JP3753967B2 - Erasure - Google Patents
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- JP3753967B2 JP3753967B2 JP2001299385A JP2001299385A JP3753967B2 JP 3753967 B2 JP3753967 B2 JP 3753967B2 JP 2001299385 A JP2001299385 A JP 2001299385A JP 2001299385 A JP2001299385 A JP 2001299385A JP 3753967 B2 JP3753967 B2 JP 3753967B2
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- plasticizer
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Description
【0001】
【発明の属する技術分野】
本発明は字消しに関し、更に詳しくは、安全性や耐環境汚染性が高く、消し屑のまとまり性及び耐折れ性に優れた字消しに関する。
【0002】
【従来の技術】
塩化ビニル系樹脂製字消しは、優れた消字性、消字作業中の感触及び装飾性から広く使用されている。
塩化ビニル系樹脂製字消しは、塩化ビニル系樹脂に可塑剤を配合し、更に必要に応じて、安定剤、着色料、香料等の字消し材料を配合し、プレス成形、射出成形、押出成形等の成形方法により成形され製品とされている。
【0003】
上記の如く、塩化ビニル系樹脂製字消しは、可塑剤の使用が必須であるため、例えば、特公昭44−25905号、特公昭46−42018号、特公昭57−22948号、特許第2655278号に記載されているような可塑剤のブリード(移行)の防止等が研究されている。
またエポキシ系可塑剤を配合した字消しが提案され、特開昭61−29597号ではフタル酸、アジピン酸系可塑剤にエポキシ化大豆油を併用することにより、消字性、透明性に優れ、削りカスが字消しから容易に分離する字消しが、また、最近では特開平9−66699号のように、エポキシ化脂肪酸エステル、エポキシ化脂肪酸トリグリセリドを添加して消し屑の散乱を防止した消しゴムが提案されている。更に、特開2001−81259号では、4,5−エポキシヘキサヒドロフタル酸ジ−2−エチルヘキシルの添加により、ブリードを起こさず、弾性強度に優れた字消しが提案されている。
【0004】
【発明が解決しようとする課題】
以上のように、塩化ビニル系樹脂字消しは、種々の可塑剤を大量に含有するため、人体への安全性や環境を汚染するという問題を有しているが、これまで、かかる観点からの字消しの研究、開発は報告されていないのが実情である。
本発明は、かかる実情に鑑み、安全性及び耐環境汚染性に優れ、消し屑のまとまり性及び耐折れ性に優れた字消しを提供するものである。
【0005】
【課題を解決するための手段】
本発明者らは、上記課題を解決するべく鋭意研究の結果、特定の可塑剤を組み合わせて使用することにより、所期の目的が達成されることを見い出し、本発明に到達した。
【0006】
即ち、本発明の請求項1は、アセチルクエン酸トリブチルからなる可塑剤(A)と、トリメリット酸系可塑剤、エポキシ系可塑剤、ポリエステル系可塑剤から選ばれる少なくとも1種の可塑剤(B)とを含有してなり、可塑剤(A)と可塑剤(B)の割合が、可塑剤(A)が25〜98.2重量%、可塑剤(B)が75〜1.8重量%であることを特徴とする塩化ビニル系樹脂製字消しである。
【0007】
本発明の請求項2は、可塑剤(B)がトリメリット酸系可塑剤、エポキシ系可塑剤から選ばれる少なくとも1種である請求項1記載の字消しである。
【0010】
【発明の実施の形態】
本発明において、可塑剤(A)として用いられるアセチルクエン酸トリブチル(アセチルトリ−n−ブチルシトレート、以下、ATBCと記す)は、無毒、無臭といわれており、食品包装関係にも使用され、耐寒性、耐候性、耐水性に優れた可塑剤である。
【0011】
しかしながら、ATBCは上記の如き利点を有しているにも拘らず、字消し用の主たる可塑剤としては殆ど使用されていないのが実情である。
例えば、前記した特開平9−66699号においても、ATBCは併用される可塑剤として、多数列記されている可塑剤のうちの1つとして記載されているにすぎない。
【0012】
従来、ATBCが字消し用の主たる可塑剤として使用されていない理由としては、大量に使用するとブリード(移行)し易く、例えば、ポリスチレン系樹脂製の鉛筆入れや鉛筆の塗装面に移行し易く、また消し屑が散らばり、使用感が悪いということが考えられる。
【0013】
本発明者らは、ATBCの持つ長所を最大限に活用すべく鋭意研究の結果、特定の他の可塑剤と併用することにより、移行性及び消し屑のまとまり性が改善されるとともに、消し屑のまとまり性の良い字消しにありがちな折れ易いという問題も一挙に解消されることを見い出し、本発明はかかる知見により完成されたものである。
【0014】
即ち、本発明は、ATBCからなる可塑剤(A)と、トリメリット酸系可塑剤、エポキシ系可塑剤、ポリエステル系可塑剤から選ばれる少なくとも1種の可塑剤(B)とを併用することを特徴とする。
【0015】
本発明に用いられるトリメリット酸としては、トリ−2−エチルヘキシルトリメリテート(TOTM)、トリイソデシルトリメリテート(TIDTM)、トリイソオクチルトリメリテート(TIOTM)、トリイソノニルトリメリテート等が挙げられ、またエポキシ可塑剤としては、エポキシ化トリグリセリド、エポキシ化脂肪酸モノエステル、エポキシ化大豆油、エポキシ化アマニ油、エポキシ化脂肪酸エステル、エポキシヘキサヒドロフタル酸ジ−2−エチルヘキシル(E−PS)、エポキシヘキサヒドロフタル酸ジ−n−オクチル(nE−PS)、エポキシヘキサヒドロフタル酸ジエポキシステアリル(E−PO)等のエポキシヘキサヒドロフタル酸エステル等が挙げられ、またポリエステル系可塑剤としては、750〜1300の分子量で、粘度が160〜1300mPa・s(cp)のもので、具体的にはアデカサイザーPN−160、PN−9302、PN−150、PN−170、PN−230、PN−1010(以上いずれも商品名、旭電化工業株式会社)、ポリサイザーW−780、W−20、W−1000、W−320、W−1200、P−103(以上いずれも商品名、大日本インキ化学工業株式会社)等が挙げられる。これらは単独で又は必要に応じ2種以上組み合わせて用いられる。これらの可塑剤の中では、トリメリット酸系可塑剤、エポキシ系可塑剤が好ましい。
【0016】
ATBCからなる可塑剤(A)と、トリメリット酸系可塑剤、エポキシ系可塑剤、ポリエステル系可塑剤から選ばれる少なくとも1種の可塑剤(B)とを併用する割合については、字消し中の可塑剤の量(合計量)により一概には規定できないが、通常、可塑剤(A)が25〜98.2重量%、可塑剤(B)が75〜1.8重量%が好ましい。
可塑剤(A)が25重量%未満では耐折れ性が不十分となり、一方、98.2重量%を越えると移行し易くなる。ATBCの安全性や耐環境汚染性の観点からは、可塑剤(A)を優位量、即ち50重量%以上用い、可塑剤(B)を劣位量、即ち50重量%未満用いるのが一層好ましい。
本発明において、可塑剤量は塩化ビニル系樹脂100重量部に対して200〜90重量部が好ましく、可塑剤(A)と可塑剤(B)との割合は、上記した配合割合に準じて適宜選択される。
【0017】
本発明に用いられる塩化ビニル系樹脂としては、従来用いられている塩化ビニル系樹脂が全て用いられ、例えば、重合度400〜3000程度のポリ塩化ビニルの他、塩化ビニル−酢酸ビニル共重合体等が挙げられ、これらは単独で又は必要に応じ2種以上組み合わせて用いられる。
【0018】
更に、必要に応じて、重質炭酸カルシウム、軽質炭酸カルシウム、シリカ、珪藻土、酸化マグネシウム、タルク、セリサイト、石英粉末、モンモリロナイト、ホタテ、カキ、しじみなどの貝殻粉末などの充填剤、有機中空粒子、無機中空粒子及び有機・無機顔料、染料などの着色材、香料、安定剤、滑剤、紫外線吸収剤、防カビ剤などの他の添加物も適宜任意に使用することも可能である。また、更にインキ等を溶解する溶剤を内包したマイクロカプセルや、インキ筆跡などを摩消する研磨剤を添加することにより、鉛筆筆跡以外の消去も可能な字消しを提供することができる。
【0019】
上記の如き成分からなる字消し組成物は、混練され、プレス成形、射出成形、押出成形等により成形され、所定の寸法に裁断されて製品とされる。
【0020】
【実施例】
以下、実施例及び比較例に基づいて本発明を更に詳細に説明するが、これらは本発明の範囲を何ら制限するものではない。
【0021】
以下の実施例及び比較例で用いた材料を表1に示す。以下の記載において、「部」は特に断らない限り「重量部」を表す。
【0022】
【表1】
【0023】
また、以下の実施例、比較例において、消字率、耐折れ性、消し屑のまとまり性及び移行性は、下記の方法により測定又は評価した。
【0024】
消字率の測定方法(JIS S 6050より):
(1)試料を厚さ5m/mの板状に切り、試験紙との接触部分を半径6m/mの円弧に仕上げたものを試験片とした。
(2)試験片を着色紙に対して垂直に、しかも着色線に対して直角になるように接触させ、試験片におもりとホルダの質量の和が0.5kgとなるようにおもりを載せ、150±10cm/min の速さで着色部を4往復摩消させた。
(3)濃度計(DENSITOMETER PDA65 sakura社製)によって、着色紙の非着色部分の濃度を0として、着色部及び摩消部の濃度をそれぞれ測定した。
(4)消字率は次の式によって算出した。
消字率(%)=(1−(摩消部の濃度÷着色部の濃度))×100
【0025】
耐折れ性の測定方法:
試料を17×43×10m/mに切断し、2回/秒の速さで試料を曲げ、完全に破断するまでの回数を4回づつ測定し、それらの平均で表した。
【0026】
消し屑のまとまり性の試験方法:
特開平9−66699号公報に準じ、消去荷重500gfで10往復させて、最も大きな消し屑の重量を試験片が減量した重量で割った値に100を乗じたものを屑のまとまり率(%)として算出した。
尚、1配合につき4回ずつ屑の重量を測定し、それらの平均をとった。
屑のまとまり率(%)
=〔最大の屑の重量/(テスト前の試験片の重量−テスト後の試験片の重量部)〕×100
【0027】
移行性の評価方法(JIS S 6050 4.3):
移行性の試験は、鉛筆を40mmに切り、これを長さ35mm、幅15mm以上及び厚さ5mm以上の試験片(字消し)の上に2本平行(試験片の長片に対して)に置き、その上に20gのおもりを載せ、60±2℃の恒温器の中に入れ、1時間後に取り出し、鉛筆の塗料が試験片に付着するかどうかを調べる。
◎:鉛筆塗料が全く試験片に付着しない。
○:試験片に鉛筆の跡が残る。
×:鉛筆塗料が試験片に付着する。
【0028】
実施例1〜9、比較例1〜4
表2に示す配合の樹脂組成物を混合攪拌し真空脱泡した後、130〜145℃に保温した100×100×10m/mの金型に流し込み26分間加熱した後冷却し、金型から取り出して試料を得た。
各試料について消字率、耐折れ性、消し屑のまとまり性及び移行性を上記方法で測定した結果を表2に示す。
【0029】
【表2】
【0030】
表2から明かなように、ATBCと、トリメリット酸系可塑剤、エポキシ系可塑剤又はポリエステル系可塑剤とを併用することにより、耐折れ性、消し屑のまとまり性、及び移行性が改善されることが分かる。
【0031】
実施例10〜14、比較例5〜6
表3に示す配合の樹脂組成物を混合攪拌し真空脱泡した後、130〜140℃に保温した100×100×10m/mの金型に流し込み26分間加熱した後冷却し、金型から取り出して試料を得た。
各試料について消字率、耐折れ性、消し屑のまとまり性及び移行性を上記方法で測定した結果を表3に示す。
【0032】
【表3】
【0033】
表3から明かなように、可塑剤量を200部又は90部とした場合においても、ATBCと、トリメリット酸系可塑剤、エポキシ系可塑剤又はポリエステル系可塑剤とを併用することにより、耐折れ性、消し屑のまとまり性、及び移行性が改善されることが分かる。
【0034】
【発明の効果】
叙上のとおり、本発明によればATBCと、トリメリット酸系可塑剤、エポキシ可塑剤、ポリエステル系可塑剤とを併用することにより、安全性、耐環境汚染性が高く、耐折れ性、消し屑のまとまり性及び移行性の改善された使い勝手の良い字消しが提供される。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to erasing, and more particularly, to erasing that has high safety and environmental pollution resistance, and is excellent in scraping ability and folding resistance.
[0002]
[Prior art]
The erasing of vinyl chloride resin is widely used because of its excellent erasability, feel during erasing and decoration.
For erasing of vinyl chloride resin, plasticizer is added to vinyl chloride resin, and if necessary, erasing materials such as stabilizers, colorants, fragrances, etc. are added, press molding, injection molding, extrusion molding. It is molded by a molding method such as
[0003]
As described above, the eraser made of vinyl chloride resin requires the use of a plasticizer. For example, Japanese Patent Publication No. 44-25905, Japanese Patent Publication No. 46-42018, Japanese Patent Publication No. 57-22948, Japanese Patent No. 2655278. The prevention of bleeding of plasticizers as described in (2) has been studied.
In addition, erasing with an epoxy plasticizer has been proposed, and in JP-A 61-29597, epoxidized soybean oil is used in combination with phthalic acid and adipic acid plasticizer, so that the erasability and transparency are excellent. An eraser in which scraps are easily separated from an eraser, and recently, as disclosed in JP-A-9-66699, an eraser in which an epoxidized fatty acid ester and an epoxidized fatty acid triglyceride are added to prevent scattering of erased chips is provided. Proposed. Furthermore, Japanese Patent Laid-Open No. 2001-81259 proposes erasing with excellent elastic strength without causing bleeding by adding di-2-ethylhexyl 4,5-epoxyhexahydrophthalate.
[0004]
[Problems to be solved by the invention]
As described above, the vinyl chloride resin eraser contains a large amount of various plasticizers, and thus has a problem of contaminating human safety and the environment. In fact, no research or development on erasing has been reported.
In view of the actual situation, the present invention provides an eraser that is excellent in safety and environmental pollution resistance, and that is excellent in scraping ability and folding resistance.
[0005]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have found that the intended purpose can be achieved by using a specific plasticizer in combination, and have reached the present invention.
[0006]
That is, claim 1 of the present invention is a plasticizer (A) comprising tributyl acetylcitrate, and at least one plasticizer (B) selected from trimellitic acid plasticizer, epoxy plasticizer, and polyester plasticizer. ) and Ri greens contain, the proportion of plasticizer (a) and the plasticizer (B) is a plasticizer (a) is 25 to 98.2 wt%, a plasticizer (B) is from 75 to 1.8 weight % der is to that vinyl chloride-based resin eraser characterized Rukoto.
[0007]
Claim 2 of the present invention is the eraser according to claim 1, wherein the plasticizer (B) is at least one selected from trimellitic acid plasticizers and epoxy plasticizers.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, tributyl acetyl citrate (acetyl tri-n-butyl citrate, hereinafter referred to as ATBC) used as the plasticizer (A) is said to be non-toxic and odorless, and is also used for food packaging. It is a plasticizer with excellent cold resistance, weather resistance and water resistance.
[0011]
However, in spite of the above-mentioned advantages, ATBC is hardly used as a main plasticizer for erasing.
For example, in the above-mentioned Japanese Patent Application Laid-Open No. 9-66699, ATBC is only described as one of many listed plasticizers as a plasticizer used in combination.
[0012]
Conventionally, as a reason why ATBC is not used as a main plasticizer for erasing, it is easy to bleed (transfer) when used in a large amount, for example, to easily shift to a pencil case made of polystyrene resin or a painted surface of a pencil, In addition, it is considered that the swarf is scattered and the usability is poor.
[0013]
As a result of intensive studies to make the best use of the advantages of ATBC, the present inventors have improved the migration and the cohesiveness of the swarf by using it together with other specific plasticizers. The present inventors have found that the problem of easy folding that tends to occur in erasing with good cohesiveness is solved at once, and the present invention has been completed based on such knowledge.
[0014]
That is, the present invention uses a plasticizer (A) made of ATBC in combination with at least one plasticizer (B) selected from trimellitic acid plasticizer, epoxy plasticizer, and polyester plasticizer. Features.
[0015]
Examples of trimellitic acid used in the present invention include tri-2-ethylhexyl trimellitate (TOTM), triisodecyl trimellitate (TIDTM), triisooctyl trimellitate (TIOTM), triisononyl trimellitate, and the like. Epoxy plasticizers include epoxidized triglycerides, epoxidized fatty acid monoesters, epoxidized soybean oil, epoxidized linseed oil, epoxidized fatty acid esters, and epoxyhexahydrophthalate di-2-ethylhexyl (E-PS). ), Epoxyhexahydrophthalic acid esters such as epoxyhexahydrophthalic acid di-n-octyl (nE-PS), epoxyhexahydrophthalic acid diepoxystearyl (E-PO) and the like, and polyester-based plasticizers Is the minute of 750-1300 In particular, the viscosity is 160 to 1300 mPa · s (cp), specifically, Adekasizer PN-160, PN-9302, PN-150, PN-170, PN-230, PN-1010 (all above Trade name, Asahi Denka Kogyo Co., Ltd.), Polycizer W-780, W-20, W-1000, W-320, W-1200, P-103 (all are trade names, Dainippon Ink and Chemicals, Inc.), etc. Is mentioned. These may be used alone or in combination of two or more as required. Among these plasticizers, trimellitic acid plasticizers and epoxy plasticizers are preferable.
[0016]
About the ratio which uses together the plasticizer (A) which consists of ATBC, and the at least 1 sort (s) of plasticizer (B) chosen from a trimellitic acid type plasticizer, an epoxy type plasticizer, and a polyester type plasticizer, Although it cannot be generally defined by the amount (total amount) of the plasticizer, usually, the plasticizer (A) is preferably 25 to 98.2% by weight and the plasticizer (B) is preferably 75 to 1.8% by weight.
If the plasticizer (A) is less than 25% by weight, the folding resistance is insufficient, while if it exceeds 98.2% by weight, the plasticizer (A) tends to migrate. From the viewpoint of safety of ATBC and environmental pollution resistance, it is more preferable to use the plasticizer (A) in a superior amount, that is, 50% by weight or more, and use the plasticizer (B) in an inferior amount, that is, less than 50% by weight.
In the present invention, the amount of the plasticizer is preferably 200 to 90 parts by weight with respect to 100 parts by weight of the vinyl chloride resin, and the ratio of the plasticizer (A) and the plasticizer (B) is appropriately determined according to the above-described blending ratio. Selected.
[0017]
As the vinyl chloride resin used in the present invention, all conventionally used vinyl chloride resins are used. For example, in addition to polyvinyl chloride having a polymerization degree of about 400 to 3000, a vinyl chloride-vinyl acetate copolymer , etc. These may be used alone or in combination of two or more as necessary.
[0018]
Furthermore, if necessary, fillers such as heavy calcium carbonate, light calcium carbonate, silica, diatomaceous earth, magnesium oxide, talc, sericite, quartz powder, shell powder such as montmorillonite, scallops, oysters, and stains, organic hollow particles Other additives such as inorganic hollow particles and coloring materials such as organic / inorganic pigments and dyes, fragrances, stabilizers, lubricants, ultraviolet absorbers and fungicides can also be used as appropriate. Further, by adding a microcapsule encapsulating a solvent that dissolves ink or the like, or an abrasive that wears away ink handwriting, it is possible to provide erasing that can be erased other than pencil handwriting.
[0019]
The eraser composition comprising the above components is kneaded, molded by press molding, injection molding, extrusion molding, or the like, and cut into a predetermined size to obtain a product.
[0020]
【Example】
EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example and a comparative example, these do not restrict | limit the scope of the present invention at all.
[0021]
The materials used in the following examples and comparative examples are shown in Table 1. In the following description, “parts” represents “parts by weight” unless otherwise specified.
[0022]
[Table 1]
[0023]
Moreover, in the following Examples and Comparative Examples, the erasure rate, folding resistance, scraping property, and transferability were measured or evaluated by the following methods.
[0024]
Measurement method of erasure rate (from JIS S 6050):
(1) The sample was cut into a plate having a thickness of 5 m / m, and the test piece was prepared by finishing the contact portion with the test paper into an arc having a radius of 6 m / m.
(2) The test piece is brought into contact with the colored paper perpendicularly and at right angles to the colored line, and a weight is placed on the test piece so that the sum of the weight of the weight and the holder is 0.5 kg. The colored part was brushed back and forth 4 times at a speed of 150 ± 10 cm / min.
(3) Using a densitometer (DENSITOMETER PDA65 made by Sakura), the density of the non-colored part of the colored paper was set to 0, and the density of the colored part and the erosion part was measured.
(4) The erasure rate was calculated by the following formula.
Erase rate (%) = (1− (density of wear part ÷ density of colored part)) × 100
[0025]
Measuring method of folding resistance:
The sample was cut to 17 × 43 × 10 m / m, the sample was bent at a rate of 2 times / second, and the number of times until it completely broke was measured four times, and the average was expressed.
[0026]
Method for testing the cohesiveness of swarf:
According to Japanese Patent Laid-Open No. 9-66699, 10 reciprocations are performed at an erasing load of 500 gf, and the value obtained by multiplying the value obtained by dividing the weight of the largest swarf by the weight reduced by the test piece is multiplied by 100. Calculated as
In addition, the weight of the waste was measured four times for each blend, and the average was taken.
Waste collection rate (%)
= [Maximum waste weight / (weight of test piece before test−weight part of test piece after test)] × 100
[0027]
Method for evaluating migration (JIS S 6050 4.3):
In the migration test, a pencil is cut into 40 mm, and two of them are parallel (with respect to the long piece of the test piece) on a test piece (erasure) having a length of 35 mm, a width of 15 mm or more and a thickness of 5 mm or more. Place a 20 g weight on it, place it in a 60 ± 2 ° C. incubator, remove it after 1 hour, and check whether the pencil paint adheres to the test piece.
(Double-circle): Pencil paint does not adhere to a test piece at all.
○: A pencil mark remains on the specimen.
X: Pencil paint adheres to the test piece.
[0028]
Examples 1-9, Comparative Examples 1-4
The resin composition shown in Table 2 was mixed and stirred and vacuum degassed, then poured into a 100 × 100 × 10 m / m mold kept at 130 to 145 ° C., heated for 26 minutes, cooled, and taken out from the mold A sample was obtained.
Table 2 shows the results of measuring the erasure rate, folding resistance, chip sizing property, and transferability of each sample by the above method.
[0029]
[Table 2]
[0030]
As can be seen from Table 2, by using ATBC in combination with trimellitic acid plasticizer, epoxy plasticizer or polyester plasticizer, the folding resistance, swarfability and migration are improved. I understand that
[0031]
Examples 10-14, Comparative Examples 5-6
The resin composition having the composition shown in Table 3 was mixed and stirred and vacuum degassed, then poured into a 100 × 100 × 10 m / m mold kept at 130 to 140 ° C., heated for 26 minutes, cooled, and taken out from the mold A sample was obtained.
Table 3 shows the results of measuring the erasure rate, crease resistance, chip sizing property and transferability of each sample by the above method.
[0032]
[Table 3]
[0033]
As can be seen from Table 3, even when the amount of plasticizer is 200 parts or 90 parts, by using ATBC in combination with trimellitic acid plasticizer, epoxy plasticizer or polyester plasticizer, It can be seen that the foldability, the smashability, and the transferability are improved.
[0034]
【The invention's effect】
As described above, according to the present invention, by using ATBC in combination with trimellitic acid plasticizer, epoxy plasticizer, and polyester plasticizer, safety, environmental pollution resistance is high, fold resistance, and anti-erasing. An easy-to-use erasure with improved waste clumping and transferability is provided.
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CN102174233A (en) * | 2011-01-24 | 2011-09-07 | 张卫华 | Phthalate-free polyvinyl chloride granule formula and preparation method thereof |
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