WO2018003475A1 - Friction body, writing implement, and writing implement set - Google Patents

Abstract

Provided is a friction body capable of reducing paper contamination after a strong force and / or a repetitive scratching operation, and a writing implement and a writing implement set provided with such a friction body. Provided are the friction body which discolors an image having thermochromic properties by frictional heat, comprising a styrene elastomer and having a compression set at 120°C of 80% or less and a shore A hardness of 60 to 98, and the writing implement and the writing implement set including the friction body. It is preferable for the styrene elastomer to be crosslinked.

Description

Friction body, writing instrument and writing instrument set

The present invention relates to a friction body, a writing instrument, and a writing instrument set.

2. Description of the Related Art Conventionally, there has been known a writing instrument that includes a thermochromic ink and a friction body, and is configured so that an image formed using the thermochromic ink can be rubbed with the friction body and discolored by frictional heat. ing. As the friction body, one made of an elastomer is known.

Patent Document 1 is characterized in that, in a friction body having elasticity that changes an image formed using reversible thermochromic ink from a first state to a second state by frictional heat, the friction body is made of silicone rubber. The friction body is described.

Patent Document 2 discloses a friction body that changes an image formed using a reversible thermochromic ink from a first state to a second state by frictional heat, which is a styrene-butylene-styrene copolymer or styrene-ethylene. A friction body comprising a butylene-styrene copolymer is described. According to the invention described in Patent Document 2, there is provided a friction body that can easily change color without peeling off the thermochromic image and can form a thermochromic image again on the rubbing portion without causing ink repelling. Indicate that it is obtained.

JP 2004-148744 A JP 2006-123324 A

The present inventors have developed an image having a thermochromic property (typically, an image formed on a paper surface using a thermochromic ink) with, for example, a styrenic co-polymer as described in Patent Document 2. When the color is changed by rubbing with a friction body made of coalescence, there is a problem that the paper surface is contaminated due to particularly heavy load, repeated rubbing operation, etc. (hereinafter also simply referred to as paper surface contamination). Pay attention. The present invention solves the above-mentioned problems, can discolor a thermally discolorable image satisfactorily by rubbing (that is, gives good discoloration), and also causes paper contamination due to strong force and / or repeated rubbing operations. It is an object of the present invention to provide a friction body capable of reducing the friction, and a writing instrument and a writing instrument set including such a friction body.

The present invention includes at least the following aspects.
[1] A friction body that discolors an image having thermochromic property by frictional heat,
Including styrenic elastomers,
Compression set at 120 ° C .: 80% or less, and Shore A hardness: 60 to 98,
Having a friction body.
[2] The friction body according to the first aspect, in which the styrene elastomer is crosslinked.
[3] The styrenic elastomer is selected from the group consisting of styrene-ethylene-propylene-styrene (SEPS), styrene-ethylene-ethylene-propylene-styrene (SEEPS), and styrene-ethylene-butadiene-styrene (SEBS). The friction body according to the aspect 1 or 2.
[4] The friction body according to any one of the above embodiments 1 to 3, containing 0.1 to 3.0% by mass of a lubricant.
[5] A writing instrument comprising a thermochromic ink and a friction body that discolors the handwriting of the thermochromic ink by frictional heat,
A writing instrument, wherein the friction body is the friction body according to any one of aspects 1 to 4.
[6] A writing instrument set comprising a writing instrument having a thermochromic ink and a friction body that discolors the handwriting by the thermochromic ink by frictional heat,
A writing instrument set, wherein the friction body is the friction body according to any one of aspects 1 to 4.

According to the present invention, it is possible to favorably discolor an image having thermochromic properties by rubbing (that is, to give good discoloration), and to reduce paper contamination due to strong force and / or repeated rubbing operations. Possible friction bodies, and writing instruments and writing instrument sets comprising such friction bodies are provided.

It is a fragmentary sectional view of the writing instrument which concerns on one embodiment of this invention. It is a perspective view of the friction body which concerns on one embodiment of this invention. It is a perspective view of the friction body which concerns on one Embodiment of this invention.

Hereinafter, exemplary embodiments of the present invention will be described, but the present invention is not limited to these embodiments. It should be noted that the various characteristic values described in the present disclosure are measured by the method described in the [Example] section of the present disclosure or a method understood by those skilled in the art to be equivalent thereto unless otherwise specified. Is intended to be the value of

<Friction body>
One embodiment of the present invention provides:
A friction body that discolors an image having thermochromic properties by frictional heat,
Including styrenic elastomers,
Compression set at 120 ° C .: 80% or less, and Shore A hardness: 60 to 98,
It is a friction body which has.

In the present disclosure, “thermochromic image” means that a predetermined color (first color) is maintained at room temperature (for example, 25 ° C.) and another color (for example, 60 ° C.) is heated to a predetermined temperature (for example, 60 ° C.). 2nd color), and optionally, after that, when cooled to a predetermined temperature (for example, −5 ° C.), it means an image having the property of returning to the original color (first color) again. An image having thermochromic properties can typically be formed using a thermochromic ink described below.

When an image having thermochromic properties is discolored by rubbing with a friction body, the cause of paper contamination due to particularly strong force and / or repeated frictional operation is not clear. However, when the surface temperature of the friction body is increased during rubbing, the present inventors change the physical properties of the friction body, causing the friction body to break down (specifically, local peeling), and The adhesion is presumed to be the cause of paper contamination, and because the elastomer is softened, the force applied to the paper surface at the time of rubbing becomes uneven, and when trying to completely discolor the ink, a strong local force is generated. It was speculated that the fact that the thermochromic color material was destroyed due to the ink was also the cause of paper contamination. And it has been found that controlling the deformation recovery property of the friction body, particularly in a high temperature region, is effective in reducing the above-described destruction of the friction body.

The friction body provided by one embodiment of the present invention has an appropriate hardness and exhibits good deformation recovery even at high temperatures by controlling the balance between Shore A hardness and compression set in a high temperature region. Therefore, an image having thermal discoloration can be favorably discolored by rubbing (that is, good discoloration is given), and the frictional body is not easily destroyed due to strong force and / or repeated rubbing operation. Can be reduced.

The friction body has a compression set at 120 ° C. (also referred to as “120 ° C. compression set” in the present disclosure): 80% or less. A small compression set at 120 ° C. is an indicator of a good deformation recovery property of the friction body under the scratching condition (that is, under a high temperature condition), and this good deformation recovery property is particularly determined under the scratching condition of the friction body ( That is, it contributes to maintaining good abrasion resistance under high temperature conditions).

The 120 ° C. compression set is 80% or less, 70% or less, or 60% or less from the viewpoint of good wear resistance under high temperature conditions of the friction body. The 120 ° C. compression set is preferably as small as possible from the viewpoint of wear resistance under high temperature conditions. In the present disclosure, the compression set is a value measured in accordance with JIS K6262-2013.

Generally, the compression set of a molded body formed from an elastomer tends to increase with increasing temperature. The friction body of the present disclosure has a small 120 ° C. compression set as in the specific range. From the viewpoint of obtaining such a 120 ° C. compression set, it is advantageous to reduce the temperature dependence of the compression set in the friction body. In the friction body, the ratio (A) / (B) of the compression set (A) at 120 ° C. to the compression set (B) at 70 ° C. is 1.0 or more and 1.7 or less, 1.0 or more and 1.5 or less. Hereinafter, it may be 1.0 or more and 1.4 or less, or 1.0 or more and 1.3 or less.

The friction body has a Shore A hardness of 60 to 98. The Shore A hardness is 60 or more, 70 or more, or 80 or more from the viewpoint of good discoloration of an image having thermochromic properties and good wear resistance of the friction body. The Shore A hardness is 98 or less, 95 or less, or 90 or less from the viewpoint that the contact area with the paper surface can be increased by pressing the friction body against the paper surface, and therefore good discoloration can be easily obtained. It may be. In the present disclosure, the Shore A hardness is a value measured according to JIS K 6253-3-2012.

The composition of the material components constituting the friction body of the present disclosure is designed to give the desired 120 ° C. compression set and Shore A hardness as described above. The friction body typically includes an elastomer component and an additive component. Hereinafter, examples of material components suitable for forming a friction body in which both the 120 ° C. compression set and the Shore A hardness are controlled within a desired range of the present disclosure will be described. Is not limited.

[Elastomer component (component (A))]
Examples of the elastomer component include styrene-based elastomers, polyester-based elastomers, and olefin-based elastomers, but the elastomer component is a styrene-based elastomer in that the desired 120 ° C. compression set and Shore A hardness can be easily realized. Preferably, it consists of a styrene-type elastomer.

In the present disclosure, the “styrene elastomer” means an elastomer containing a styrene constituent unit in the main chain, and is typically a thermoplastic elastomer. In view of easy realization of desired 120 ° C. compression set and Shore A hardness, the styrenic elastomer is composed of a polymer block mainly composed of structural units derived from a styrene skeleton-containing compound and a conjugated diene compound. A block copolymer having a polymer block mainly composed of units (hereinafter referred to as a styrene block copolymer), a hydrogenated product of the block copolymer, or a mixture thereof is preferable. The “polymer block mainly composed of a structural unit derived from a styrene skeleton-containing compound (or conjugated diene compound)” means that the structural unit present in the highest mass ratio in the polymer block is a styrene skeleton-containing compound ( Or a polymer block which is a structural unit derived from a conjugated diene compound).

The styrenic block copolymer is usually one or more polymer blocks X mainly composed of structural units derived from a styrene skeleton-containing compound, preferably two or more from the viewpoint of mechanical properties, and a conjugated diene compound. It is a block copolymer having one or more polymer blocks Y mainly composed of derived structural units. For example, a block copolymer having a structure such as XY, XYX, YXYX, and XYXYX can be given.

The hydrogenated product of the styrene block copolymer can be obtained by adding hydrogen to the carbon / carbon double bond in the styrene block copolymer to form a carbon / carbon single bond. The hydrogenation can be performed by a known method, for example, by hydrogenation using a hydrogenation catalyst in an inert solvent.

Hydrogenation rate of hydrogenated product of the above styrenic block copolymer (that is, carbon / carbon single bond produced by hydrogenation relative to the number of carbon / carbon double bonds in the styrene block copolymer before hydrogenation) May be 50% or more, 70% or more, or 90% or more from the viewpoint of improvement in erasing performance, paper surface contamination resistance, and wear resistance. The above hydrogenation rate means a value measured by ¹ H-NMR unless otherwise specified.

The styrene skeleton-containing compound is a polymerizable monomer having a polymerizable carbon / carbon double bond and an aromatic ring. Examples of the styrene skeleton-containing compound include styrene, t-butylstyrene, α-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N-diethyl-p-aminoethylstyrene, and p-tert-butylstyrene. And alkylstyrene in which at least one of the alkyl groups having 1 to 8 carbon atoms is bonded to the benzene ring. Among these, styrene and alkylstyrene in which at least one alkyl group having 1 to 8 carbon atoms is bonded to the benzene ring are preferable. One or more of these can be used as the styrene skeleton-containing compound.

Examples of the alkyl styrene in which at least one of the alkyl groups having 1 to 8 carbon atoms is bonded to the benzene ring include, for example, o-alkyl styrene, m-alkyl styrene, p-alkyl styrene, 2,4-dialkyl styrene, 3, Alkyl styrenes such as 5-dialkyl styrene and 2,4,6-trialkyl styrene, and halogenated alkyl styrenes in which one or more hydrogen atoms of the alkyl group in these alkyl styrenes are substituted with halogen atoms , Etc. More specifically, for example, 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, o-chloromethylstyrene, m -Chloromethylstyrene, p-chloromethylstyrene, 2,4-bis (chloromethyl) styrene, 3,5-bis (c Romechiru) styrene, 2,4,6-tri (chloromethyl) styrene, o- dichloro-methylstyrene, m- dichloromethyl styrene, and p- dichloro-methylstyrene, and the like. Among these, p-methylstyrene is particularly preferable from the viewpoint of crosslinkability.

The alkyl styrene in which at least one of the alkyl groups having 1 to 8 carbon atoms is bonded to the benzene ring is suitably used as a material for a crosslinked styrene elastomer.

In the polymer block X, the proportion of alkylstyrene in which at least one of the alkyl groups having 1 to 8 carbon atoms is bonded to the benzene ring is preferably 1% by mass or more, more preferably 50% by mass or more from the viewpoint of crosslinkability. Preferably, it may be 100% by mass.

The above conjugated diene compound is a polymerizable monomer having a structure in which two carbon / carbon double bonds are connected by one carbon / carbon single bond. Examples of the 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), and the like. Of these, 1,3-butadiene and isoprene are preferred. One or more of these can be used as the conjugated diene compound.

The content of the structural unit derived from the styrene skeleton-containing compound in the styrenic block copolymer or hydrogenated product thereof is not particularly limited, but from the viewpoint of mechanical strength, cold resistance, heat resistance, and flexibility, 5 It may be ˜50 mass%, or 20˜40 mass%.

The polymer block X is preferably a polymer block derived only from the styrene skeleton-containing compound or a copolymer block of the styrene skeleton-containing compound and the conjugated diene compound. When the polymer block X is the copolymer block, the content of the structural unit derived from the styrene skeleton-containing compound in the polymer block X in the copolymer block is not particularly limited, From the viewpoint of heat resistance, it is usually 50% by mass or more, and may be 70% by mass or more, or 90% by mass or more. The distribution of the structural unit derived from the conjugated diene compound in the polymer block X is not particularly limited. When two or more polymer blocks X are present in the styrene elastomer molecule, these may have the same structure or different structures.

The polymer block Y is preferably a polymer block composed only of the conjugated diene compound or a copolymer block of the styrene skeleton-containing compound and the conjugated diene compound. When the polymer block Y is the copolymer block, the content of the structural unit derived from the conjugated diene compound in the polymer block Y in the copolymer block is not particularly limited. From a viewpoint of property, it is 50 mass% or more normally, and may be 70 mass% or more, or 90 mass% or more. The distribution of the structural unit derived from the styrene skeleton-containing compound in the polymer block Y is not particularly limited. The bonding mode between the conjugated diene compound and the styrene skeleton-containing compound is not particularly limited. When two or more polymer blocks Y are present in the styrene elastomer molecule, these may have the same structure or different structures.

Examples of the styrene block copolymer include styrene-butadiene-styrene block copolymer (SBS) and styrene-isoprene-styrene block copolymer (SIS).

Examples of the hydrogenated styrene block copolymer include styrene-ethylene-butene copolymer (SEB), styrene-ethylene-propylene copolymer (SEP), and styrene-ethylene-butene-styrene copolymer. (SEBS), styrene-ethylene-propylene-styrene copolymer (SEPS), and styrene-ethylene-ethylene-propylene-styrene copolymer (SEEPS).

Among these, styrene-ethylene-propylene-styrene (SEPS), styrene-ethylene-ethylene-propylene-styrene (SEEPS), and styrene-ethylene-butadiene-styrene (SEBS) are preferable, and styrene-ethylene-propylene- is particularly preferable. Styrene copolymer (SEPS) and styrene-ethylene-ethylene-propylene-styrene copolymer (SEEPS) are preferred from the viewpoint of wear resistance.

The above-mentioned styrenic block copolymers and / or hydrogenated products thereof can be used alone or in a mixture of two or more.

The styrene elastomer may be cross-linked. Increasing the degree of crosslinking contributes to a reduction in 120 ° C. compression set and an increase in Shore A hardness. In this case, SEBS, SEPS, and SEEPS in which styrene is replaced with p-methylstyrene are preferable from the viewpoints of heat resistance and wear resistance. Whether the styrenic elastomer is cross-linked is determined by visually observing whether the gel content remains after immersion in hot xylene at 120 ° C. for 24 hours, or measuring the remaining weight. Can be distinguished. For crosslinking, for example, a crosslinking agent (component (E)) described later can be used. In an exemplary embodiment, the friction body may be free of 120 ° C. hot xylene insoluble polymer other than the cross-linked styrenic elastomer. In this case, whether or not the styrene-based elastomer is crosslinked can also be evaluated by subjecting the friction body to the thermal xylene treatment.

The mass average molecular weight (Mw) of the styrene elastomer is preferably 150,000 to 500,000. The mass 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 good wear resistance. On the other hand, the mass average molecular weight may be 500,000 or less, 450,000 or less, or 400,000 or less from the viewpoint of good workability during production of the friction body. In the present disclosure, the molecular weight means a value in terms of polystyrene measured by a gel permeation chromatography (GPC) method unless otherwise specified.

[Other ingredients]
Other components include, for example, a propylene resin (hereinafter referred to as component (B)), a rubber softener (hereinafter referred to as component (C)), a lubricant (hereinafter referred to as component (D)), a crosslinking agent (hereinafter referred to as component ( E)), a crosslinking aid (hereinafter referred to as component (F)), a colorant (hereinafter referred to as component (G)), a polymer component other than the propylene-based resin, a stabilizer, a filler, etc. it can.

[Propylene resin (component (B))]
Use of the propylene-based resin (component (B)) is advantageous in improving the wear resistance and paper surface contamination resistance of the friction body. As said component (B), a propylene homopolymer, a propylene-type random copolymer, and a propylene-type block copolymer can be illustrated, and these can be used 1 type or in combination of 2 or more types. From the viewpoint of heat resistance, a propylene homopolymer and a propylene-based block copolymer are more preferable, and a propylene homopolymer is still more preferable.

The propylene homopolymer is a polymer composed of only propylene units, and is most preferable as the component (B) because of high crystallinity and melting point.

Examples of the propylene random copolymer include a propylene / ethylene random copolymer obtained by copolymerizing propylene and ethylene, and a copolymer obtained by copolymerizing propylene and at least one α-olefin having 4 to 20 carbon atoms. Examples include propylene / α-olefin random copolymers and propylene / ethylene / α-olefin random copolymers obtained by copolymerizing propylene, ethylene and at least one α-olefin having 4 to 20 carbon atoms. it can.

Examples of the α-olefin 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-butene, Nonene, 1-decene, 1-undecene, and 1-dodecene, and the like. The α-olefin having 4 to 20 carbon atoms is preferably 1-butene, 1-pentene, 1-hexene and 1-octene, more preferably 1-butene and 1-hexene.

Specific examples of the propylene-based random copolymer include, for example, propylene-ethylene random copolymer, propylene-1-butene random copolymer, propylene-1-hexene random copolymer, propylene-1-octene random copolymer And a propylene-ethylene-1-butene random copolymer, a propylene-ethylene-1-hexene random copolymer, a propylene-ethylene-1-octene random copolymer, and the like, preferably propylene-ethylene random Copolymer, propylene-1-butene random copolymer, propylene-1-hexene random copolymer, propylene-ethylene-1-butene random copolymer, propylene-ethylene-1-hexene random copolymer, etc. It is.

Examples of the propylene block copolymer include a block copolymer composed of a crystalline propylene polymer portion and an amorphous propylene / α-olefin copolymer portion.

Examples of the crystalline propylene polymer include a homopolymer of propylene or a random copolymer of propylene and a small amount of other α-olefin.

On the other hand, examples of the amorphous propylene / α-olefin copolymer include an amorphous random copolymer of propylene and another α-olefin. Other α-olefins preferably have 2 or 4 to 12 carbon atoms, and specific examples include ethylene, 1-butene, 3-methyl-1-butene, 3-methyl-1-pentene, and 4-methyl. -1-pentene, 4,4-dimethyl-1-pentene, vinylcyclopentane, vinylcyclohexane, and the like. These α-olefins can be used alone or in combination of two or more.

As propylene-based block copolymers, in addition to the above other α-olefins, 1,4-hexadiene, 5-methyl-1,5-hexadiene, 1,4-octadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, A ternary or quaternary or higher copolymer obtained by copolymerization of a non-conjugated diene such as 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, and 5-isopropenyl-2-norbornene. Copolymers can also be used.

From the viewpoint of moldability, the melt mass flow rate of the component (B) is 0.01 to 100 g / 10 min, 0 when measured under the conditions of 230 ° C. and 21.18 N in accordance with JIS K 7210-1999. It may be from 1 to 50 g / 10 min, or from 0.3 to 10 g / 10 min.

The melting point of the component (B) may be 150 ° C. or higher, or 160 ° C. or higher from the viewpoint of heat resistance. Although the upper limit of melting | fusing point is not restrict | limited in particular, Since it is a polypropylene resin, about 167 degreeC is an upper limit, for example. The melting point is determined by using a DSC type differential scanning calorimeter (for example, Diamond of Perkin Elmer Japan Co., Ltd.), maintained at 230 ° C. for 5 minutes → cooled to −10 ° C. at 10 ° C./minute→held at −10 ° C. for 5 minutes. → In the second melting curve (that is, the melting curve measured in the last heating process) measured with a program of raising the temperature to 230 ° C. at 10 ° C./min, the peak top melting point of the peak appearing on the highest temperature side is intended To do.

The compounding amount of the component (B) may be 30 to 300 parts by mass, 35 to 250 parts by mass, or 40 to 180 parts by mass with respect to 100 parts by mass of the component (A). By being in this range, the balance of flexibility, abrasion resistance, and paper surface contamination resistance is improved.

[Rubber softener (component (C))]
As the rubber softener (component (C)), various compounds that can be understood by those skilled in the art to function as softeners in the art can be used. Use of component (C) is advantageous in improving the flexibility of the friction body. The component (C) is typically a non-aromatic rubber softener. Examples of non-aromatic rubber softeners are non-aromatic mineral oils (that is, hydrocarbon compounds derived from petroleum, etc., and are not classified as aromatic in the later-described classification (that is, the number of aromatic carbons is Less than 30%)) or non-aromatic synthetic oils (ie, synthetic hydrocarbon compounds that do not use aromatic monomers). The non-aromatic rubber softener is usually liquid, gel or gum at normal temperature.

The mineral oil used as component (C) is a mixture of compounds having one or more of a paraffin chain, a naphthene ring, and an aromatic ring, and those having a naphthene ring of 30 to 45% based on the number of carbon atoms are naphthenic minerals. Oils and oils with 30% or more aromatic rings are called aromatic mineral oils, do not belong to naphthenic mineral oils or aromatic mineral oils, and have 50% or more paraffin chains on a carbon number basis Is called paraffinic mineral oil.

Examples of the component (C) include paraffinic mineral oils such as linear saturated hydrocarbons, branched saturated hydrocarbons, and derivatives thereof; naphthenic mineral oils; hydrogenated polyisobutylene, polyisobutylene, and polybutene. Synthetic oils, and the like. Among these, paraffinic mineral oil is preferable from the viewpoint of compatibility with the elastomer component, and paraffinic mineral oil having a small number of aromatic carbon atoms is more preferable. From the viewpoint of handleability, those which are liquid at room temperature are preferred.

From the viewpoint of heat resistance and handleability, the dynamic viscosity of the component (C) measured at 37.8 ° C. according to JIS K2283-2000 may be 20 to 1000 cSt, or 50 to 500 cSt. From the viewpoint of handleability, the pour point of component (C) measured in accordance with JIS K2269-1987 may be -10 to -25 ° C. Further, from the viewpoint of safety, the flash point (COC) of the component (C) measured in accordance with JIS K2265-2007 may be 170 to 300 ° C.

The blending amount of the component (C) is 1 to 400 parts by weight, 10 to 250 parts by weight, or 40 to 180 parts by weight with respect to 100 parts by weight of the component (A) from the viewpoint of the balance between flexibility and mechanical properties. Part.

[Lubricant (Component (D))]
As the lubricant (component (D)), various compounds that are understood by those skilled in the art to function as lubricants in the art can be used. The use of component (D) is advantageous in terms of mold releasability and suppression of paper surface friction.

Examples of the component (D) include silicone compounds, fluorine compounds, surfactants, and the like, and silicone compounds are preferable from the viewpoint of suppressing friction on the paper surface.

As the silicone compound, silicone oil, silicone gum and the like can be used. Among these, those having a high molecular weight are preferable from the viewpoint of heat resistance, bleed resistance, and suppression of friction on paper. However, since a high molecular weight silicone compound generally has a high-viscosity liquid or a gum shape and tends to have poor handling properties, a blend with a resin or a copolymer with a resin is suitable for use. The resin used here is selected in consideration of compatibility with other components constituting the friction body, particularly the component (A). Generally, olefin resins such as polyethylene and polypropylene are suitable. It is.

Polyvinylidene fluoride, polyvinyl fluoride, etc. can be used as the fluorine compound. Among these, polyvinylidene fluoride is preferable from the viewpoint of suppressing friction on the paper surface.

Any of anionic, cationic and nonionic surfactants can be used as the surfactant.

The blending amount of the component (D) is 0.1 to 30 parts by mass, 0.5 to 20 parts by mass, or 1 to 10 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of suppressing friction on the paper surface. Part.

The content of component (D) in the friction body (content of silicone oil in a preferred embodiment, or content of fluorine-based compound in another preferred embodiment) is preferably 0.1 to 3.0% by mass. . The content may be 0.1% by mass or more, 0.3% by mass or more, or 0.5% by mass or more from the viewpoint of suppressing friction on the paper surface, and has good erasing performance and paper surface contamination resistance. From the viewpoint of obtaining, it may be 3.0% by mass or less, 2.5% by mass or less, or 2.0% by mass or less.

[Crosslinking agent (component (E))]
As the crosslinking agent (component (E)), various compounds that are understood by those skilled in the art to function as a crosslinking agent in the art can be used. In the friction body, the component (E) is blended mainly for the purpose of crosslinking the component (A). The use of component (E) is advantageous in reducing 120 ° C. compression set and increasing Shore A hardness.

Examples of the component (E) include organic peroxides and phenolic compounds, and organic peroxides are preferable from the viewpoint of wear resistance.

The organic peroxide is a compound in which one or two hydrogen atoms of hydrogen peroxide are substituted with a free organic group. Since the organic peroxide has a peroxide bond in the molecule, a radical is generated during the production of the friction body (for example, when the material composition is melt-kneaded), and the radical reacts in a chain reaction. It functions to crosslink the component (A).

Examples of the organic peroxide 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-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert -Butylperoxyisopropyl carbonate, diacetyl peroxide, laur Yl peroxide, and tert- butyl cumyl peroxide, and the like. Among these, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane and 2,5-dimethyl-2 are used from the viewpoint of low odor, low coloring and scorch safety. , 5-Di- (tert-butylperoxy) hexyne-3 is preferred.

In addition, when using an organic peroxide as a component (E), it is preferable to also use the below-mentioned crosslinking adjuvant (component (F)). By using the component (F), a uniform and efficient crosslinking reaction can be performed.

The phenolic compound is preferably a resol resin from the viewpoint that it is usually liquid. Resole resins are made by condensation of alkyl-substituted phenols or unsubstituted phenols with aldehydes (preferably formaldehyde) in an alkaline medium, or condensation of bifunctional phenol dialcohols. The alkyl substituent portion of the alkyl substituted phenol typically has 1 to 10 carbon atoms. Preference is given to dimethylolphenol or phenolic resins substituted with alkyl groups having 1 to 10 carbon atoms in the p-position.

Among the above phenolic compounds, alkylphenol formaldehyde resins, methylolated alkylphenol resins, brominated alkylphenol resins, and the like are preferable. From the environmental point of view, a non-brominated material is desirable, but it may be a brominated terminal hydroxyl group. In particular, an alkylphenol formaldehyde resin is preferable.

The compounding amount of the component (E) may be 0.01 to 20 parts by mass, 0.1 to 10 parts by mass, or 0.5 to 5 parts by mass with respect to 100 parts by mass of the component (A). Being equal to or higher than the above lower limit value is preferable in that the crosslinking reaction proceeds favorably. On the other hand, being equal to or lower than the upper limit value is preferable in terms of maintaining good moldability without excessive crosslinking.

[Crosslinking aid (component (F))]
As the crosslinking aid (component (F)), various compounds that are understood by those skilled in the art to function as a crosslinking aid or a crosslinking accelerator in the art can be used.

Examples of the component (F) include polyethylene glycol diacrylate having 9 to 14 repeating units of triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and ethylene glycol. Polyfunctional methacrylate compounds such as methacrylate, trimethylolpropane trimethacrylate, allyl methacrylate, 2-methyl-1,8-octanediol dimethacrylate, 1,9-nonanediol dimethacrylate, etc .; polyethylene glycol diacrylate, 1 , 6-hexanediol diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate, etc. Polyfunctional acrylate compounds; polyfunctional vinyl compounds such as vinyl butyrate or vinyl stearate; and the like. One or more of these can be used as the component (F).

Among the above components (F), polyfunctional acrylate compounds and polyfunctional methacrylate compounds are preferable, and triallyl cyanurate, triethylene glycol dimethacrylate, and tetraethylene glycol dimethacrylate are particularly preferable. These compounds are easy to handle, have an organic peroxide solubilizing action, and act as a dispersion aid for organic peroxides. Therefore, when used in combination with organic peroxides, crosslinking is more uniform. And can be effective.

The compounding amount of the component (F) may be 0.01 to 50 parts by mass, 0.5 to 30 parts by mass, or 1 to 20 parts by mass with respect to 100 parts by mass of the component (A). Being above the lower limit is preferable in that the crosslinking reaction proceeds favorably. On the other hand, being not more than the upper limit is that crosslinking does not proceed excessively and the dispersion of the cross-linked product in the friction body is good. It is preferable at the point maintained.

[Colorant (component (G))]
As the colorant (component (G)), various compounds that are understood by those skilled in the art to function as a colorant in the art can be used. As the component (G), inorganic pigments, organic pigments and the like are preferable.

<Manufacture of friction body>
Although a friction body is not limited to this, For example, it can manufacture with the following method. First, a material composition is prepared by mechanically melting and kneading the above material components. For the melt-kneading, a general melt-kneader such as a Banbury mixer, various kneaders, a single-screw or twin-screw extruder can be used. Next, the obtained material composition is molded by a general thermoplastic resin molding method such as injection molding, extrusion molding, blow molding or the like, whereby a friction body having a desired shape can be obtained. An example of a suitable shape of the friction body will be described later with reference to the drawings.

<Writing instrument and writing instrument set>
The present disclosure also includes a writing instrument and a writing instrument set including the friction body described above.

Another aspect of the present invention provides:
A writing instrument having a thermochromic ink and a friction body that discolors the handwriting by the thermochromic ink by frictional heat,
A writing instrument is provided in which the friction body is a friction body of the present disclosure.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. Corresponding components are marked with common reference numerals throughout the drawings.

FIG. 1 is a partial cross-sectional view of a writing instrument according to an embodiment of the present invention. The writing instrument 1 includes a shaft cylinder 2 formed in a cylindrical shape, a refill (not shown) that is a writing body disposed in the shaft cylinder 2 and provided with a writing section 3 at one end, and a shaft via a holding member 4. A friction body 5 provided at the rear end of the cylinder 2, a cover member 6 that covers the friction body 5 and can be attached to and detached from the friction body 5, and is attached to a side surface of the rear end of the shaft cylinder 2 and an article. And a clip 7 to be gripped. In the present disclosure, in the axial direction of the writing instrument 1, the writing unit 3 side is defined as the “front” side, and the opposite side of the writing unit 3 is defined as the “rear” side. Unless otherwise specified, the central axis refers to the central axis of the writing instrument 1.

The writing instrument 1 is a thermochromic writing instrument that contains thermochromic ink in a refill, and the handwriting of the writing instrument 1 can be discolored by frictional heat generated when it is rubbed by the friction body 5.

The friction body 5 can move with respect to the shaft cylinder 2 by pressing forward. In the writing instrument 1, the refill moves in the axial direction in the axial cylinder 2 by a knocking operation that presses the friction body 5 forward against the urging force of the spring arranged in the axial cylinder 2. At this time, a state where the writing unit 3 protrudes from the shaft cylinder 2 is referred to as a writing state (FIG. 1), and a state where the writing unit 3 is immersed in the shaft tube 2 is referred to as a non-writing state (not shown).

FIG. 2 is a perspective view of the friction body 5 and the holding member 4 of the writing instrument 1. In FIG. 2, the lower side is the front side of the writing instrument 1. The friction body 5 is provided to the holding member 4 by fitting or two-color molding.

The friction body 5 is formed in a tapered truncated triangular pyramid shape having a substantially triangular cross-sectional shape. Specifically, in the cross section, the apex of the triangle is formed in a circular arc shape, and the radius of curvature of the arc is larger on the rear end side of the friction body 5. The rear end surface 5a of the friction body 5 is formed in a curved surface shape. Therefore, the boundary between the rear end surface 5a and the peripheral surface 5b of the friction body 5 forms a ridge 5c.

In the friction body 5, a wider area can be scraped by using the rear end face 5a. Further, the friction body 5 can scrape a wider area by using the portion of the ridge line 5c corresponding to the side of the triangle, and can reduce a smaller area by using the portion corresponding to the vertex of the triangle. Can be scraped. That is, the fact that the friction body has one or more corners (such as the apex of the triangle) as viewed from the axial direction means that both a wider area and a narrower area are excellently scratched. Is advantageous. As a matter of course, the cross-sectional shape is not limited to a triangle, and may be other polygons such as a quadrangle and a hexagon.

In addition, you may provide a friction body not in the rear-end part of the axial cylinder 2, but in the other part of the writing instrument 1, for example, the front-end part of the axial cylinder 2, or the clip 7. FIG. Moreover, you may provide a friction body in the rear-end part of the axial cylinder of a thermochromic writing instrument other than a knock type writing instrument as shown in FIG. 1, for example, a cap type writing instrument, or the top part of a cap.

Another aspect of the present invention provides:
A writing instrument set comprising a writing instrument having a thermochromic ink, and a friction body that discolors the handwriting by the thermochromic ink by frictional heat,
A writing instrument set is provided in which the friction body is the friction body of the present disclosure.

The friction body of the present disclosure may be provided separately from the writing instrument having the thermochromic ink and may be a writing instrument set including the writing instrument and the friction body. FIG. 3 is a perspective view of a separate friction body 10. In FIG. 3, the friction body 10 has a rectangular parallelepiped shape accommodated in the case 11, but may be a cubic shape or a cylindrical shape.

[Thermochromic ink]
The writing instrument of the present disclosure has a thermochromic ink. In the present disclosure, the “thermochromic ink” means a predetermined color (first color) at room temperature (for example, 25 ° C.) and another color (second color) when the temperature is raised to a predetermined temperature (for example, 60 ° C.). An ink having a property of returning to the original color (first color) when it is cooled to a predetermined temperature (for example, −5 ° C.) and then optionally cooled to a predetermined temperature (for example, −5 ° C.). It is possible to design colors according to applications, such as a combination in which one of the first color and the second color is colored and the other is colorless, and a combination in which the first color and the second color are colored.

The thermochromic ink contains a thermochromic color material. As the thermochromic microcapsule pigment that becomes a thermochromic color material, those that change color due to heat such as frictional heat, for example, those that have a function from colored to colorless, colored to colored, colorless to colored, etc. There are no particular limitations, and various types can be used. Examples include microencapsulated thermochromic compositions containing at least a leuco dye, a developer, and a color change temperature adjusting agent.

The leuco dye that can be used is not particularly limited as long as it is an electron-donating dye and functions as a color former. Specifically, from the viewpoint of obtaining an ink having excellent color development characteristics, conventionally known ones such as triphenylmethane, spiropyran, fluorane, diphenylmethane, rhodamine lactam, indolylphthalide, leucooramine, It can be used alone (one kind) or in a mixture of two or more kinds (hereinafter simply referred to as “at least one kind”).

The developer that can be used is a component having the ability to develop the leuco dye, such as a phenol resin compound, a salicylic acid metal chloride, a salicylic acid resin metal salt compound, a solid acid compound, etc. Is mentioned.

The amount of the developer to be used may be arbitrarily selected according to the desired color density, and is not particularly limited, but is usually 0.1 to 1 part by weight with respect to 1 part by mass of the leuco dye described above. It is preferable to select within a range of about 100 parts by mass.

The color change temperature adjusting agent that can be used is a substance that controls the color change temperature in the coloration of the leuco dye and the developer. Conventionally known color change temperature adjusting agents can be used. Specific examples include alcohols, esters, ketones, ethers, acid amides, azomethines, fatty acids, hydrocarbons and the like.

The amount of the color-change temperature adjusting agent used may be appropriately selected according to the desired hysteresis width and color density at the time of color development, and is not particularly limited, but is usually based on 1 part by mass of the leuco dye. It is preferably used within the range of about 1 to 100 parts by mass.

The thermochromic microcapsule pigment is obtained by microencapsulating a thermochromic composition containing at least the leuco dye, the developer, and the color change temperature adjusting agent so that the average particle diameter is 0.2 to 3 μm. Can be manufactured. Examples of the microencapsulation method include interfacial polymerization method, interfacial polycondensation method, in situ polymerization method, liquid curing coating method, phase separation method from aqueous solution, phase separation method from organic solvent, melt dispersion cooling method, air A suspension coating method, a spray drying method, etc. can be mentioned, and can be appropriately selected according to the application.

The content of these leuco dyes, developer, and color change temperature adjusting agent varies depending on the type of leuco dye, developer, color change temperature adjusting agent used, microencapsulation method, etc. In terms of mass ratio, the developer is 0.1 to 100, and the color change temperature adjusting agent is 1 to 100. The capsule membrane agent is 0.1 to 1 in mass ratio with respect to the capsule contents.

The thermochromic microcapsule pigment is a combination of the above-described leuco dye, color developer, and color change temperature adjusting agent, and the amount, color development temperature of each color (for example, color development at 0 ° C. or higher), decolorization temperature ( For example, it is preferable that the color disappears at a temperature of 50 ° C. or higher, and the color changes from colored to colorless by frictional heat provided by the friction body of the present disclosure.

In the thermochromic microcapsule pigment, the wall film is preferably formed of a urethane resin, a urea / urethane resin, an epoxy resin, or an amino resin from the viewpoint of further improving the drawing density, storage stability, and writing property. The thickness of the wall film of the microcapsule coloring material is appropriately determined according to the required strength of the wall film and the drawn line density.

In the thermochromic ink, in addition to the thermochromic microcapsule pigment described above, the balance is water (tap water, purified water, distilled water, ion-exchanged water, pure water, etc.), and other writing instruments (for ballpoint pens, Depending on the application of the marking pen or the like, a water-soluble organic solvent, a thickener, a lubricant, a rust inhibitor, an antiseptic or a fungicide can be appropriately contained within a range not impairing the effect.

In order to produce a thermochromic ink, a conventionally known method can be employed. For example, in addition to the thermochromic and photochromic microcapsule pigment, a predetermined amount of each component in the aqueous composition is blended. It can be obtained by stirring and mixing with a homomixer or a stirrer such as a disper. Further, if necessary, coarse particles in the thermochromic ink may be removed by filtration or centrifugation.

The viscosity value of the thermochromic ink is preferably 500 to 2000 mPa · s at 25 ° C. and a shear rate of 3.83 / s, and 20 to 100 mPa · s at a shear rate of 383 / s. By setting the viscosity within the above range, it is possible to obtain an ink excellent in writing property and stability over time.

The surface tension of the thermochromic ink is preferably 25 to 45 mN / m, more preferably 30 to 40 mN / m. Within this range, the balance between the inside of the nib and the wettability of the ink becomes appropriate, and the occurrence of ink back can be prevented.

Further details of the thermochromic ink are described in, for example, Japanese Patent Application Laid-Open No. 2015-229708, International Publication No. 2015/033750, International Publication No. 2011/070966, and the like.

Hereinafter, specific embodiments of the present invention will be further described with reference to examples, but the present invention is not limited to the examples.

<Materials used>

Ingredient (A)
(A-1) Kuraray Co., Ltd. Septon 4077 (trade name)
SEEPS, mass average molecular weight 330,000
(A-2) Kuraray Co., Ltd. Septon 4055 (trade name)
SEEPS, weight average molecular weight 260,000
(A-3) Kuraray Co., Ltd. Septon 2005 (trade name)
SEPS, weight average molecular weight 250,000
(A-4) Clayton Polymer Co., Ltd. Clayton G1651H (trade name)
SEBS, mass average molecular weight 260,000
(A-5) Kuraray Co., Ltd. Septon V9461 (trade name)
SEEPS with styrene replaced by p-methylstyrene, weight average molecular weight 300,000
(A-6) Kuraray Co., Ltd. Septon V9827 (trade name)
SEBS with styrene replaced by p-methylstyrene, weight average molecular weight 90,000
(A-7) Kuraray Co., Ltd. Septon 4033 (trade name)
SEEPS, weight average molecular weight 100,000
(A-8) Dow Chemical Company Engage EG8100 (trade name)
Ethylene-α olefin copolymer elastomer

Ingredient (B)
(B-1) Sun Allomer VS200A (trade name)
Propylene homopolymer, MFR 0.5, melting point 165 ° C
(B-2) Sun Allomer Co., Ltd. PM940M (trade name)
Propylene-ethylene random copolymer, MFR30, melting point 136 ° C

Ingredient (C)
(C-1) Idemitsu Kosan Co., Ltd. Dyna Process Oil PW-380 (trade name)
Paraffin mineral oil

Ingredient (D)
(D-1) Toray Dow Corning Co., Ltd. BY27-001 (trade name)
Silicone compound (alloy product of polypropylene and ultra high molecular weight silicone polymer, ultra high molecular weight silicone polymer ratio 50wt%)
(D-2) Daikin Industries, Ltd. NEOFLON ETFE (trade name)
Fluorine compound (copolymer of tetrafluoroethylene and ethylene)

Ingredient (E)
(E-1) NOF Corporation Perhexa 25B (trade name)
Organic peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane

Ingredient (F)
(F-1) Nippon Kasei Corporation TAIC (trade name)
Triallyl isocyanurate

<Production of friction body>
A material composition containing the components shown in Table 1 was kneaded with a twin screw extruder to obtain a friction body.

<Evaluation>
(Mass average molecular weight of elastomer component)
The mass average molecular weights of (A-1) to (A-7) were measured using gel permeation chromatography (manufactured by JASCO Corporation, high performance liquid chromatography system “LC-2000Plus (trade name)”) with chloroform as the mobile phase. Obtained in terms of standard polystyrene.

(Friction body evaluation)
Compression set In accordance with JIS K6262-2013, a small test piece was prepared from a 6.3 mm thick press sheet, and compression set at 70 ° C. × 22 hours and 120 ° C. × 72 hours at a compression rate of 25%. Was measured.

Shore A hardness In accordance with JIS K 6253-3-2012, a 6.3 mm-thick press sheet was measured using a durometer type A after 15 seconds.

Discoloration property A sample piece was prepared by uniformly stretching the thermochromic ink with a bar coater (No. 6 manufactured by Yasuda Seiki Co., Ltd.) on a test paper specified in ISO12757-1. After the sample piece was sufficiently dried, the friction body was brought into contact with the paper surface at 60 degrees, and the paper surface was rubbed back and forth while maintaining a speed of about 8 to 10 m / sec under a load of 5 N. Thereafter, the rubbing portion was measured for a contamination grade Ns value with a spectrocolorimeter (SC-P manufactured by Suga Test Instruments Co., Ltd.), and the discoloration was evaluated according to the following criteria.
A: Ns value 4.0 or more B: Ns value 3.0 or more to less than 4.0 C: Ns value 2.0 or more to less than 3.0 D: Ns value less than 2.0

Contamination resistance The friction body is pressed against the paper (test paper specified in ISO12757-1) at an angle of 60 to 90 degrees, and the speed of about 8 to 10 m / sec is maintained under a load of about 15 to 20 N. In this state, a contamination test was conducted by reciprocating rubbing and confirming that there was no adhesion of debris on the paper surface or destruction of the paper surface itself, and the contamination resistance was evaluated according to the following criteria.
A: A state where no adhesion of debris or destruction of the paper surface itself is observed on the paper surface B: A state where a small amount of adhesion of debris or destruction of the paper surface itself is observed D: Debris adhesion or paper surface itself on the paper surface State of destruction

The friction body of the present disclosure is suitably used in a writing instrument or a writing instrument set configured to discolor thermochromic handwriting by frictional heat.

DESCRIPTION OF SYMBOLS 1 Writing instrument 2 Shaft cylinder 3 Writing part 4 Holding member 5 Friction body 6 Cover member 7 Clip 10 Friction body 11 Case

Claims (6)

1. A friction body that discolors an image having thermochromic properties by frictional heat,
   Including styrenic elastomers,
   Compression set at 120 ° C .: 80% or less, and Shore A hardness: 60 to 98,
   Having a friction body.
2. The friction body according to claim 1, wherein the styrenic elastomer is crosslinked.
3. The styrenic elastomer is selected from the group consisting of styrene-ethylene-propylene-styrene (SEPS), styrene-ethylene-ethylene-propylene-styrene (SEEPS), and styrene-ethylene-butadiene-styrene (SEBS). The friction body according to 1 or 2.
4. The friction body according to any one of claims 1 to 3, comprising 0.1 to 3.0 mass% of a lubricant.
5. A writing instrument having a thermochromic ink and a friction body that discolors the handwriting by the thermochromic ink by frictional heat,
   A writing instrument, wherein the friction body is the friction body according to any one of claims 1 to 4.
6. A writing instrument set comprising a writing instrument having a thermochromic ink, and a friction body that discolors the handwriting by the thermochromic ink by frictional heat,
   A writing instrument set, wherein the friction body is the friction body according to any one of claims 1 to 4.

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