EP3480028A1 - Corps de frottement, instrument d'écriture, et ensemble d'instruments d'écriture - Google Patents

Corps de frottement, instrument d'écriture, et ensemble d'instruments d'écriture Download PDF

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Publication number
EP3480028A1
EP3480028A1 EP17819839.6A EP17819839A EP3480028A1 EP 3480028 A1 EP3480028 A1 EP 3480028A1 EP 17819839 A EP17819839 A EP 17819839A EP 3480028 A1 EP3480028 A1 EP 3480028A1
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EP
European Patent Office
Prior art keywords
friction body
styrene
weight
aforementioned
component
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP17819839.6A
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German (de)
English (en)
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EP3480028A4 (fr
Inventor
Kazuhiko Furukawa
Yusuke Nakamura
Ryota Nakanishi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Pencil Co Ltd
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Mitsubishi Pencil Co Ltd
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Application filed by Mitsubishi Pencil Co Ltd filed Critical Mitsubishi Pencil Co Ltd
Publication of EP3480028A1 publication Critical patent/EP3480028A1/fr
Publication of EP3480028A4 publication Critical patent/EP3480028A4/fr
Pending legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
    • B43K—IMPLEMENTS FOR WRITING OR DRAWING
    • B43K29/00—Combinations of writing implements with other articles
    • B43K29/02—Combinations of writing implements with other articles with rubbers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
    • B43L—ARTICLES FOR WRITING OR DRAWING UPON; WRITING OR DRAWING AIDS; ACCESSORIES FOR WRITING OR DRAWING
    • B43L19/00—Erasers, rubbers, or erasing devices; Holders therefor

Definitions

  • the present invention relates to a friction body, a writing instrument and a writing instrument set.
  • thermochromic ink and a friction body and are configured so as to rub an image formed using the thermochromic ink with the friction body and allow the image to change color by frictional heat.
  • friction bodies include those composed of an elastomer.
  • PTL1 describes a friction body having elasticity that allows an image formed using a reversible thermochromic ink to change color from a first state to a second state by frictional heat, wherein the friction body is composed of silicone rubber.
  • PTL2 describes a friction body that allows an image formed using a reversible thermochromic ink to change color from a first state to a second state by frictional heat, wherein the friction body is composed of a styrene-butylene-styrene copolymer or styrene-ethylenebutylene-styrene copolymer.
  • PTL2 describes to the effect that a friction body is obtained which, in addition to being able to allow a thermochromic image to easily change color without peeling off, is capable of reforming the thermochromic image on a rubbed portion without repelling the ink.
  • thermochromicity and typically, an image formed on paper using a thermochromic ink
  • a friction body composed of a styrene-based copolymer as described in PTL2
  • the problem occurs in which a state results in which the paper becomes soiled due in particular to a strong load or repeated rubbing motion and the like (also simply referred to as "paper soiling” below).
  • An object of the present invention is to solve the aforementioned problem by providing a friction body, which in addition to being capable of favorably allowing an image having thermochromicity to change color by rubbing (namely, impart a favorable color change), is capable of reducing soiling of paper caused by a strong force and/or repeated rubbing motion, and to provide a writing instrument and writing instrument set provided with this friction body.
  • the present invention at least includes the aspects indicated below.
  • a friction body capable of favorably allowing an image having thermochromicity to change color (namely, imparting a favorable color change) by rubbing in addition to reducing paper soiling caused by strong force and/or repeated rubbing motion, along with a writing instrument and writing instrument set provided with such a friction body, can be provided.
  • One aspect of the present invention is a friction body that allows an image having thermochromicity to change color with frictional heat, the friction body containing a styrene-based elastomer and having compression set at 120°C of 80% or less and Shore A hardness of 60 to 98.
  • an "image having thermochromicity” refers to an image that has the property of maintaining a prescribed color (first color) at normal temperature (such as 25°C), changing to a different color (second color) when the temperature thereof is raised to a prescribed temperature (such as 60°C), and optionally returning to the original color (first color) when subsequently cooled to a prescribed temperature (such as -5°C).
  • An image having thermochromicity can typically be formed using a thermochromic ink to be subsequently described.
  • the cause of a paper surface becoming soiled particularly by strong force and/or repeated rubbing motion when changing the color of an image having thermochromicity by rubbing with a friction body is not clear.
  • the cause thereof may be that the physical properties of the friction body change as the surface temperature of the friction body rises during rubbing, and that destruction of the friction body (and more specifically, local separation) occurs causing the friction body to adhere to the paper surface, thereby causing soiling of the paper surface.
  • the inventors of the present invention surmised that the force applied to the paper surface during rubbing becomes uneven due to softening of the elastomer, thereby resulting in a locally strong force being applied to the ink when the color of the ink is attempted to be changed completely, with the resulting destruction of the thermochromic coloring material causing soiling of the paper surface.
  • the inventors of the present invention found that controlling deformation recovery of the friction body particularly in the high-temperature range is effective for reducing the aforementioned destruction of the friction body.
  • the friction body provided by one aspect of the present invention has suitable hardness and demonstrates favorable deformation recovery even at high temperatures as a result of controlling the balance between Shore A hardness and compression set in the high-temperature range, in addition to allowing an image having thermochromicity to favorably change color (namely, impart a favorable color change) by rubbing, it is capable of reducing soiling of the paper surface due to infrequent occurrence of destruction of the friction body attributable to strong force and/or repeated rubbing motion.
  • the friction body has compression set at 120°C (also referred to as "120°C compression set" in the present disclosure) of 80% or less.
  • a small 120°C compression set is an indicator of favorable deformation recovery of the friction body under rubbing conditions (namely, under high-temperature conditions), and this favorable deformation recovery contributes to maintaining favorable wear resistance of the friction body particularly under rubbing conditions (namely, under high-temperature conditions).
  • 120°C compression set may be 80% or less, 70% or less or 60% or less from the viewpoint of favorable wear resistance of the friction body under high-temperature conditions. 120°C compression set is preferably as small as possible from the viewpoint of wear resistance under high-temperature conditions. Furthermore, in the present disclosure, compression set is a value measured in compliance with JIS K6262-2013.
  • the compression set of a molded body formed from an elastomer tends to increase accompanying a rise in temperature.
  • the friction body of the present disclosure has a small 120°C compression set within a specific range as described above. It is advantageous from the viewpoint of obtaining this 120°C compression set that there is little temperature dependency of the compression set of the friction body.
  • the ratio (A)/(B) of the compression set of the friction body at 120°C (A) to the compression set of the friction body at 70°C (B) may be 1.0 to 1.7, 1.0 to 1.5, 1.0 to 1.4 or 1.0 to 1.3.
  • the friction body has Shore A hardness of 60 to 98. From the viewpoints of favorable color change of an image having thermochromicity and favorable wear resistance of the friction body, Shore A hardness may be 60 or more, 70 or more or 80 or more. From the viewpoint of increasing contact area with the paper surface as a result of pressing the friction body onto the paper surface, and therefore allowing a favorable color change to be easily obtained, Shore A hardness may be 98 or less, 95 or less or 90 or less. Furthermore, in the present disclosure, Shore A hardness is a value measured in compliance with JIS K 6253-3-2012.
  • composition of material components composing the friction body of the present disclosure is designed so as to impart the desired 120°C compression set and Shore A hardness as described above.
  • the friction body contains an elastomer component and an additive component.
  • the elastomer component examples include styrene-based elastomers, polyester-based elastomers and olefin-based elastomers, from the viewpoint of easily realizing the desired 120°C compression set and Shore A hardness, the elastomer component contains a styrene-based elastomer and is preferably composed of a styrene-based elastomer.
  • a "styrene-based elastomer” refers to an elastomer that contains a styrene constituent unit in the main chain thereof, and is typically a thermoplastic elastomer.
  • the styrene-based elastomer is preferably a block copolymer having a polymer block composed mainly of a constituent unit derived from a styrene skeleton-containing compound and a polymer block composed mainly of a constituent unit derived from a conjugated diene compound (to be referred to as a "styrene-based block copolymer), a hydrogenation product of the block copolymer, or a mixture thereof.
  • polymer block composed mainly of a constituent unit derived from a styrene skeleton-containing compound (or conjugated diene compound) refers to a polymer block such that the constituent unit present at the highest weight ratio in the polymer block is a constituent unit derived from a styrene skeleton-containing compound (or conjugated diene compound).
  • the aforementioned styrene-based block copolymer is normally a block copolymer having one or more polymer blocks X mainly composed of a constituent unit derived from a styrene skeleton-containing compound, preferably 2 or more from the viewpoint of mechanical properties, and one or more polymer blocks Y mainly composed of a constituent unit derived from a conjugated diene compound.
  • Examples thereof include block copolymers having the structures X-Y, X-Y-X, Y-X-Y-X or X-Y-X-Y-X.
  • Hydrogenation products of the aforementioned styrene-based block copolymer are obtained by adding hydrogen to carbon-carbon double bonds present in the aforementioned styrene-based block copolymer to convert to carbon-carbon single bonds.
  • the aforementioned hydrogenation can be carried out by a known method such as hydrogen treatment using a hydrogenation catalyst in an inert solvent.
  • the hydrogenation rate of the aforementioned hydrogenated styrene-based block copolymer (namely, the ratio of the number of carbon-carbon single bonds formed during hydrogenation to the number of carbon-carbon double bonds in the styrene-based block copolymer prior to hydrogenation) may be 50% or more, 70% or more or 90% or more. Furthermore, the aforementioned hydrogenation rate refers to a value measured by 1 H-NMR unless specifically indicated otherwise.
  • the styrene skeleton-containing compound is a polymerizable monomer having a polymerizable carbon-carbon double bond and an aromatic ring.
  • examples of the aforementioned styrene skeleton-containing compound include styrene, t-butylstyrene, ⁇ -methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N,N-diethyl-p-aminoethylstyrene, p-t-butylstyrene and alkylstyrenes in which at least one alkyl group having 1 to 8 carbon atoms is bound to a benzene ring.
  • styrene and alkylstyrenes in which at least one alkyl group having 1 to 8 carbon atoms is bound to a benzene ring are preferable.
  • One of more types of these compounds can be used for the aforementioned styrene skeleton-containing compound.
  • alkylstyrenes such as o-alkylstyrenes, m-alkylstyrenes, p-alkylstyrenes, 2,4-dialkylstyrenes, 3,5-dialkylstyrenes or 2,4,6-trialkylsty
  • Specific examples thereof include o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 3,5-dimethylstyrene, 2,4,6-trimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, 2,4-diethylstyrene, 3,5-diethylstyrene, 2,4,6-triethylstyrene, o-propylstyrene, m-propylstyrene, p-propylstyrene, 2,4-dipropylstyrene, 3,5-dipropylstyrene, 2,4,6-tripropylstyrene, 2-methyl-4-ethylstyrene, 3-methyl-5-ethylstyrene,
  • alkylstyrenes in which at least one alkyl group having 1 to 8 carbon atoms is bound to a benzene ring are used preferably as materials of crosslinked styrene-based elastomers.
  • the ratio of the aforementioned alkylstyrene in which at least one alkyl group having 1 to 8 carbon atoms is bound to a benzene ring in the aforementioned polymer block X is preferably 1% by weight or more, more preferably 50% by weight or more, and even more preferably 100% by weight from the viewpoint of crosslinkability.
  • the aforementioned conjugated diene compound is a polymerizable monomer having a structure in which two carbon-carbon double bonds are bound by a single carbon-carbon single bond.
  • Examples of the aforementioned conjugated diene compound include 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl-1,3-butadiene and chloroprene (2-chloro-1,3-butadiene). Among these, 1,3-butadiene and isoprene are preferable.
  • One or more types of these conjugated diene compounds can be used for the aforementioned conjugated diene compound.
  • the content of the aforementioned constituent unit derived from a styrene skeleton-containing compound in the aforementioned styrene-based block copolymer or hydrogenation product thereof may be 5% by weight to 50% by weight or 20% by weight to 40% by weight from the viewpoints of mechanical strength, cold resistance, heat resistance and flexibility.
  • the aforementioned polymer block X is preferably a polymer block derived only from the aforementioned styrene skeleton-containing compound or a copolymer block consisting of the aforementioned styrene skeleton-containing compound and the aforementioned conjugated diene compound.
  • the polymer block X is the aforementioned copolymer block, although there are no particular limitations thereon, the content of the aforementioned constituent unit derived from the styrene skeleton-containing compound in the aforementioned polymer block X may normally be 50% by weight or more, 70% by weight or more or 90% by weight or more from the viewpoint of heat resistance.
  • the polymer blocks X may have the same structure or may have mutually different structures.
  • the aforementioned polymer block Y is preferably a polymer block composed only of the aforementioned conjugated diene compound or a copolymer block consisting of the aforementioned styrene skeleton-containing compound and the conjugated diene compound.
  • the polymer block Y is the aforementioned copolymer block, although there are no particular limitations thereon, the content of the aforementioned constituent unit derived from the conjugated diene compound in the polymer block Y may normally be 50% by weight or more, 70% by weight or more or 90% by weight or more from the viewpoint of heat resistance.
  • the distribution of the aforementioned constituent unit derived from the styrene skeleton-containing compound in the polymer block Y There are no particular limitations on the distribution of the aforementioned constituent unit derived from the styrene skeleton-containing compound in the polymer block Y.
  • the bonding form between the aforementioned conjugated diene compound and the aforementioned styrene skeleton-containing compound there are also no particular limitations on the bonding form between the aforementioned conjugated diene compound and the aforementioned styrene skeleton-containing compound.
  • the polymer blocks Y may have the same structure or may have mutually different structures.
  • styrene-based block copolymer examples include styrenebutadiene-styrene block copolymer (SBS) and styrene-isoprene-styrene block copolymer (SIS).
  • SBS styrenebutadiene-styrene block copolymer
  • SIS styrene-isoprene-styrene block copolymer
  • Examples of hydrogenation products of the aforementioned styrene-based block copolymer include styrene-ethylene-butene copolymer (SEB), styrene-ethylene-propylene copolymer (SEP), styrene-ethylene-butene-styrene copolymer (SEBS), styrene-ethylene-propylene-styrene copolymer (SEPS) and styrene-ethylene-ethylene-propylene-styrene copolymer (SEEPS).
  • SEB styrene-ethylene-butene copolymer
  • SEP styrene-ethylene-propylene copolymer
  • SEBS styrene-ethylene-butene-styrene copolymer
  • SEPS styrene-ethylene-propylene-styrene copolymer
  • SEEPS styrene-ethylene-ethylene-propy
  • SEPS styrene-ethylene-propylene-styrene copolymer
  • SEEPS styrene-ethylene-ethylene-propylene-styrene copolymer
  • SEBS styrene-butadiene-styrene copolymer
  • SEPS styrene-ethylene-propylene-styrene copolymer
  • SEEPS styrene-ethylene-ethylene-propylene-styrene copolymer
  • SEEPS styrene-ethylene-ethylene-propylene-styrene copolymer
  • One or two or more types of the aforementioned examples of styrene-based block copolymers and/or hydrogenation products thereof can be used as a mixture.
  • the styrene-based elastomer may be crosslinked. Increasing the degree of crosslinking contributes to a decrease in 120°C compression set and an increase in Shore A hardness.
  • SEBS, SEPS and SEEPS in which styrene is substituted with p-methylstyrene, are preferable from the viewpoints of heat resistance and wear resistance.
  • whether or not the styrene-based elastomer is crosslinked can be distinguished by immersing in hot xylene at 120°C for 24 hours followed by visually observing whether a gel fraction remains or measuring residual weight.
  • a crosslinking agent to be subsequently described (component (E)) can be used for crosslinking.
  • the friction body is not required to contain a polymer insoluble in hot xylene at 120°C other than a crosslinked styrene-based elastomer.
  • whether or not the styrene-based elastomer is crosslinked can be evaluated by subjecting the friction body to the aforementioned hot xylene treatment.
  • the weight average molecular weight (Mw) of the styrene-based elastomer is preferably 150,000 to 500,000.
  • the weight average molecular weight may be 150,000 or more, 180,000 or more or 200,000 or more from the viewpoint of obtaining a friction body having favorable wear resistance.
  • the weight average molecular weight may be 500,000 or less, 450,000 or less or 400,000 or less from the viewpoint of favorable processability during production of the friction body.
  • molecular weight refers to the value as polystyrene when measured according to gel permeation chromatography (GPC) unless specifically indicated otherwise.
  • propylene-based resin Component (B)
  • rubber softening agent Component (C)
  • lubricant Component (D)
  • crosslinking agent Component (E)
  • crosslinking assistant Component (F)
  • colorant Component (G)
  • polymer component other than the aforementioned propylene-based resin, stabilizer and filler can be used as other components.
  • Component (B) is advantageous for improving wear resistance and paper soiling resistance of the friction body.
  • Component (B) include propylene homopolymers, propylene-based random copolymers and propylene-based block copolymers, and one type of these components can be used alone or two or more types can be used in combination. From the viewpoint of heat resistance, a propylene homopolymer or propylene-based block copolymer is more preferable, while a propylene homopolymer is even more preferable.
  • Component (B) is most preferably a propylene homopolymer since polymers composed of a propylene unit only have high crystallinity and melting point.
  • propylene-based random copolymers examples include propylene-ethylene random copolymers obtained by copolymerizing propylene and ethylene, propylene- ⁇ -olefin random copolymers obtained by copolymerizing propylene and at least one type of ⁇ -olefin having 4 to 20 carbon atoms, and propylene-ethylene- ⁇ -olefin random copolymers obtained by copolymerizing propylene, ethylene and at least one type of ⁇ -olefin having 4 to 20 carbon atoms.
  • Examples of ⁇ -olefins having 4 to 20 carbon atoms include 1-butene, 2-methyl-1-propene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene, 1-heptene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl-1-butene, 1-octene, methyl-1-pentene, ethyl-1-hexene, dimethyl-1-hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pentene, propyl-1-pentene, diethyl-1-but
  • propylene-based random copolymers include propylene-ethylene random copolymers, propylene-1-butene random copolymers, propylene-1-hexene random copolymers, propylene-1-octene random copolymers, propylene-ethylene-1-butene random copolymers, propylene-ethylene-1-hexene random copolymers and propylene-ethylene-1-octene random copolymers, and preferably include propylene-ethylene random copolymers, propylene-1-butene random copolymers, propylene-1-hexene random copolymers, propylene-ethylene-1-butene random copolymers and propylene-ethylene-1-hexene random copolymers.
  • propylene-based block copolymers examples include block copolymers composed of a crystalline propylene-based polymer site and an amorphous propylene- ⁇ -olefin copolymer site.
  • Examples of crystalline propylene-based polymers include propylene homopolymers and random copolymers consisting of propylene and a small amount of another ⁇ -olefin.
  • examples of amorphous propylene- ⁇ -olefin copolymers include amorphous random copolymers of propylene and another ⁇ -olefin.
  • examples of other ⁇ -olefins preferably include those having 2 or 4 to 12 carbon atoms, specific examples of which include ethylene, 1-butene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, vinylcyclopentane and vinylcyclohexane.
  • One type of these ⁇ -olefins can be used alone or two or more types can be used in combination.
  • Ternary, quaternary or multiple copolymers obtained by copolymerizing, in addition to the aforementioned other ⁇ -olefins, a non-conjugated diene can also be used as propylene-based block copolymers, examples of which include 1,4-hexadiene, 5-methyl-1,5-hexadiene, 1,4-octadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene and 5-isopropenyl-2-norbornene.
  • the melt mass-flow rate of the aforementioned Component (B) may be 0.01 g/10 min to 100 g/10 min, 0.1 g/10 min to 50 g/10 min or 0.3 g/10 min to 10 g/10 min when measured under conditions of 230°C and 21.18 N in compliance with JIS K 7210-1999.
  • the melting point of Component (B) may be 150°C or higher or 160°C or higher from the viewpoint of heat resistance.
  • the upper limit of the melting point since Component (B) is a polypropylene-based resin, the upper limit of the melting point thereof is about 167°C.
  • the aforementioned melting point refers to a melting point corresponding to the top of the peak appearing at the highest temperature on the second melting curve (namely, the melting curve measured during the final heating process) when measuring according to a heating program consisting of holding for 5 minutes at 230°C, cooling to -10°C at the rate of 10°C/min, holding at -10°C for 5 minutes and heating to 230°C at the rate of 10°C/min using a DSC type differential scanning calorimeter (such as the Diamond System manufactured by PerkinElmer Japan).
  • the incorporated amount of Component (B) may be 30 parts by weight to 300 parts by weight, 35 parts by weight to 250 parts by weight or 40 parts by weight to 180 parts by weight based on 100 parts by weight of the aforementioned Component (A). As a result of making the incorporated amount to be within these ranges, the balance among flexibility, wear resistance and paper soiling resistance becomes favorable.
  • Component (C) Various compounds understood by persons with ordinary skill in the art to function as a softening agent in the art can be used as the rubber softening agent (Component (C)).
  • component (C) is advantageous for improving flexibility of the friction body.
  • Component (C) is typically a non-aromatic rubber softening agent.
  • non-aromatic rubber softening agents include non-aromatic mineral oils (namely, hydrocarbon compounds derived from petroleum and the like that are not classified as aromatics according to the classifications to be subsequently described (namely, those in which the number of aromatic carbon atoms is less than 30%)) and non-aromatic synthetic oils (namely, synthetic hydrocarbon compounds that do not use aromatic monomers).
  • Non-aromatic rubber softening agents are normally in the form of a liquid, gel or rubber at normal temperature.
  • the mineral oils used as Component (C) are mixtures of compounds having at least one type of paraffin chain, naphthene ring and aromatic ring, and are distinguished based on the number of carbons by referring to that in which the naphthene ring accounts for 30% to 45% as a naphthene-based mineral oil, that in which the aromatic ring accounts for 30% or more as an aromatic-based mineral oil, and that which is not classified as a naphthene-based mineral oil or aromatic-based mineral oil and in which the paraffin chain accounts for 50% or more based on the number of carbons as a paraffin-based mineral oil.
  • Examples of the aforementioned Component (C) include paraffin-based mineral oils such as linear saturated hydrocarbons, branched saturated hydrocarbons or derivatives thereof, naphthene-based mineral oils, synthetic oils such as hydrogenated polyisobutylene, polyisobutylene or polybutene.
  • paraffin-based mineral oils are preferable and paraffin-based mineral oils having a small number of aromatic carbons are more preferable from the viewpoint of compatibility with an elastomer component.
  • those that are a liquid at room temperature are preferable from the viewpoint of handling ease.
  • dynamic viscosity of the aforementioned Component (C) at 37.8°C as measured in compliance with JIS K2283-2000 may be 20 cSt to 1000 cSt or 50 cSt to 500 cSt.
  • pour point of Component (C) as measured in compliance with JIS K2269-1987 may be -10°C to - 25°C.
  • flash point (COC) of Component (C) as measured in compliance with JIS K2265-2007 may be 170°C to 300°C.
  • the incorporated amount of the aforementioned Component (C) may be 1 part by weight to 400 parts by weight, 10 parts by weight to 250 parts by weight or 40 parts by weight to 180 parts by weight based on 100 parts by weight of the aforementioned Component (A) from the viewpoints the balance between flexibility and mechanical properties.
  • Component (D) Various compounds understood by persons with ordinary skill in the art to function as a lubricant in the art can be used as lubricant (Component (D)).
  • Use of Component (D) is advantageous for mold release properties and inhibiting friction of the paper surface.
  • Examples of the aforementioned Component (D) include silicone-based compounds, fluorine-based compounds and surfactants, and silicone-based compounds are preferable from the viewpoint of inhibiting friction of the paper surface.
  • Silicone oil or silicone rubber for example, can be used for the aforementioned silicone-based compound.
  • those having a high molecular weight are preferable from the viewpoints of heat resistance, bleed resistance and inhibiting friction of the paper surface.
  • resin blends or copolymers with resin are preferable in terms of use.
  • resins used here are selected in consideration of such factors as compatibility with other components composing the friction body and compatibility with the aforementioned Component (A) in particular, typically polyethylene, polypropylene or other olefin-based resins are preferable.
  • Polyvinylidene fluoride or polyvinyl fluoride for example, can be used for the aforementioned fluorine-based compound.
  • polyvinylidene fluoride is preferable from the viewpoint of inhibiting friction of the paper surface.
  • anionic, cationic or nonionic surfactants can be used for the aforementioned surfactant.
  • the incorporated amount of the aforementioned Component (D) may be 0.1 parts by weight to 30 parts by weight, 0.5 parts by weight to 20 parts by weight or 1 part by weight to 10 parts by weight based on 100 parts by weight of the aforementioned Component (A) from the viewpoint of inhibiting friction of the paper surface.
  • the content of Component (D) in the friction body is preferably 0.1% by weight to 3.0% by weight.
  • the aforementioned content may be 0.1% by weight or more, 0.3% by weight or more or 0.5% by weight or more from the viewpoint of inhibiting friction of the paper surface, and 3.0% by weight or less, 2.5% by weight or less or 2.0% by weight or less from the viewpoint of obtaining favorable erasing performance and paper soiling resistance.
  • crosslinking agent Various compounds understood by persons with ordinary skill in the art to function as a crosslinking agent in the art can be used as crosslinking agent (Component (E)).
  • Component (E) is incorporated in the friction body mainly for the purpose of crosslinking the aforementioned Component (A).
  • Use of Component (E) is advantageous for reducing 120°C compression set and increasing Shore A hardness.
  • Organic peroxides and phenol-based compounds for example, can be used for the aforementioned Component (E) and organic peroxides are preferable from the viewpoint of wear resistance.
  • organic peroxides are compounds in which one or two or more hydrogen atoms of hydrogen peroxide are substituted with free organic groups. Since organic peroxides have a peroxide bond in a molecule thereof, these organic peroxides generate radicals during production of the friction body (such as during melting and kneading of the material composition) and these radicals react in the manner of chain reaction to act to crosslink the aforementioned Component (A).
  • organic peroxides examples include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexyne-3, 1-3-bis(tert-butylperoxyisopropyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(tert-butylperoxy)valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dicyclobenzoyl peroxide, tert-butylperoxy benzoate, tert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide and tert-butylcumy
  • 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane and 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexyne-3 are preferable from the viewpoints of low odor intensity, low colorability and scorch safety.
  • Component (F) a crosslinking assistant (Component (F)) to be subsequently described is also used preferably.
  • the use of Component (F) makes it possible to carry out a uniform and efficient crosslinking reaction.
  • a resole resin is preferable for the aforementioned phenol-based compound from the viewpoint of normally being in a liquid state.
  • Resole resins are produced by condensation of an aldehyde (and preferably formaldehyde) in an alkaline medium or by condensation of a bifunctional phenol dialcohol.
  • the alkyl-substituent portion of an alkyl-substituted phenol typically has 1 to 10 carbon atoms. Dimethylol phenol or phenol resin substituted at the p-position with an alkyl group having 1 to 10 carbon atoms is preferable.
  • alkylphenol formaldehyde resins methylolated alkylphenol resins and brominated alkylphenol resins, for example, are preferable.
  • the terminal hydroxyl group may be brominated.
  • Alkylphenol formaldehyde resins are particularly preferable.
  • the incorporated amount of the aforementioned Component (E) may be 0.01 parts by weight to 20 parts by weight, 0.1 parts by weight to 10 parts by weight or 0.5 parts by weight to 5 parts by weight based on 100 parts by weight of Component (A).
  • An incorporated amount equal to or greater than the aforementioned lower limit values is preferable from the viewpoint of allowing the crosslinking reaction to proceed favorably, while on the other hand, an incorporated amount equal to or less than the aforementioned upper limit values is preferable from the viewpoint of favorably maintaining moldability without allowing crosslinking to proceed excessively.
  • crosslinking assistant Various compounds understood by persons with ordinary skill in the art to function as a crosslinking assistant or crosslinking promoter in the art can be used as crosslinking assistant (Component (F)).
  • Examples of the aforementioned Component (F) include multifunctional methacrylate compounds in the manner of triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate having 9 to 14 repeating ethylene glycol units, trimethylolpropane trimethacrylate, allyl methacrylate, 2-methyl-1,8-octanediol dimethacrylate or 1,9-nonanediol dimethacrylate; multifunctional acrylate compounds in the manner of polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate or propylene glycol diacrylate; and multifunctional vinyl compounds in the manner of vinyl butyrate or vinyl stearate. One or more types of these compounds can be used for Component (F).
  • multifunctional acrylate compounds and multifunctional methacrylate compounds are preferable, and triallyl cyanurate, triethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate are particularly preferable.
  • triallyl cyanurate, triethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate are particularly preferable.
  • crosslinking can be made to be more uniform and efficient when used in combination with an organic peroxide.
  • the incorporated amount of the aforementioned Component (F) may be 0.01 parts by weight to 50 parts by weight, 0.5 parts by weight to 30 parts by weight or 1 part by weight to 20 parts by weight based on 100 parts by weight of Component (A).
  • An incorporated amount equal to or greater than the aforementioned lower limit values is preferable from the viewpoint of allowing the crosslinking reaction to proceed favorably, while on the other hand, an incorporated amount equal to or less than the aforementioned upper limit values is preferable from the viewpoint of favorably maintaining dispersion of the crosslinked product in the friction body without allowing crosslinking to proceed excessively.
  • Component (G) Various compounds understood by persons with ordinary skill in the art to function as a colorant in the art can be used as colorant (Component (G)).
  • the friction body can be produced by, for example, the method indicated below, although there are no particular limitations thereon.
  • a material composition is prepared by mechanically melting and kneading the aforementioned material components.
  • An ordinary melting-kneading machine such as a Banbury mixer, various types of kneaders or single- or twin-screw extruder can be used for melting and kneading.
  • the resulting material composition is molded with an ordinary method used to mold thermoplastic resin such as injection molding, extrusion molding or blow molding to obtain a friction body of a desired shape. Examples of preferable shapes of the friction body are subsequently described with reference to the drawings.
  • the present disclosure includes a writing instrument and writing instrument set provided with the previously described friction body.
  • Another aspect of the present invention provides:
  • FIG. 1 is a partial cross-sectional view of a writing instrument according to one embodiment of the present invention.
  • a writing instrument 1 has a cylindrical barrel 2, a writing body in the form of a refill cartridge (not shown) arranged within the barrel 2 and provided with a writing portion 3 on one end thereof, a friction body 5 provided on the rear end of the barrel 2 via a retaining member 4, a cover member 6 covering the friction body 5 and is removable from the friction body 5, and a clip 7 attached to the side of the rear end of the barrel 2 that clips onto an article.
  • the side of the writing portion 3 in the axial direction of the writing instrument 1 is defined as the "front”, while the opposite side from the writing portion 3 is defined as the "rear”.
  • the central axis refers to the central axis of the writing instrument 1.
  • the writing instrument 1 is a thermochromic writing instrument that houses a thermochromic ink in the refill cartridge thereof, and allows handwriting written with the writing instrument 1 to thermally change color due to frictional heat generated when rubbed with the friction body 5.
  • the friction body 5 can be moved relative to the barrel 2 by pressing forward.
  • the refill cartridge is moved forward and backward within the barrel 2 by a knocking operation in which the friction body 5 is pushed forward in opposition to the urging force of a spring arranged within the barrel 2.
  • the state in which the writing portion 3 protrudes from the barrel 2 is referred to as the writing state ( FIG. 1 )
  • the non-writing state is referred to as the non-writing state (not shown).
  • FIG. 2 is a perspective view of the friction body 5 and retaining member 4 of the writing instrument 1.
  • the bottom of the drawing indicates the front side of the writing instrument 1.
  • the friction body 5 is provided on the retaining member 4 by engaging therewith or by two-color molding.
  • the friction body 5 is formed into the shape of a tapered truncated triangular pyramid having a roughly triangular cross-sectional shape. More specifically, in a cross-section thereof, the vertex of the triangle is rounded and formed into the shape of an arc, and the radius of curvature of that arc becomes larger towards the rear end of the friction body 5.
  • a rear end surface 5a of the friction body 5 is formed into the shape of a curve. Thus, the boundaries between the rear end surface 5a and peripheral surfaces 5b of the friction body 5 constitute ridgelines 5c.
  • the use of the rear end surface 5a makes it possible to rub a wider area.
  • the friction body 5 is also able to rub a wider area by using the ridgelines 5c equivalent to the sides of a triangle, and is able to rub a narrower area by using the portion equivalent to the vortex of a triangle.
  • the employing of a shape having one or more corners (such as the vertexes of a triangle) as viewed from the axial direction by the friction body 5 is advantageous from the viewpoint of favorably rubbing both wide areas and narrow areas.
  • the cross-sectional shape of the friction body 5 is naturally not limited to a triangle, but rather may be that of a tetragon, hexagon or other polygon.
  • the friction body may also be provided on a portion, other than the rear end portion of the barrel 2, of the writing instrument 1 such as the front end portion of the barrel 2 or the clip 7.
  • the friction body may also be provided on a thermochromic writing instrument other than a knock-type writing instrument as shown in FIG. 1 , such as on the rear end portion of the barrel or on the tip of a cap in a capped writing instrument.
  • Another aspect of the present invention provides:
  • FIG. 3 is a perspective view of a separate friction body 10.
  • the friction body 10 in FIG. 3 is in the shape of a rectangular parallelepiped housed in a case 11, it may also be in the shape of a cube or cylindrical column.
  • thermochromic ink refers to an ink that has the property of maintaining a prescribed color (first color) at normal temperature (such as 25°C), changing to a different color (second color) when the temperature thereof is raised to a prescribed temperature (such as 60°C), and optionally returning to the original color (first color) when subsequently cooled to a prescribed temperature (such as -5°C).
  • first color at normal temperature
  • second color when the temperature thereof is raised to a prescribed temperature
  • second color optionally returning to the original color (first color) when subsequently cooled to a prescribed temperature (such as -5°C).
  • the thermochromic ink can be designed corresponding to the application, such as employing a combination in which one of the first color and second color is colored while the other is colorless, or a combination in which both the first color and second color are colored.
  • thermochromic ink has a thermochromic colorant.
  • thermochromic microcapsule pigment serving as the thermochromic colorant is that which changes color due to frictional heat or other heat, such as that which changes from colored to colorless, one color to a different color, or from colorless to colored, and various such pigments can be used, examples of which include those in which a thermochromic composition at least containing a leuco pigment, developer and color change temperature adjusting agent is microencapsulated.
  • leuco pigment that can be used provided it is an electron-donating dye that functions as a coloring agent. More specifically, triphenylmethane-based, spiropyran-based, fluoran-based, diphenylmethane-based, rhodamine lactam-based, indolyl phthalide-based, leuco oramine-based and other conventionally known leuco pigments can be used alone (one type) or two or more types can be used as a mixture (to be simply referred to as "at least one type") from the viewpoint of obtaining an ink having superior coloring properties.
  • the developer that can be used serves as a component that has the ability to cause the aforementioned leuco pigment to become colored, and examples thereof include phenol resin-based compounds, salicylic acid-based metal chlorides, salicylic acid resin-based metal chlorides and solid acid-based compounds.
  • the amount of developer used is arbitrarily selected corresponding to the desired color density, and although there are no particular limitations thereon, normally the amount used thereof is preferably selected within the range of about 0.1 parts by weight to 100 parts by weight based on 1 part by weight of the aforementioned leuco pigment.
  • the color change temperature adjusting agent that can be used is a substance that controls the temperature of the color change during coloring by the aforementioned leuco pigment and developer.
  • a conventionally known color change temperature adjusting agent can be used for the color change temperature adjusting agent able to be used. Specific examples thereof include alcohols, esters, ketones, ethers, acid amides, azomethines, fatty acids and hydrocarbons.
  • this color change temperature adjusting agent used is suitably selected corresponding to such factors as the desired hysteresis error or color density during coloring, and although there are no particular limitations thereon, normally the amount used thereof is preferably selected within the range of about 1 part by weight to 100 parts by weight based on 1 part by weight of the leuco pigment.
  • thermochromic microcapsule pigment can be produced microencapsulating a thermochromic composition at least containing the aforementioned leuco pigment, developer and color change temperature adjusting agent so that the mean particle diameter thereof is 0.2 ⁇ m to 3 ⁇ m.
  • microencapsulation methods include interfacial polymerization, interfacial polycondensation, in situ polymerization, liquid cured coating, phase separation from an aqueous solution, phase separation from an organic solvent, melt dispersion cooling, air suspension coating and spray drying, and can be suitably selected corresponding to the application.
  • the contents of the leuco pigment, developer and color change temperature adjusting agent vary according to such factors as the types of leuco pigment, developer and color change temperature adjusting agent used or type of microencapsulation method, the content thereof based on weight ratio is 0.1 to 100 of the color developer and 1 to 100 of the color change temperature adjusting agent based on 1 part of the leuco pigment.
  • the content of capsule membrane agent is 0.1 to 1 as the weight ratio based on the weight of the capsule contents.
  • the coloring temperature (such as coloring at 0°C or higher) and decoloring temperature (such as decoloring at 50°C or higher) of each color of the thermochromic microcapsule pigment can be set to a preferable temperature by preferably combining the types and quantities of the aforementioned leuco pigment, developer and color change temperature adjusting agent, and the thermochromic microcapsule pigment preferably is changed from colored to colorless by frictional heat imparted by the friction body of the present disclosure.
  • the wall film of the thermochromic microcapsule pigment is preferably formed with urethane resin, urea/urethane resin, epoxy resin or amino resin from the viewpoints of improving drawn line concentration, storage stability and writing properties.
  • the thickness of the wall film of the microcapsule colorant is suitably determined corresponding to the required wall film strength and drawn line concentration.
  • thermochromic ink can suitably also contain as the remainder thereof a solvent in the form of water (such as tap water, purified water, distilled water, ion exchange water or pure water) as well as a water-soluble organic solvent, thickener, lubricant, rust inhibitor, preservative or antibacterial agent and the like corresponding to the application of each type of writing instrument (such as a ball pen or marking pen) within a range that does not impair the effect thereof.
  • a solvent in the form of water such as tap water, purified water, distilled water, ion exchange water or pure water
  • thermochromic ink A conventionally known method can be employed to produce the thermochromic ink, and for example, the thermochromic ink can be obtained incorporating prescribed amounts of the aforementioned thermochromic or photochromic microcapsule pigment and each of the aforementioned aqueous components followed by stirring and mixing with a homomixer or stirrer such as a disperser. Coarse particles present in the thermochromic ink may be further removed by filtration or centrifugal separation as is necessary.
  • the viscosity value of the thermochromic ink at 25°C and shear velocity of 3.83/s is preferably 500 mPa ⁇ s to 2000 mPa ⁇ s while that at a shear velocity of 383/s is preferably 20 mPa ⁇ s to 100 mPa ⁇ s.
  • An ink demonstrating superior writing properties and stability over time can be obtained by setting the viscosity value to be within the aforementioned viscosity ranges.
  • thermochromic ink is preferably 25 mN/m to 45 mN/m and more preferably 30 mN/m to 40 mN/m. If within these ranges, balance between the wettability of the inside of the pen tip and the ink becomes suitable, thereby making it possible to prevent the ink from backing up.
  • thermochromic ink Additional details regarding the thermochromic ink are described in, for example, JP-A-2015-229708 , WO 2015/033750 and WO 2011/070966 .
  • the weight average molecular weights of Components (A-1) to (A-7) were obtained by gel permeation chromatography ("LC-2000 Plus” (trade name) High-Performance Chromatography System, JASCO) using chloroform for the mobile phase based on polystyrene standards.
  • Compression set was measured at a compression ratio of 25% for 22 hours at 70°C and for 72 hours at 120°C for small test pieces fabricated from pressed sheets having a thickness of 6.3 mm in compliance with JIS K6262-2013.
  • Shore A hardness was determined by measuring the value for a pressed sheet having a thickness of 6.3 mm after 15 seconds using a type A durometer in compliance with JIS K6253-3-2012.
  • Test pieces were fabricated by uniformly spreading the thermochromic ink over a test paper defined in ISO 12757-1 with a bar coater (No. 6, Yasuda Seiki). After allowing the test pieces to dry completely, the friction body was contacted with the paper at an angle of 60 degrees from the paper surface and the paper surface was rubbed back and forth in a state in which the load applied to the paper was 5 N while maintaining a speed of about 8 m/sec to 10 m/sec. Subsequently, Ns values representing the soiling level of the rubbed portions were measured with a spectrocolorimeter (SC-P, Suga Test Instruments) followed by evaluating color change based on the criteria indicated below.
  • SC-P spectrocolorimeter
  • Soiling resistance was evaluated based on the criteria indicated below by carrying out a soiling test consisting of pressing the friction body against the paper surface (test paper defined in ISO 12757-1) at an angle of 60 degrees to 90 degrees and rubbing back and forth in a state in which the load applied to the paper was about 15 N to 20 N while maintaining a speed of about 8 m/sec to 10 m/sec followed by confirming the presence of adhesion of debris to the paper surface or destruction of the paper surface per se.
  • the friction body of the present disclosure is preferably used in a writing instrument or writing instrument set composed so as to allow thermochromic handwriting to change color with frictional heat.

Landscapes

  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Pens And Brushes (AREA)
EP17819839.6A 2016-06-30 2017-06-12 Corps de frottement, instrument d'écriture, et ensemble d'instruments d'écriture Pending EP3480028A4 (fr)

Applications Claiming Priority (2)

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JP2016130701A JP2018001573A (ja) 2016-06-30 2016-06-30 摩擦体、筆記具及び筆記具セット
PCT/JP2017/021671 WO2018003475A1 (fr) 2016-06-30 2017-06-12 Corps de frottement, instrument d'écriture, et ensemble d'instruments d'écriture

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EP3480028A1 true EP3480028A1 (fr) 2019-05-08
EP3480028A4 EP3480028A4 (fr) 2020-02-26

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JP7261009B2 (ja) * 2018-12-27 2023-04-19 株式会社パイロットコーポレーション 筆記具
JP7456825B2 (ja) * 2020-03-25 2024-03-27 三井化学株式会社 摩擦体用組成物、摩擦体及び筆記具
EP4129710A4 (fr) * 2020-03-31 2024-05-29 Kabushiki Kaisha Pilot Corporation (also trading as Pilot Corporation) Instrument d'écriture thermochromique

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JP4308359B2 (ja) * 1999-03-25 2009-08-05 パイロットインキ株式会社 熱変色性字消体
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JP4087664B2 (ja) * 2002-08-27 2008-05-21 アロン化成株式会社 エラストマー組成物
JP4688541B2 (ja) * 2004-04-06 2011-05-25 リケンテクノス株式会社 架橋剤マスターバッチ
JP2006123324A (ja) * 2004-10-28 2006-05-18 Pilot Ink Co Ltd 摩擦体及びそれを備えた筆記具、筆記具セット
JP5415671B2 (ja) * 2006-01-27 2014-02-12 パイロットインキ株式会社 摩擦体及びそれを備えた筆記具、筆記具セット
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JP2018001573A (ja) 2018-01-11

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