JP2021100804A5 - - Google Patents
Download PDFInfo
- Publication number
- JP2021100804A5 JP2021100804A5 JP2019232852A JP2019232852A JP2021100804A5 JP 2021100804 A5 JP2021100804 A5 JP 2021100804A5 JP 2019232852 A JP2019232852 A JP 2019232852A JP 2019232852 A JP2019232852 A JP 2019232852A JP 2021100804 A5 JP2021100804 A5 JP 2021100804A5
- Authority
- JP
- Japan
- Prior art keywords
- friction body
- methyl
- pentene
- writing instrument
- shore
- 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.)
- Granted
Links
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 30
- 239000011342 resin composition Substances 0.000 claims description 18
- 239000004711 α-olefin Substances 0.000 claims description 14
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 13
- 229920000098 polyolefin Polymers 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 6
- 210000004283 incisor Anatomy 0.000 claims description 5
- 238000005259 measurement Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- 239000000049 pigment Substances 0.000 claims description 4
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 3
- 238000001746 injection moulding Methods 0.000 claims description 2
- 239000002932 luster Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000003094 microcapsule Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- 239000004713 Cyclic olefin copolymer Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
Description
本発明は、４－メチル－１－ペンテン・α－オレフィン共重合体を含む摩擦体用樹脂組成物及び摩擦体と、摩擦体を備えた筆記具に関する。詳細には黒鉛や熱変色性インキ等による筆跡や印刷像等を摩擦により熱変色させるための摩擦体用樹脂組成物及び摩擦体と、摩擦体を備えた筆記具に関する。 The present invention relates to a friction body resin composition containing a 4-methyl-1-pentene/α-olefin copolymer , a friction body, and a writing instrument having the friction body. More particularly, the present invention relates to a resin composition for a friction body, a friction body, and a writing instrument having the friction body for thermally discoloring handwriting, printed images, etc., made of graphite, thermochromic ink, etc., by friction.
すなわち、本発明の主旨は次の通りである。
［１］下記要件（ａ）～（ｂ）を満たす４－メチル－１－ペンテン・α‐オレフィン共重合体（Ａ）と熱可塑性エラストマー（Ｂ）とを含有し、前記４－メチル－１－ペンテン・α－オレフィン共重合体（Ａ）と前記熱可塑性エラストマー（Ｂ）との質量の比率［（Ａ）／（Ｂ）］が１０／９０～６７／３３である摩擦体用樹脂組成物（Ｘ）。
要件（ａ）；示差走査型熱量計（ＤＳＣ）による熱量測定において共重合体（Ａ）の融点（Ｔｍ）が観測されない。
要件（ｂ）；共重合体（Ａ）は、４－メチル－１－ペンテンから導かれる構成単位（ｉ）と、α－オレフィン（ただし、４－メチル－１－ペンテンを除く。）から導かれる構成単位（ii）とを含み、前記構成単位（ｉ）と構成単位（ii）との合計を１００モル％として、当該構成単位（ｉ）６０～７８モル％と、当該構成単位（ii）２２～４０モル％とを含む。
［２］さらに結晶性ポリオレフィン（Ｃ）を含むことを特徴とする［１］に記載の摩擦体用樹脂組成物（Ｘ）。
［３］下記要件（ｘ）～（ｙ）を満たす［１］または［２］に記載の摩擦体用樹脂組成物（Ｘ）。
要件（ｘ）；ＪＩＳ Ｋ６２５３に準拠して、厚さ２ｍｍのシートを３枚重ねた状態で測定される、押針接触開始から１５秒後における４－メチル－１－ペンテン・α－オレフィン共重合体（Ａ）のショアＡ硬度は、６０以上９０以下である。
要件（ｙ）；ＪＩＳ Ｋ６２５３に準拠して、厚さ２ｍｍのシートを３枚重ねた状態で測定される、前記４－メチル－１－ペンテン・α－オレフィン共重合体（Ａ）のショアＡ硬度において、下記式で表される、押針接触直後におけるショアＡ硬度の値と押針接触から１５秒後におけるショアＡ硬度の値との差ΔＨＳが、１０以上３５以下である。
ΔＨＳ＝（押針接触直後のショアＡ硬度値－押針接触１５秒後のショアＡ硬度値）［４］前記４－メチル－１－ペンテン・α－オレフィン共重合体（Ａ）が下記要件（ｃ）を満たす［１］～［３］のいずれかに記載の摩擦体用樹脂組成物（Ｘ）。
要件（ｃ）；－４０～１５０℃の温度範囲で、１０ｒａｄ／s（１．６Ｈｚ）の周波数で動的粘弾性測定を行って得られるｔａｎδピーク温度が１０℃以上３８℃以下である。
［５］［１］～［４］のいずれかに記載の摩擦体用樹脂組成物（Ｘ）を含んでなることを特徴とする摩擦体。
［６］摩擦体が射出成形で作製させることを特徴とする［５］に記載の摩擦体。
［７］筆記具本体と、該筆記具本体に装着された［５］または［６］に記載の摩擦体とを備え、前記筆記具本体内に熱変色性インキを内蔵する筆記具。
［８］前記熱変色性インキ中に、平均粒子径が０．０５μｍ以上、５．０μｍ以下である熱変色性マイクロカプセル顔料を含む［７］に記載の筆記具。
［９］前記熱変色性インキ中に、平均粒子径が０．１μｍ以上、５０μｍ以下である金属光沢顔料を含むことを特徴とする［７］に記載の筆記具。
That is, the gist of the present invention is as follows.
[1] A 4-methyl-1-pentene/α-olefin copolymer (A) that satisfies the following requirements (a) to (b) and a thermoplastic elastomer (B), and the 4-methyl-1- A friction body resin composition ( X).
Requirement (a) : Melting point (Tm) of copolymer (A) is not observed in calorimetric measurement with a differential scanning calorimeter (DSC).
Requirement (b) ; Copolymer (A) is derived from structural unit (i) derived from 4-methyl-1-pentene and α-olefin (excluding 4-methyl-1-pentene) 60 to 78 mol% of the structural unit (i) and 22 of the structural unit (ii), where the total of the structural unit (i) and the structural unit (ii) is 100 mol%. ~40 mol%.
[2] The friction body resin composition (X) according to [1], further comprising a crystalline polyolefin (C).
[3] The friction body resin composition (X) according to [1] or [2], which satisfies the following requirements (x) to (y).
Requirement (x) : 4-methyl-1-pentene/α-olefin copolymer weight 15 seconds after the start of contact with the incisor needle, measured with three 2 mm thick sheets stacked in accordance with JIS K6253 The Shore A hardness of coalescence (A) is 60 or more and 90 or less.
Requirement (y) ; Shore A hardness of the 4-methyl-1-pentene/α-olefin copolymer (A) measured with three 2 mm thick sheets stacked in accordance with JIS K6253 , the difference ΔHS between the value of Shore A hardness immediately after contact with the indenter and the value of Shore A hardness 15 seconds after contact with the indenter, represented by the following formula, is 10 or more and 35 or less.
ΔHS = (Shore A hardness value immediately after contact with incisor needle - Shore A hardness value 15 seconds after contact with incisor needle) [4] The 4-methyl-1-pentene/α-olefin copolymer (A) satisfies the following requirements ( The friction body resin composition (X) according to any one of [1] to [3], which satisfies c).
Requirement (c) : The tan δ peak temperature obtained by performing dynamic viscoelasticity measurement at a frequency of 10 rad/s (1.6 Hz) in the temperature range of -40 to 150°C is 10°C or higher and 38°C or lower.
[5] A friction body comprising the friction body resin composition (X) according to any one of [1] to [4].
[6] The friction body according to [5], characterized in that the friction body is produced by injection molding.
[7] A writing instrument comprising a writing instrument main body, and the friction body according to [5] or [6] attached to the writing instrument main body, wherein thermochromic ink is incorporated in the writing instrument main body.
[8] The writing instrument according to [7], wherein the thermochromic ink contains a thermochromic microcapsule pigment having an average particle size of 0.05 μm or more and 5.0 μm or less.
[9] The writing instrument according to [7], wherein the thermochromic ink contains a metallic luster pigment having an average particle size of 0.1 μm or more and 50 μm or less.
本発明の摩擦体用樹脂組成物（Ｘ）は、下記要件（ｘ）と（ｙ）を満たすことが好ましい。
要件（ｘ）；
ＪＩＳ Ｋ６２５３に準拠して、厚さ２ｍｍのシートを３枚重ねた状態で測定される、押針接触開始から１５秒後における共重合体（Ａ）のショアＡ硬度は、６０以上９５以下であり、好ましくは、６５以上９５以下であり、より好ましくは、７０以上９０以下である。
The friction body resin composition (X) of the present invention preferably satisfies the following requirements (x) and (y).
Requirement (x) ;
The Shore A hardness of the copolymer (A) 15 seconds after the start of contact with the indenter, which is measured in a state in which three sheets with a thickness of 2 mm are stacked in accordance with JIS K6253, is 60 or more and 95 or less. , preferably 65 or more and 95 or less, more preferably 70 or more and 90 or less.
本発明の摩擦体用樹脂組成物（Ｘ）は、さらに下記要件（ｚ）を満たすことが好ましい。
要件（ｚ）；
－４０～１５０℃の温度範囲で、１０ｒａｄ／s（１．６Ｈｚ）の周波数で動的粘弾性測定を行って得られる、共重合体（Ａ）のｔａｎδピーク温度は、１０℃以上３０℃以下であり、１０℃以上２８℃以下であることが好ましく、１０℃以上２５℃以下であることがより好ましく、１４℃以上２５℃以下であることがさらに好ましい。摩擦体用樹脂組成物（Ｘ）のｔａｎδピーク温度を上記の温度範囲にすることで、室温での粘性特性が増加し、結果として摩擦体の黒鉛や熱変色性インキの消去性が向上する。
The friction body resin composition (X) of the present invention preferably further satisfies the following requirement (z).
Requirement (z) ;
The tan δ peak temperature of the copolymer (A) obtained by dynamic viscoelasticity measurement at a frequency of 10 rad/s (1.6 Hz) in the temperature range of -40 to 150 ° C. is 10 ° C. or higher and 30 ° C. or lower. The temperature is preferably 10° C. or higher and 28° C. or lower, more preferably 10° C. or higher and 25° C. or lower, and even more preferably 14° C. or higher and 25° C. or lower. By setting the tan δ peak temperature of the friction body resin composition (X) within the above temperature range, the viscosity characteristics at room temperature are increased, and as a result, the erasability of graphite and thermochromic ink on the friction body is improved.
＜結晶性ポリオレフィン（Ｃ）＞
本発明の摩擦体用樹脂組成物（Ｘ）は、結晶性ポリオレフィン（Ｃ）を含んでいてもよい。結晶性ポリオレフィン（Ｃ）は、従来公知である、低密度、中密度、高密度ポリエチレン、高圧法低密度ポリエチレン、アイソタクティックポリプロピレン、シンジオタクティックポリプロピレン、ポリ１－ブテン、ポリ４－メチル－１－ペンテン、ポリ３－メチル－１－ブテン、エチレン・α－オレフィン共重合体、プロピレン・α－オレフィン共重合体、１－ブテン・α－オレフィン共重合体、環状オレフィン共重合体、塩素化ポリオレフィンなどが挙げられる。
結晶性ポリオレフィン（Ｃ）の配合量が上記範囲内にあることで、得られる摩擦体に適度な硬度を付与することができ消去性に寄与することが可能となる。
<Crystalline polyolefin (C)>
The friction body resin composition (X) of the present invention may contain a crystalline polyolefin (C). Crystalline polyolefin (C) is conventionally known low density, medium density, high density polyethylene, high pressure low density polyethylene, isotactic polypropylene, syndiotactic polypropylene, poly 1-butene, poly 4-methyl-1 - pentene, poly 3-methyl-1-butene, ethylene/α-olefin copolymer, propylene/α-olefin copolymer, 1-butene/α-olefin copolymer, cyclic olefin copolymer, chlorinated polyolefin etc.
When the blending amount of the crystalline polyolefin (C) is within the above range, it is possible to impart appropriate hardness to the resulting friction body and contribute to erasability.
＜摩擦体用樹脂組成物（Ｘ）を有する筆記具＞
前記摩擦体用樹脂組成物（Ｘ）および摩擦体は、筆跡を擦過できる形態で構成され実用に供される。その際、摩擦体は単独で構成される他、摩擦部分が筆跡（紙面）に接触できる形態で硬質樹脂等の他部材へ併設する等、把持できる状態で構成されればよい。その他、熱変色性インキを内蔵する筆記具に設けた熱変色性筆記具形態や、別体からなる熱変色性インキを内蔵する筆記具形態などとして構成することができる。例えば、本発明の筆記具は、筆記具本体と、該筆記具本体に装着された前記摩擦体とを備え、前記筆記具本体内に熱変色性インキを内蔵する。
<Writing instrument having friction body resin composition (X) >
The resin composition (X) for a friction body and the friction body are constructed in a form capable of rubbing handwriting and put to practical use. In this case, the friction body may be configured independently, or may be configured in such a manner that it can be gripped, such as by attaching it to another member such as a hard resin so that the friction portion can come into contact with the handwriting (paper surface). In addition, it can be configured as a thermochromic writing instrument form provided in a writing instrument containing thermochromic ink, or as a writing instrument form containing thermochromic ink as a separate body. For example, the writing instrument of the present invention includes a writing instrument body and the friction body attached to the writing instrument body, and the writing instrument body incorporates thermochromic ink.
Claims (9)
要件（ａ）；示差走査型熱量計（ＤＳＣ）による熱量測定において共重合体（Ａ）の融点（Ｔｍ）が観測されない。
要件（ｂ）；共重合体（Ａ）は、４－メチル－１－ペンテンから導かれる構成単位（ｉ）と、α－オレフィン（ただし、４－メチル－１－ペンテンを除く。）から導かれる構成単位（ii）とを含み、前記構成単位（ｉ）と構成単位（ii）との合計を１００モル％として、構成単位（ｉ）６０～７８モル％と、当該構成単位（ii）２２～４０モル％とを含む。 A 4-methyl-1-pentene/α-olefin copolymer (A) that satisfies the following requirements (a) to (b) and a thermoplastic elastomer (B), wherein the 4-methyl-1-pentene/α - A friction body resin composition (X), wherein the mass ratio [(A)/(B)] of the olefin copolymer (A) and the thermoplastic elastomer (B) is from 10/90 to 67/33.
Requirement (a) : Melting point (Tm) of copolymer (A) is not observed in calorimetric measurement with a differential scanning calorimeter (DSC).
Requirement (b) ; Copolymer (A) is derived from structural unit (i) derived from 4-methyl-1-pentene and α-olefin (excluding 4-methyl-1-pentene) 60 to 78 mol% of the structural unit (i) and 22 to 22 mol% of the structural unit (ii) and 40 mol %.
要件（ｘ）；ＪＩＳ Ｋ６２５３に準拠して、厚さ２ｍｍのシートを３枚重ねた状態で測定される、押針接触開始から１５秒後における前記４－メチル－１－ペンテン・α‐オレフィン共重合体（Ａ）のショアＡ硬度は、６０以上９０以下である。
要件（ｙ）；ＪＩＳ Ｋ６２５３に準拠して、厚さ２ｍｍのシートを３枚重ねた状態で測定される、前記４－メチル－１－ペンテン・α‐オレフィン共重合体（Ａ）のショアＡ硬度において、下記式で表される、押針接触直後におけるショアＡ硬度の値と押針接触から１５秒後におけるショアＡ硬度の値との差ΔＨＳが、１０以上３５以下である。
ΔＨＳ＝（押針接触直後のショアＡ硬度値－押針接触１５秒後のショアＡ硬度値） 3. The friction body resin composition (X) according to claim 1 or 2, which satisfies the following requirements (x) and (y).
Requirement (x) : According to JIS K6253, the above 4-methyl-1-pentene/α-olefin is measured in a state where three sheets with a thickness of 2 mm are stacked, 15 seconds after the start of contact with the incisor needle. The Shore A hardness of the polymer (A) is 60 or more and 90 or less.
Requirement (y) : Shore A hardness of the 4-methyl-1-pentene/α-olefin copolymer (A) measured with three 2 mm-thick sheets stacked in accordance with JIS K6253. , the difference ΔHS between the value of Shore A hardness immediately after contact with the indenter and the value of Shore A hardness 15 seconds after contact with the indenter, represented by the following formula, is 10 or more and 35 or less.
ΔHS = (Shore A hardness value immediately after contact with the incisor-Shore A hardness value 15 seconds after contact with the incisor)
要件（ｃ）；－４０～１５０℃の温度範囲で、１０ｒａｄ／s（１．６Ｈｚ）の周波数で動的粘弾性測定を行って得られるｔａｎδピーク温度が１０℃以上３８℃以下である。 4. The friction body resin composition according to any one of claims 1 to 3, wherein the 4-methyl-1-pentene/α-olefin copolymer (A) satisfies the following requirement (c): Thing (X).
Requirement (c ): The tan δ peak temperature obtained by performing dynamic viscoelasticity measurement at a frequency of 10 rad/s (1.6 Hz) in the temperature range of -40 to 150°C is 10°C or higher and 38°C or lower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019232852A JP7410709B2 (en) | 2019-12-24 | 2019-12-24 | Composition for friction body, friction body and writing instrument |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019232852A JP7410709B2 (en) | 2019-12-24 | 2019-12-24 | Composition for friction body, friction body and writing instrument |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2021100804A JP2021100804A (en) | 2021-07-08 |
| JP2021100804A5 true JP2021100804A5 (en) | 2023-01-04 |
| JP7410709B2 JP7410709B2 (en) | 2024-01-10 |
Family
ID=76651119
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2019232852A Active JP7410709B2 (en) | 2019-12-24 | 2019-12-24 | Composition for friction body, friction body and writing instrument |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP7410709B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6900746B2 (en) * | 2017-03-31 | 2021-07-07 | 株式会社三洋物産 | Pachinko machine |
| JP2020014904A (en) * | 2019-10-30 | 2020-01-30 | 株式会社三洋物産 | Game machine |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5268227B2 (en) * | 2004-12-28 | 2013-08-21 | 三井化学東セロ株式会社 | Solar cell encapsulant |
| JP5794730B2 (en) * | 2011-05-31 | 2015-10-14 | 三菱鉛筆株式会社 | Writing instrument cap with writing instrument and erasable ink |
| JP6673704B2 (en) * | 2016-01-28 | 2020-03-25 | 三井化学株式会社 | Thermoplastic polymer composition for vibration damping material, method for producing molded article, and molded article |
| EP3556570A4 (en) * | 2016-12-19 | 2020-07-22 | Kabushiki Kaisha Pilot Corporation (also trading as Pilot Corporation) | Friction body, and writing tool and writing set |
-
2019
- 2019-12-24 JP JP2019232852A patent/JP7410709B2/en active Active
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2021100804A5 (en) | ||
| US9988546B2 (en) | Colour pencil lead | |
| US9441079B2 (en) | Block copolymer comprising polyorganosiloxane block and polyolefin block | |
| EP1981099A3 (en) | Packaging material for flat electrochemical cell | |
| RU2700063C2 (en) | Pencil lead for paper | |
| EP1911803A4 (en) | Polypropylene resin composition, film or sheet, stretched film obtained from such film or sheet, multilayer body, and stretched film obtained from such multilayer body | |
| RU2014142698A (en) | OBTAINING PIGMENTS | |
| BR112016006965B1 (en) | CONSIDERLY LOADED FLEXIBLE POLYOLEFIN COMPOSITION FOR COVERING MEMBRANES AS WELL AS ARTICLE, SHEETS OR FILM FOR COATING AND INTERNAL FILLING FOR INDUSTRIAL CABLES OR COVERING OF CABLES CONTAINING SUCH COMPOSITION | |
| US3355348A (en) | Heat sealable-aluminum foil paper laminate | |
| US11072722B2 (en) | Pencil lead | |
| TWI221475B (en) | Water resistant composition, coating agent, and recording material | |
| JP7410709B2 (en) | Composition for friction body, friction body and writing instrument | |
| JP2006199952A (en) | Thermoplastic elastomer and molded product thereof | |
| BR112019002051B1 (en) | THERMOPLATIC POLYOLEFIN ELASTOMER FILM, AND, ARTICLE | |
| JP6515014B2 (en) | Elastomer composition for foam molding and foam molded article | |
| CN108699412A (en) | Low energy surface base material adhesive composition | |
| ES2498925T3 (en) | Use, in paper-coating colors, of amphiphilic and non-water-soluble (meth) acrylic polymers | |
| JP2021050295A (en) | Polypropylene-based resin composition and film for heat seal | |
| JP7456825B2 (en) | Composition for friction body, friction body and writing instrument | |
| JP5007104B2 (en) | Resin composition for liquid container and liquid container comprising the same | |
| JP2005219818A (en) | Melting bag | |
| JP2023122346A (en) | Resin composition, friction body, and writing utensil | |
| JP5181903B2 (en) | Pencil lead | |
| JP7039004B2 (en) | Hot melt adhesive | |
| BR102020023663A2 (en) | PENCIL TIP FOR WRITING, DRAWING, MARKING, PLOTTING AND/OR COLORING |