力応答性粒子を試料にして、フローテスター(島津製作所製、CFT−500)にて、温度T1及び温度T3を測定し、温度差(T1−T3)を算出した。表8に温度差(T1−T3)を示す。
[Evaluation of pressure-responsive phase transition]
Using each pressure-responsive particle as a sample, the temperature T1 and the temperature T3 were measured with a flow tester (CFT-500 manufactured by Shimadzu Corporation), and the temperature difference (T1-T3) was calculated. Table 8 shows the temperature difference (T1-T3).
[接着性の評価]
圧力応答性粒子(1)等と同様に、先述の[接着性の評価]の評価方法により接着性を評価した。表8に結果を示す。
[Evaluation of adhesiveness]
Similar to the pressure-responsive particles (1) and the like, the adhesiveness was evaluated by the evaluation method of [evaluation of adhesiveness] described above. The results are shown in Table 8.
<電子写真方式による印刷物の製造>
圧力応答性粒子(1)〜(31)、(c1)〜(c3)及び(50)〜(55)のいずれか10部と下記の樹脂被覆キャリア(1)100部とをV型ブレンダーに入れ20分間攪拌し、次いで、目開き212μmの振動篩で篩分して現像剤(1)〜(31)、(c1)〜(c3)及び(50)〜(55)をそれぞれ得た。
<Manufacturing printed matter by electrophotographic method>
10 parts of any 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) are placed in a V-type blender. The mixture was stirred for 20 minutes and then sieved with a vibrating sieve having a mesh size of 212 μm to obtain developers (1) to (31), (c1) to (c3) and (50) to (55), respectively.
−樹脂被覆キャリア(1)−
・Mn−Mg−Sr系フェライト粒子(平均粒径40μm):100部
・トルエン : 14部
・ポリメタクリル酸メチル : 2部
・カーボンブラック(VXC72:キャボット製) :0.12部
フェライト粒子を除く上記材料とガラスビーズ(直径1mm、トルエンと同量)とを混合し、関西ペイント社製サンドミルを用いて回転速度1200rpmで30分間攪拌し、分散液を得た。この分散液とフェライト粒子とを真空脱気型ニーダーに入れ、攪拌しながら減圧し乾燥させることにより、樹脂被覆キャリア(1)を得た。
-Resin coated carrier (1)-
-Mn-Mg-Sr-based ferrite particles (average particle size 40 μm): 100 parts-Toluene: 14 parts-Polymethyl methacrylate: 2 parts-Carbon black (VXC72: manufactured by Cabot): 0.12 parts Excluding ferrite particles The material and glass beads (diameter 1 mm, the same amount as toluene) were mixed and stirred at a rotation speed of 1200 rpm for 30 minutes using a sand mill manufactured by Kansai Paint Co., Ltd. to obtain a dispersion liquid. The dispersion liquid and the ferrite particles were placed in a vacuum degassing type kneader, and the pressure was reduced while stirring to dry the mixture to obtain a resin-coated carrier (1).
印刷物の製造装置として、図3に示す形態の装置を用意した。すなわち、記録媒体への本実施形態に係る圧力応答性粒子の配置と有色画像形成とを一括で行う5連タンデム方式且つ中間転写方式の印刷手段と、折り装置及び加圧装置を有する圧着手段とを備える印刷物の製造装置を用意した。
印刷手段が有する5つの現像器にそれぞれ、本実施形態に係る現像剤(又は比較用の現像剤)、イエローの現像剤、マゼンタの現像剤、シアンの現像剤及びブラックの現像剤を入れた。イエロー等の各色の現像剤は、富士ゼロックス社製の市販品を使用した。
記録媒体として富士ゼロックス社製のハガキ用紙V424を用意した。
ハガキ用紙に形成する画像は、黒色文字とフルカラー写真画像とが混在した面積密度30%の画像とし、ハガキ用紙の片面に形成した。
本実施形態に係る圧力応答性粒子(又は比較用の圧力応答性粒子)の付与量は、ハガキ用紙の画像形成面の画像形成領域に、3g/m2とした。
折り装置は、画像形成面が内側になるようにハガキ用紙を二つ折りにする装置とした。
加圧装置は、圧力90MPaとした。
上記の装置及び条件で、画像形成面が内側になるように二つ折りにされ、且つ画像形成面どうしが接着されたハガキを連続して10通作製した。
10通目のハガキを長辺方向に幅15mmで裁断し長方形の試験片を作製して、90度剥離試験を行った。90度剥離試験の剥離速度は20mm/分とし、測定開始後10mmから50mmまでの荷重(N)を0.4mm間隔で採取し、その平均を算出し、さらに試験片3枚の荷重(N)を平均した。剥離に要する荷重(N)を下記のとおり分類した。表9、表10及び表11に結果を示す。
As a printed matter manufacturing apparatus, an apparatus having the form shown in FIG. 3 was prepared. That is, a five-series tandem and intermediate transfer printing means for collectively arranging pressure-responsive particles and forming a colored image according to the present embodiment on a recording medium, and a crimping means having a folding device and a pressurizing device. A printed matter manufacturing apparatus equipped with the above was prepared.
A developer (or a developer for comparison), a yellow developer, a magenta developer, a cyan developer, and a black developer according to the present embodiment were put into each of the five developing machines of the printing means. As the developer for each color such as yellow, a commercially available product manufactured by Fuji Xerox Co., Ltd. was used.
A postcard paper V424 manufactured by Fuji Xerox Co., Ltd. was prepared as a recording medium.
The image formed on the postcard paper was an image having an area density of 30% in which black characters and a full-color photographic image were mixed, and was formed on one side of the postcard paper.
The amount of the pressure-responsive particles (or pressure-responsive particles for comparison) according to the present embodiment was set to 3 g / m 2 in the image-forming region of the image-forming surface of the postcard paper.
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 was 90 MPa.
Under the above equipment and conditions, 10 postcards were continuously produced, which were folded in half so that the image forming surfaces were on the inside and the image forming surfaces were adhered to each other.
The tenth postcard was cut in the long side direction with a width of 15 mm to prepare a rectangular test piece, and a 90-degree peeling test was performed. The peeling speed of the 90-degree peeling test was set to 20 mm / min, and after the start of measurement, loads (N) from 10 mm to 50 mm were collected at 0.4 mm intervals, the average was calculated, and the load (N) of three test pieces was further calculated. Was averaged. The load (N) required for peeling was classified as follows. The results are shown in Table 9, Table 10 and Table 11.
A:0.8N以上
B:0.6N以上、0.8N未満
C:0.4N以上、0.6N未満
D:0.2N以上、0.4N未満
E:0.2N未満
A: 0.8N or more B: 0.6N or more 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
100 配置手段
110 付与装置
120 固定装置
200 圧着手段
220 折り装置
230 加圧装置
231、232 加圧ロール
M 圧力応答性粒子
P 記録媒体
P1 画像上に圧力応答性粒子が付与された記録媒体
P2 折り重なった記録媒体
P3 圧着印刷物
100 Arrangement means 110 Applying device 120 Fixing device 200 Crimping means 220 Folding device 230 Pressurizing device 231, 232 Pressurizing roll M Pressure-responsive particles P Recording medium P1 Recording medium P2 to which pressure-responsive particles are applied on an image are folded. Recording medium P3 Crimped printed matter
101 感光体
102 帯電ロール(帯電手段の一例)
103 露光装置(静電荷像形成手段の一例)
104 現像装置(現像手段の一例)
105 転写ロール(転写手段の一例)
106 感光体クリーニング装置(クリーニング手段の一例)
107 固定装置(固定手段の一例)
101 Photoreceptor 102 Charging roll (an example of charging means)
103 Exposure device (an example of static charge image forming means)
104 Developing device (an example of developing means)
105 Transfer roll (an example of transfer means)
106 Photoreceptor cleaning device (an example of cleaning means)
107 Fixing device (an example of fixing means)
300 印刷手段
1T、1Y、1M、1C、1K 感光体
2T、2Y、2M、2C、2K 帯電ロール(帯電手段の一例)
3T、3Y、3M、3C、3K 露光装置(静電荷像形成手段の一例)
4T、4Y、4M、4C、4K 現像装置(現像手段の一例)
5T、5Y、5M、5C、5K 一次転写ロール(一次転写手段の一例)
6T、6Y、6M、6C、6K 感光体クリーニング装置(クリーニング手段の一例)
8T 圧力応答性粒子カートリッジ
8Y、8M、8C、8K トナーカートリッジ
10T、10Y、10M、10C、10K ユニット
20 中間転写ベルト(中間転写体の一例)
21 中間転写体クリーニング装置
22 駆動ロール
23 支持ロール
24 対向ロール
26 二次転写ロール(二次転写手段の一例)
28 熱定着装置(熱定着手段の一例)
300 Printing means 1T, 1Y, 1M, 1C, 1K Photoreceptor 2T, 2Y, 2M, 2C, 2K Charging roll (an example of charging means)
3T, 3Y, 3M, 3C, 3K exposure equipment (an example of electrostatic charge image forming means)
4T, 4Y, 4M, 4C, 4K developing equipment (an example of developing means)
5T, 5Y, 5M, 5C, 5K primary transfer roll (example of primary transfer means)
6T, 6Y, 6M, 6C, 6K Photoreceptor cleaning device (an example of cleaning means)
8T Pressure Responsive Particle Cartridge 8Y, 8M, 8C, 8K Toner Cartridge 10T, 10Y, 10M, 10C, 10K Unit 20 Intermediate Transfer Belt (Example of Intermediate Transfer)
21 Intermediate transfer body cleaning device 22 Drive roll 23 Support roll 24 Opposing roll 26 Secondary transfer roll (an example of secondary transfer means)
28 Heat fixing device (an example of heat fixing means)
Claims (23)
少なくとも2種の(メタ)アクリル酸エステルを重合成分に含み、重合成分全体に占める(メタ)アクリル酸エステルの質量割合が90質量%以上である(メタ)アクリル酸エステル系樹脂と、を含み、
少なくとも2つのガラス転移温度を有し、最も低いガラス転移温度と最も高いガラス転移温度との差が30℃以上である、
圧力応答性粒子。 Styrene-based resin containing styrene and other vinyl monomers as polymerization components,
A (meth) acrylic acid ester-based resin containing at least two kinds of (meth) acrylic acid esters in the polymerization component and having a mass ratio of the (meth) acrylic acid ester to the total polymerization component of 90% by mass or more is included.
It has at least two glass transition temperatures, and the difference between the lowest glass transition temperature and the highest glass transition temperature is 30 ° C. or more.
Pressure responsive particles.
前記コア部を被覆するシェル層と、
を有する、請求項1〜請求項11のいずれか1項に記載の圧力応答性粒子。 A core portion containing the styrene resin and the (meth) acrylic acid ester resin, and
The shell layer that covers the core portion and
The pressure-responsive particle according to any one of claims 1 to 11.
前記記録媒体を折り重ねて圧着する、又は、前記記録媒体と別の記録媒体とを重ねて圧着する圧着手段と、
を含む印刷物の製造装置。 An arrangement means for accommodating the pressure-responsive particles according to any one of claims 1 to 14 and arranging the pressure-responsive particles on a recording medium.
A crimping means for folding and crimping the recording medium, or stacking and crimping the recording medium and another recording medium.
Printed matter manufacturing equipment including.
前記記録媒体を折り重ねて圧着する、又は、前記記録媒体と別の記録媒体とを重ねて圧着する圧着工程と、
を含む印刷物の製造方法。 An arrangement step of arranging the pressure-responsive particles on a recording medium using the pressure-responsive particles according to any one of claims 1 to 14.
A crimping step in which the recording medium is folded and crimped, or the recording medium and another recording medium are overlapped and crimped.
A method for manufacturing printed matter including.
基材と、前記基材上に配置された前記圧力応答性粒子と、を有する印刷物製造用シート。 The pressure-responsive particles according to any one of claims 1 to 14 are used.
A printed matter manufacturing sheet having a base material and the pressure-responsive particles arranged on the base material.
印刷物製造用シートの製造方法。 A step of arranging the pressure-responsive particles on a substrate by using the pressure-responsive particles according to any one of claims 1 to 14.
A method for manufacturing a sheet for manufacturing printed matter.
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