JP4097311B2 - Interdental brush - Google Patents

Description

【００２３】
［ＩＩ］柄部材用樹脂試料
前記［Ｉ］で用いたＡ−型の抗菌性ゼオライトを低密度ポリエチレン（商品名；ＭＩＲＡＳＯＮ ４０１：三井石油化学工業（株）製）に対し０．５重量％、および、１．０重量％それぞれ溶融混合して調製し、これを、成形金型内に射出し、成形温度１７０℃、成形時間１０秒で成形して厚さ３ｍｍの抗菌性ゼオライトを０．５重量％含有する樹脂板と、抗菌性ゼオライトを１．０重量％含有する樹脂板とを成形した。また、前記低密度ポリエチレンのみを成形金型内に射出し、成形温度１７０℃、成形時間１０秒で成形して厚さ３ｍｍの樹脂板（ブランク品）を成形した。これら樹脂板を以下の試料Ｎｏ．の順で試料とした。
Ｎｏ．５ ゼオミック０．５重量％含有品
Ｎｏ．６ ゼオミック１．０重量％含有品
Ｎｏ．７ ブランク品
試料Ｎｏ．５〜Ｎｏ．７を５０ｍｍ×５０ｍｍに切断し、その抗菌性試験を黄色ブドウ球菌と大腸菌について行った。黄色ブドウ球菌に対する抗菌性試験は、リンゲル液で調製した黄色ブドウ球菌懸濁液（５．４×１０⁵ 個／ｍｌ）０．５ｍｌを滅菌したシャーレ中の試料に滴下し、試料上に紫外線滅菌した試料とほぼ同サイズのポリエチレンフィルムを被せ、３５℃、湿度９３％以上の雰囲気中で２４時間培養した。培養後、滅菌済みリンゲル液１０ｍｌにて試料の表面を洗い出した。この洗い出した液中の生存菌数（個／ｍｌ）を標準寒天培地を用いて混釈平板法（寒天平板培養法；３５℃、４８時間）により測定した。大腸菌に対する抗菌性試験は、リンゲル液で調製した大腸菌懸濁液（１．０×１０⁵ 個／ｍｌ）０．５ｍｌをシャーレ中の試料に滴下し、試料上に前記したと同様のポリエチレンフィルムを被せ、３５℃、湿度９３％以上の雰囲気中で２４時間培養した。培養後、滅菌済みリンゲル液１０ｍｌにて試料の表面を洗い出した。この洗い出した液中の生存菌数（個／ｍｌ）を標準寒天培地を用いて混釈平板法（寒天平板培養法；３５℃、４８時間）により測定した。
なお、対照として菌液のみの試験も行った。対照の試験は、柄部材用樹脂試料を使用せず、滅菌したシャーレに菌液を０．５ｍｌ滴下し、前記した抗菌性試験と同一操作を行うものである。
結果は表２に示す通りである。
前記［Ｉ］、［ＩＩ］の抗菌性試験におけるリンゲル液は、試験に先立ちオートクレーブ中１２０℃、２０分間処理したものを使用した。
【００２４】
【表２】

【００２５】
（参考例１）
前記［Ｉ］の試料Ｎｏ．１のナイロンフィラメントをブラシ毛として使用し、中央で２つ折りにして松葉状にした直径０．３ｍｍのステンレスワイヤーの屈曲部から順次これを挟み込み、撚り数２２回／ｃｍで放射状に植毛しブラシ部材を作製した。次いで、柄部材への埋設用にワイヤー部をくの字状に折り曲げ、これをインサート成形に供した。前記［ＩＩ］の試料Ｎｏ．６と同一組成に溶融混合したものを、ブラシ部材のワイヤー部を挿入した柄部材成形金型内に射出し、成形温度１７０℃、成形時間１０秒でインサート成形して歯間ブラシを製造した。 得られた歯間ブラシの抗菌性を以下のようにしてモニター試験した。
すなわち、得られた歯間ブラシを、モニターに渡し、毎朝夕食後に通常通り使用し、水道水により１０秒間流水洗浄した。これを１週間繰り返した後、歯間ブラシ保管用のスリーブに挿入し、これをポリエチレン袋に入れて密封し、３７℃で１週間保管した。１週間後、ポリエチレン袋を開封し、歯間ブラシをスリーブから抜き出し、その際の歯間ブラシの臭い、外観を観察した。また、比較のために、市販品の歯間ブラシ（（株）ヘルステック製）についても同様のモニター試験を行った。試験結果は表３に示す通りである。
【００２６】
（参考例２）
参考例１における抗菌性ゼオライトの量をブラシ毛、柄部材いずれも５．０重量％とした以外は参考例１と同様にして歯間ブラシを製造した。
得られた歯間ブラシの抗菌力の効果について参考例１と同様なモニター試験を行った。試験結果は表３に示す通りである。
【００２７】
（参考例３）
［Ｉ］で用いたＡ−型の抗菌性ゼオライトをポリブチレンテレフタレート（商品名；ＬＵＭＩＣＯＮ １１０１Ｇ−３０：東レ（株）製）に対し０．１重量％溶融混合し、押し出し成形によってＭサイズのブラシ毛用のフィラメントを製造した。これを用いて、参考例１と同様にしてブラシ部材を作製した。次いで、柄部材への埋設用にワイヤー部をくの字状に折り曲げ、これをインサート成形に供した。
ポリプロピレン（商品名；ＧＲＡＮＤ ＰＯＬＹＰＲＯ Ｅ１０１：（株）グランドポリマー製）に対し［Ｉ］で用いたＡ−型の抗菌性ゼオライトを０．１重量％溶融混合したものを、ブラシ部材のワイヤー部を挿入した柄部材成形金型内に射出し、成形温度２３０℃、成形時間１０秒でインサート成形して歯間ブラシを製造した。
得られた歯間ブラシの抗菌力の効果について参考例１と同様なモニター試験を行った。試験結果は表３に示す通りである。
【００２８】
（参考例４）
参考例３における抗菌性ゼオライトの量をブラシ毛、柄部材いずれも３．５重量％とした以外は参考例１と同様にして歯間ブラシを製造した。
得られた歯間ブラシの抗菌力の効果について参考例１と同様なモニター試験を行った。試験結果は表３に示す通りである。
【００２９】
（参考例５）
ブラシ部材として参考例３と同一のものを使用した。柄部材用として、ポリプロピレン（商品名；ＧＲＡＮＤ ＰＯＬＹＰＲＯ Ｅ１０１：（株）グランドポリマー製）に対し［Ｉ］で用いたＡ−型の抗菌性ゼオライトを１．０重量％溶融混合したものを、ブラシ部材のワイヤー部を挿入した柄部材成形金型内に射出し、成形温度２３０℃、成形時間１０秒でインサート成形して歯間ブラシを製造した。
得られた歯間ブラシの抗菌力の効果について参考例１と同様なモニター試験を行った。試験結果は表３に示す通りである。
【００３０】
（実施例１、２）
［Ｉ］で用いたＡ−型の抗菌性ゼオライトを［Ｉ］で用いたポリアミドに対し２．５重量％溶融混合し、押し出し成形によってＭサイズのブラシ毛用のフィラメントを製造した。これを用いて、参考例１と同様にしてブラシ部材を作製した。
柄部材に用いる熱可塑性合成樹脂として、超低密度ポリエチレンにカルボン酸がグラフト反応により導入されてなる金属接着性ポリオレフィン（商品名；アドマー グレードＸＥ−０７０：三井石油化学工業（株）製）３０重量部、ＥＶＡ（商品名；ＥＶＡＦＬＥＸ Ｐ−１４０７：三井デュポンケミカル（株）製）４５重量部、軟質ポリエチレン（商品名；ＵＬＴＺＥＸ ２０２００Ｊ：三井石油化学工業（株）製）２５重量部を用い、［Ｉ］で用いたＡ−型の抗菌性ゼオライトを前記熱可塑性合成樹脂総量に対し０．５重量％、および、１．０重量％用い、これらを２３０℃、２時間３０分間溶融して混練し、それぞれ抗菌性ゼオライト０．５重量％含有のポリマーブレンド、１．０重量％含有のポリマーブレンドを得た。
作製したブラシ部材の直線状のワイヤー部の表面をエチルアルコールによって脱脂した後、ワイヤー部を金型内に挿入し、成形温度１８０℃、成形時間１０秒にて得られたポリマーブレンドを射出してインサート成形し、柄部材の成形と同時にワイヤー部と柄部材とを接着させ、抗菌性ゼオライトを０．５重量％含有する歯間ブラシＩと、１．０重量％含有する歯間ブラシＩＩを得た。なお、ワイヤー部の柄部材中への埋設距離は、１８．５ｍｍに設定した。
得られた歯間ブラシＩ、ＩＩをそれぞれ実施例１、２として抗菌力の効果について参考例１と同様なモニター試験を行った。試験結果は表３に示す通りである。
【００３１】
【表３】

【００３２】
なお、以下のようにして抗菌性ゼオライトが混入されていないポリマーブレンドを用いた柄部材を有する歯間ブラシも作製した。
前記金属接着性ポリオレフィン３０重量部、ＥＶＡ４５重量部、軟質ポリエチレン２５重量部を２３０℃、２時間３０分間溶融して混練し、ポリマーブレンドを得た。
作製したブラシ部材の直線状のワイヤー部の表面をエチルアルコールによって脱脂した後、ワイヤー部を金型内に挿入し、成形温度１８０℃、成形時間１０秒にて得られたポリマーブレンドを射出してインサート成形し、柄部材の成形と同時にワイヤー部と柄部材と接着させ、抗菌性ゼオライトを含有しない歯間ブラシＩＩＩを得た。ワイヤー部の柄部材中への埋設距離は、１８．５ｍｍと１６．５ｍｍとに設定した。
【００３３】
歯間ブラシＩ、ＩＩ、ＩＩＩのワイヤー部と柄部材との接着性を、柄部材からのワイヤー部の引抜き抵抗により評価した。引抜き抵抗は、オートグラフ ＡＧＳ−５００Ｄ（島津製作所製）を用い、クロスヘッドスピード１０ｍｍ／ｍｉｎで引っ張り試験によって測定した。歯間ブラシは成型後、表４に示す保存条件で保存したものを用いた。ここにおいて、６０℃で保存したのは、金属接着性ポリオレフィンの金属との接着性は、時間の経過とともに向上すると言われており、歯間ブラシの実際の使用が、成型後、市場を経て、消費者が使用するまでに所定の期間がかかることから、６０℃にて保存してその効果を促進させ、引抜き抵抗試験をより現実に近いものとするためである。
結果は、表４に示す通りである。
【００３４】
【表４】

【００３５】
表４に示される引抜き抵抗値であれば、歯間ブラシの使用により、歯間ブラシの柄部材に埋設されたワイヤー部を回転したり、引き抜いたりするような外力を作用させても、容易に柄部材からワイヤー部が抜けることがなく、長期間にわたり使用することができ、歯間ブラシとして十分使用に耐えるものである。従って、柄部材に埋め込むワイヤー部の一部をコの字形やくの字形に折曲げたりするといった細かく、面倒で困難な作業をする必要がなく、折曲げ加工工程を省略することができる。さらには、インサート成形においても、直線状のワイヤー部を金型内に挿入するだけでよいことから作業が容易であって、作業効率を向上させることができ、安価な歯間ブラシを提供することになる。また、従来技術における如く、直線状のワイヤー部を使用する場合においても、該ワイヤー部に接着剤を塗布する工程、または、ワイヤー部にプライマーを塗布する工程が必要でなくなる。また、金属ワイヤーを脱脂して表面を清浄し、成形に供するだけでよいことから、作業も安全でかつ容易であり、歯間ブラシの製造コストを上昇させることがない。なお、歯間ブラシからステンレスワイヤーが抜け出さないで通常の使用を可能とするには、インサートによる埋設距離を、この組成においては、１６．５ｍｍ以上とすることが好ましい。
ステンレスワイヤーが柄部材に接着される機構については、はっきりしていないが、金属接着性ポリオレフィン中のグラフト反応により導入されたカルボン酸とステンレス表面の不動態層との水素結合が大きな役割を果たしているものと考えられる。
また、表４から明らかなように、抗菌性ゼオライトを混入した樹脂を柄部材に使用した場合の柄部材からのワイヤーの引抜き抵抗には、抗菌性ゼオライトを混入しないものと比べ大きな差は認められていない。また、一般に、成型後の保存条件では、６０℃で１日は、室温で１カ月放置したものに相当しているとされており、このことは、歯間ブラシＩＩＩのＡとＢの結果からも明らかである。
【００３６】
（実施例３）
前記金属接着性ポリオレフィンに対し、［Ｉ］で用いたＡ−型の抗菌性ゼオライトを２．５重量％用い、２３０℃、２時間３０分間溶融して混練し、混合物を得た。
実施例１と同一のブラシ部材を用い、直線状のワイヤー部の表面をエチルアルコールによって脱脂した後、ワイヤー部を金型内に挿入し、成形温度１８０℃、成形時間２０秒にて得られた混合物を射出してインサート成形し、柄部材の成形と同時にワイヤー部と柄部材と接着させ歯間ブラシを得た。なお、成形に先立ち、金型内にフッ素系ノンシリコンタイプ離型剤を塗布した。また、ワイヤー部の柄部材中への埋設距離は、１８．５ｍｍに設定した。
得られた歯間ブラシの抗菌力の効果について参考例１と同様なモニター試験を行った。試験結果は表３に示す通りである。
また、得られた歯間ブラシのワイヤー部と柄部材との接着性を、成型後、６０℃で１日保存して、前期と同様な引抜き試験を行い評価したところ、８．６５ｋｇｆ／１８．５ｃｍであった。
【００３７】
次に、抗菌性ゼオライトを用いた歯間ブラシの金属ワイヤーとして、抗菌性の金属ワイヤーを用いた実施例を参考例とともに示しさらに説明する。
実施例に先立ち、以下のようにして、抗菌性の金属ワイヤーの抗菌性能試験を行った。
【００３８】
［ＩＩＩ］抗菌性の合金試料
抗菌性の金属ワイヤー用の合金として表５に示すような組成Ｎｉ６６．５重量％、Ｃｕ３１．５重量％、Ｆｅ１．２重量％を含有するＮｉ−Ｃｕ系合金（商品名；ＭＯＮＥＬ ａｌｌｏｙ ４００：大同特殊鋼（株）製）を使用した。また、比較のために、オーステナイト系ステンレスとしてＳｕｓ３０４、Ｓｕｓ３１６、ＳｕｓＸＭ７の３種類を使用した。これらの組成（重量％）は表５に示す通りであり、以下の試料Ｎｏ．の順で試料とした。
Ｎｏ．８ Ｎｉ−Ｃｕ系合金
Ｎｏ．９ Ｓｕｓ３０４
Ｎｏ．１０ Ｓｕｓ３１６
Ｎｏ．１１ ＳｕｓＸＭ７
【００３９】
【表５】

【００４０】
前記試料はいずれも５０ｍｍ×５０ｍｍであり、その抗菌性試験を以下のようにして、黄色ブドウ球菌と大腸菌について行った。
１）試験菌株
Ｓｔａｐｈｙｌｏｃｏｃｃｕｓ ａｕｒｅｕｓ ＩＦＯ １２７３２（黄色ブドウ球菌）
Ｅｓｃｈｅｒｉｃｈｉａ ｃｏｌｉ ＩＦＯ ３９７２（大腸菌）
２）試験培地
ＮＡ培地：普通寒天培地（栄研化学（株））
１／５０ＮＢ培地：肉エキス０．２％を添加した普通ブイヨン（栄研化学（株））を精製水で５０倍に希釈し、ｐＨを７．０±０．２に調整したもの
ＳＣＤＬＰ培地：ＳＣＤＬＰ培地（日本製薬（株））
ＳＡ培地：標準寒天培地（栄研化学（株））
３）菌液の調製
ＮＡ培地で３７℃、１６〜２４時間前培養した試験菌株をＮＡ培地に再度接種して３７℃、１６〜２０時間培養した菌体を１／５０ＮＢ培地に均一に分散させ、１ｍｌ当たりの菌数が１．０×１０⁶ 〜５．０×１０⁶ となるように調製した。
４）試料の調製
抗菌性試験に先立ち、試料を、９９．５％（Ｖ／Ｖ）エタノールをしみ込ませた脱脂綿で軽く拭いた後、風乾させた。
５）試験操作
黄色ブドウ球菌に対する抗菌性試験は、試料に菌液０．１ｍｌを滴下し、試料上に紫外線滅菌した５０×５０ｍｍ² の前記［ＩＩ］で使用したと同じポリエチレンフィルムを被せ密着させ、３５℃、相対湿度９０％以上の雰囲気中で２４時間培養した。培養後、ＳＣＤＬＰ培地で試料から生残菌を洗い出し、この洗い出した液中の生存菌数をＳＡ培地を用いて寒天平板培養法（３５℃、４８時間）により測定し、試料１個当たりに換算した。また、プラスチックシャーレを対照試料として、同様に試験した。なお、接種直後の測定は対照試料について行い、プラスチックシャーレ１個当たり２．９×１０⁵ 個であった。
大腸菌に対する抗菌性試験は、試料に菌液０．１ｍｌを滴下し、試料上に紫外線滅菌した５０×５０ｍｍ² の前記［ＩＩ］で使用したと同じポリエチレンフィルムを被せ密着させ、３５℃、相対湿度９０％以上の雰囲気中で２４時間培養した。培養後、ＳＣＤＬＰ培地で試料から生残菌を洗い出し、この洗い出した液中の生存菌数をＳＡ培地を用いて寒天平板培養法（３５℃、４８時間）により測定し、試料１個当たりに換算した。また、プラスチックシャーレを対照試料として、同様に試験した。なお、接種直後の測定は対照試料について行い、プラスチックシャーレ１個当たり１．５×１０⁵ 個であった。
結果は、表６に示すとおりであり、試料Ｎｏ．８のＮｉ−Ｃｕ系合金は試料９〜１１のステンレスと比べても良好な抗菌性を示すものである。しかも、試料Ｎｏ．８のＮｉ−Ｃｕ系合金はワイヤーとしてもステンレスワイヤーに比べ、耐食性が良好で、しかも靱性が優れワイヤーの折れ破損が生じにくいものである。
【００４１】
【表６】

【００４２】
（参考例６）
ブラシ毛として参考例１と同一のものを使用し、中央で２つ折りにして松葉状にした直径０．３ｍｍのＮｉ−Ｃｕ系合金（商品名；ＭＯＮＥＬ ａｌｌｏｙ ４００：大同特殊鋼（株）製）ワイヤーの屈曲部から順次これを挟み込み、撚り数２２回／ｃｍで放射状に植毛しブラシ部材を作製した。次いで、柄部材への埋設用にワイヤー部をくの字状に折り曲げ、これをインサート成形に供した。柄部材用として、前記［ＩＩ］の試料Ｎｏ．６と同一組成に溶融混合したものを、ブラシ部材のワイヤー部を挿入した柄部材成形金型内に射出し、成形温度１７０℃、成形時間１０秒でインサート成形して歯間ブラシを製造した。
得られた歯間ブラシの抗菌力の効果について参考例１と同様なモニター試験を行った。試験結果は表７に示す通りである。
【００４３】
（参考例７）
参考例６における抗菌性ゼオライトの量をブラシ毛、柄部材いずれも５．０重量％とした以外は参考例６と同様にして歯間ブラシを製造した。
得られた歯間ブラシの抗菌力の効果について参考例１と同様なモニター試験を行った。試験結果は表７に示す通りである。
【００４４】
（参考例８）
ブラシ毛として参考例３と同一のものを使用し、参考例６で使用したと同一のＮｉ−Ｃｕ系合金ワイヤーを用い参考例６と同様にしてブラシ部材を製造した。次いで、柄部材への埋設用にワイヤー部をくの字状に折り曲げ、これをインサート成形に供した。
柄部材として参考例３と同一のものを使用して、ブラシ部材のワイヤー部を挿入した柄部材成形金型内に射出し、成形温度２３０℃、成形時間１０秒でインサート成形して歯間ブラシを製造した。
得られた歯間ブラシの抗菌力の効果について参考例１と同様なモニター試験を行った。試験結果は表７に示す通りである。
【００４５】
（実施例４、５）
ブラシ毛として実施例１と同一のものを使用し、参考例６で使用したＮｉ−Ｃｕ系合金ワイヤーを用い参考例６と同様にしてブラシ部材を製造した。
柄部材に用いる熱可塑性合成樹脂として、実施例１と同様に超低密度ポリエチレンにカルボン酸がグラフト反応により導入されてなる金属接着性ポリオレフィン（商品名；アドマー グレードＸＥ−０７０：三井石油化学工業（株）製）３０重量部、ＥＶＡ（商品名；ＥＶＡＦＬＥＸ Ｐ−１４０７：三井デュポンケミカル（株）製）４５重量部、軟質ポリエチレン（商品名；ＵＬＴＺＥＸ ２０２００Ｊ：三井石油化学工業（株）製）２５重量部を用い、［Ｉ］で用いたＡ−型の抗菌性ゼオライトを前記熱可塑性合成樹脂総量に対し０．５重量％、および、１．０重量％用い、これらを２３０℃、２時間３０分間溶融して混練し、それぞれ抗菌性ゼオライト０．５重量％含有のポリマーブレンド、１．０重量％含有のポリマーブレンドを得た。
作製したブラシ部材の直線状のワイヤー部の表面をエチルアルコールによって脱脂した後、ワイヤー部を金型内に挿入し、成形温度１８０℃、成形時間１０秒にて得られたポリマーブレンドを射出してインサート成形し、柄部材の成形と同時にワイヤー部と柄部材と接着させ、抗菌性ゼオライトを０．５重量％含有する歯間ブラシＩＶと、１．０重量％含有する歯間ブラシＶを得た。なお、ワイヤー部の柄部材中への埋設距離は、１８．５ｍｍに設定した。
得られた歯間ブラシＩＶ、Ｖをそれぞれ実施例４、５として抗菌力の効果について参考例１と同様なモニター試験を行った。試験結果は表７に示す通りである。
【００４６】
【表７】

【００４７】
なお、以下のようにして抗菌性ゼオライトが混入されていないポリマーブレンドを用いた柄部材を有する歯間ブラシも作製した。
前記金属接着性ポリオレフィン３０重量部、ＥＶＡ４５重量部、軟質ポリエチレン２５重量部を２３０℃、２時間３０分間溶融して混練し、ポリマーブレンドを得た。
作製したブラシ部材の直線状のＮｉ−Ｃｕ系合金ワイヤーからなるワイヤー部の表面をエチルアルコールによって脱脂した後、ワイヤー部を金型内に挿入し、成形温度１８０℃、成形時間１０秒にて得られたポリマーブレンドを射出してインサート成形し、柄部材の成形と同時にワイヤー部と柄部材と接着させ、抗菌性ゼオライトを含有しない歯間ブラシＶＩを得た。ワイヤー部の柄部材中への埋設距離は、１８．５ｍｍと１６．５ｍｍとに設定した。
【００４８】
歯間ブラシＩＶ、Ｖ、ＶＩのワイヤー部と柄部材との接着性を、実施例１と同様にして柄部材からのワイヤー部の引抜き抵抗により評価した。
結果は、表８に示す通りである。
【００４９】
【表８】

【００５０】
表８に示されるように直線状のＮｉ−Ｃｕ系合金ワイヤーであっても、実施例１〜３において使用した直線状のステンレスワイヤーとほぼ同等の引抜き抵抗値であり、歯間ブラシの使用により、歯間ブラシの柄部材に埋設された抗菌性のあるワイヤー部を回転したり、引き抜いたりするような外力を作用させても、容易に柄部材からワイヤー部が抜けることがなく、長期間にわたり使用することができ、歯間ブラシとして十分使用に耐えるものである。従って、柄部材に埋め込むワイヤー部の一部をコの字形やくの字形に折曲げたりするといった細かく、面倒で困難な作業をする必要がなく、折曲げ加工工程を省略することができる。さらには、インサート成形においても、直線状のワイヤー部を金型内に挿入するだけでよいことから作業が容易であって、作業効率を向上させることができることから、ワイヤー部も抗菌性を有する安価な歯間ブラシを提供することになる。また、従来技術における如く、直線状のワイヤー部を使用する場合においても、該ワイヤー部に接着剤を塗布する工程、または、ワイヤー部にプライマーを塗布する工程が必要でなくなる。また、金属ワイヤーを脱脂して表面を清浄し、成形に供するだけでよいことから、作業も安全でかつ容易であり、歯間ブラシの製造コストを上昇させることがない。なお、歯間ブラシからＮｉ−Ｃｕ系合金ワイヤーが抜け出さないで通常の使用を可能とするには、インサートによる埋設距離を、この組成においては、１６．５ｍｍ以上とすることが好ましい。
Ｎｉ−Ｃｕ系合金ワイヤーが柄部材に接着される機構については、はっきりしていないが、金属接着性ポリオレフィン中のグラフト反応により導入されたカルボン酸とＮｉ−Ｃｕ系合金表面の不動態層との水素結合が大きな役割を果たしているものと考えられる。
また、表８から明らかなように、抗菌性ゼオライトを混入した樹脂を柄部材に使用した場合の柄部材からのワイヤーの引抜き抵抗には、抗菌性ゼオライトを混入しないものと比べ大きな差は認められていない。また、一般に、成型後の保存条件では、６０℃で１日は、室温で１カ月放置したものに相当しているとされており、このことは、歯間ブラシＶＩのＥとＦの結果からも明らかである。
【００５１】
（実施例６）
前記金属接着性ポリオレフィンに対し、［Ｉ］で用いたＡ−型の抗菌性ゼオライトを２．５重量％用い、２３０℃、２時間３０分間溶融して混練し、混合物を得た。
実施例４と同一のブラシ部材を用い、直線状のＮｉ−Ｃｕ系合金ワイヤーからなるワイヤー部の表面をエチルアルコールによって脱脂した後、ワイヤー部を金型内に挿入し、成形温度１８０℃、成形時間２０秒にて得られた混合物を射出してインサート成形し、柄部材の成形と同時にワイヤー部と柄部材と接着させ歯間ブラシを得た。なお、成形に先立ち、金型内にフッ素系ノンシリコンタイプ離型剤を塗布した。また、ワイヤー部の柄部材中への埋設距離は、１８．５ｍｍに設定した。
得られた歯間ブラシの抗菌力の効果について参考例１と同様なモニター試験を行った。試験結果は表７に示す通りである。
また、得られた歯間ブラシのワイヤー部と柄部材との接着性を、成型後、６０℃で１日保存して、前期と同様な引抜き試験を行い評価したところ、７．７３ｋｇｆ／１８．５ｃｍであった。
【００５２】
＜２＞さらに、抗菌性ゼオライトとして耐変色性に優れた抗菌性ゼオライトを使用した歯間ブラシの実施例について以下、詳しく説明する。
実施例に先立ち、以下のようにして、耐変色性に優れた抗菌性ゼオライトの抗菌性能試験、耐変色性試験を行った。
［ＩＶ］耐変色性樹脂試料
熱可塑性合成樹脂として、超低密度ポリエチレンにカルボン酸がグラフト反応により導入されてなる金属接着性ポリオレフィン（商品名；アドマー グレードＸＥ−０７０：三井石油化学工業（株）製）３０重量部、ＥＶＡ（商品名；ＥＶＡＦＬＥＸ Ｐ−１４０７：三井デュポンケミカル（株）製）４５重量部、軟質ポリエチレン（商品名；ＵＬＴＺＥＸ ２０２００Ｊ：三井石油化学工業（株）製）２５重量部を用いた。これに、酸化チタン、カーボンブラック、チタンイエロー、酸化鉄を含有してなる白色系顔料を前記熱可塑性合成樹脂総量に対し１．６重量％混入してなるものに、耐変色性に優れた抗菌性ゼオライトとして、Ａｇ、Ｚｎイオンを担持したＡ−型の抗菌性ゼオライト（商品名；バクテキラーＢＭ−１０２ＧＳＫ：カネボウ化成（株）製）を前記熱可塑性合成樹脂総量に対し０．５重量％、および、１．０重量％用い、これらを、２３０℃、２時間３０分間溶融して混練し、成形金型内に射出し、成形温度１８０℃、成形時間１０秒で成形して厚さ３ｍｍの抗菌性ゼオライトを０．５重量％、１．０重量％含有する樹脂板を成形した。この耐変色性に優れた抗菌性ゼオライトの平均粒径としては１．７μｍのものを採用した。また、前記熱可塑性合成樹脂に前記顔料を同重量％混入してなるものを成形金型内に射出し、成形温度１８０℃、成形時間１０秒で成形して厚さ３ｍｍの樹脂板（ブランク品）を成形した。これら樹脂板を以下の試料Ｎｏ．の順で試料とした。
Ｎｏ．１２ バクテキラーＢＭ−１０２ＧＳＫ０．５重量％含有品
Ｎｏ．１３ バクテキラーＢＭ−１０２ＧＳＫ１．０重量％含有品
Ｎｏ．１４ ブランク品
また、熱可塑性合成樹脂として、ポリプロピレン（商品名；ノバテック ＭＡ３Ｍ：日本ポリテム（株）製）を用いた。これに、酸化チタン、焼成顔料イエロー、焼成顔料グリーン、群青を含有してなるクリーム色系顔料を前記ポリプロピレンに対し２．０重量％混入してなるものに、耐変色性に優れた抗菌性ゼオライトであるＡｇ、Ｚｎイオンを担持したＡ−型の抗菌性ゼオライト（商品名；バクテキラーＢＭ−１０２ＧＳＫ：カネボウ化成（株）製）を前記ポリプロピレンに対し１．０重量％溶融して混練し、成形金型内に射出し、成形温度２３０℃、成形時間１０秒で成形して厚さ３ｍｍの抗菌性ゼオライトを１．０重量％含有する樹脂板を成形した。また、前記ポリプロピレンに前記顔料を同重量％混入してなるものを成形金型内に射出し、成形温度２３０℃、成形時間１０秒で成形して厚さ３ｍｍの樹脂板（ブランク品）を成形した。これら樹脂板を以下の試料Ｎｏ．の順で試料とした。
Ｎｏ．１５ バクテキラーＢＭ−１０２ＧＳＫ１．０重量％含有品
Ｎｏ．１６ ブランク品
【００５３】
（ａ）抗菌性試験
試料Ｎｏ．１２〜Ｎｏ．１６を５０ｍｍ×５０ｍｍに切断し、その抗菌性試験を以下のようにして、黄色ブドウ球菌と大腸菌について行った。
１）試験菌株
Ｓｔａｐｈｙｌｏｃｏｃｃｕｓ ａｕｒｅｕｓ ＩＦＯ １２７３２（黄色ブドウ球菌）
Ｅｓｃｈｅｒｉｃｈｉａ ｃｏｌｉ ＩＦＯ ３９７２（大腸菌）
２）試験培地
ＮＡ培地：普通寒天培地（栄研化学（株））
１／５００ＮＢ培地：肉エキス０．２％を添加した普通ブイヨン（栄研化学（株））を精製水で５００倍に希釈し、ｐＨを７．０±０．２に調整したもの
ＳＣＤＬＰ培地：ＳＣＤＬＰ培地（日本製薬（株））
ＳＡ培地：標準寒天培地（栄研化学（株））
３）菌液の調製
ＮＡ培地で３７℃、１６〜２４時間前培養した試験菌株をＮＡ培地に再度接種して３７℃、１６〜２０時間培養した菌体を１／５００ＮＢ培地に均一に分散させ、１ｍｌ当たりの菌数が２．０×１０⁵ 〜１．０×１０⁶ となるように調製した。
４）試料の調製
抗菌性試験に先立ち、試料を、９９．５％（Ｖ／Ｖ）エタノールをしみ込ませた脱脂綿で軽く拭いた後、風乾させた。
５）試験操作
黄色ブドウ球菌に対する抗菌性試験は、試料に菌液０．５ｍｌを滴下し、試料上に紫外線滅菌したポリエチレンフィルムを被せ密着させ、３５℃、相対湿度９０％以上の雰囲気中で２４時間培養した。培養後、ＳＣＤＬＰ培地で試料から生残菌を洗い出し、この洗い出した液中の生存菌数をＳＡ培地を用いて寒天平板培養法（３５℃、４８時間）により測定し、試料１個当たりに換算した。また、プラスチックシャーレを対照試料として、同様に試験した。なお、接種直後の測定は対照試料について行い、プラスチックシャーレ１個当たり２．９×１０⁵ 個であった。
大腸菌に対する抗菌性試験は、試料に菌液０．５ｍｌを滴下し、試料上に紫外線滅菌したポリエチレンフィルムを被せ密着させ、３５℃、相対湿度９０％以上の雰囲気中で２４時間培養した。培養後、ＳＣＤＬＰ培地で試料から生残菌を洗い出し、この洗い出した液中の生存菌数をＳＡ培地を用いて寒天平板培養法（３５℃、４８時間）により測定し、試料１個当たりに換算した。また、プラスチックシャーレを対照試料として、同様に試験した。なお、接種直後の測定は対照試料について行い、プラスチックシャーレ１個当たり４．１×１０⁵ 個であった。
結果は、表９に示す通りである。
【００５４】
【表９】

【００５５】
（ｂ）耐変色性試験
試料Ｎｏ．１２〜Ｎｏ．１６について、日光暴露を行い、試料の色調（Ｌ^* ・ａ^* ・ｂ^* ）をカラーコンピューター（Σ８０ ＣＯＬＯＲ ＭＥＡＳＵＲＩＮＧ ＳＹＳＴＥＭ：ＮＩＰＯＮ ＤＥＮＳＨＯＫＵ ＩＮ．ＣＯ．ＬＴＤ製）を用いて測定し、色調の結果から、色差（ΔＥ）を求めた。色差（ΔＥ）は、初期の色調（Ｌ^* ・ａ^* ・ｂ^* ）から一週間毎の色調（Ｌ^* ・ａ^* ・ｂ^* ）の差を２乗し、その合計の平方根をとったものである。
結果は表１０に示す通りである。
赤色系顔料、黄色系顔料等を混入した耐変色性樹脂材料を前記したと同様に作製し同様の耐変色性試験を行ったところ、良好な結果が得られた。
【００５６】
【表１０】

【００５７】
（実施例７）
ブラシ部材として参考例１と同一のものを使用した。柄部材には、前記［ＩＶ］の試料Ｎｏ．１３と同一組成のものを溶融混合し、インサート成形に供した。歯間ブラシの製造に際し、ブラシ部材の直線状のワイヤー部の表面をエチルアルコールによって脱脂した後、ワイヤー部を柄部材成形金型内に挿入し、成形温度１８０℃、成形時間１０秒にて溶融した前記混合物を射出してインサート成形し、柄部材の成形と同時にワイヤー部と柄部材とを接着させ歯間ブラシを得た。
なお、ワイヤー部の柄部材中への埋設距離は、１８．５ｍｍに設定した。また、６０℃で７日間保存後、実施例１と同様にして引き抜き抵抗を測定したところ、７．６８（ｋｇｆ）であった。
そして、得られた歯間ブラシの抗菌力の効果については、参考例１と同様なモニター試験を行ったところ、臭い、外観に異常はなく、変色も認められなかった。
【００５８】
【発明の効果】
この発明は、以上詳しく説明したように構成されているので、以下に記載されるような効果を奏する。
ブラシ毛が先端から所定長さにわたり金属ワイヤーに撚り込まれたブラシ部とワイヤー部とからなるブラシ部材の、ワイヤー部の末端から所定長さが柄部材に埋設されてなる歯間ブラシにおいて、前記ブラシ毛は、熱可塑性合成樹脂に対し無機系抗菌剤を０．１〜５．０重量％含有させることにより、無機系抗菌剤によりブラシ毛に付着した歯垢等にいる細菌を滅菌させることができ、歯垢等が付着した歯間ブラシを放置しても細菌、カビ等の微生物が増殖することがなく無菌状態を維持することができる。
また、前記柄部材は、熱可塑性合成樹脂に対し無機系抗菌剤を０．１〜５．０重量％含有していてもよく、これによれば、ブラシ毛および柄部材に細菌、カビ等の微生物が増殖することがなく無菌状態を維持することができる。
永続的な抗菌性を示す無機系抗菌剤によって抗菌性を付与することで、歯間ブラシは、衛生的であって、使用により歯垢等が付着したまま放置しておいても細菌やカビが増殖することがない。従って、歯間ブラシには、特有の不快な臭いも付かず、色も付かないことから気持ち良く使用できることになる。また、細菌やカビが付着していないことから歯間ブラシを歯間空隙に挿入して使用しても、口臭や口内炎の原因にならず、不適当な歯間ブラシの取り扱い方によってブラシ毛で歯間の歯肉を痛めたりしても、細菌やカビによって炎症を起こしたりする等といった恐れがない。
そして、ブラシ毛が先端から所定長さにわたり金属ワイヤーに撚り込まれたブラシ部とワイヤー部とからなるブラシ部材の、ワイヤー部の末端から所定長さが柄部材に埋設されてなる歯間ブラシにおいて、前記ブラシ毛に、熱可塑性合成樹脂に対し抗菌性ゼオライトを０．１〜５．０重量％含有させることにより、抗菌性ゼオライトによりブラシ毛に付着した歯垢等にいる細菌を死滅させることができ、歯垢等が付着した歯間ブラシを放置しても細菌、カビ等の微生物が増殖することがなく無菌状態を維持することができる。そして、前記柄部材は、熱可塑性合成樹脂に対し抗菌性ゼオライトを０．１〜５．０重量％含有させることで、ブラシ毛および柄部材に細菌、カビ等の微生物が増殖することがなく無菌状態を維持することができる。
永続的な抗菌性を示す抗菌性ゼオライトによって抗菌性を付与することで、歯間ブラシは、衛生的であって、使用により歯垢等が付着したまま放置しておいても細菌やカビが増殖することがない。従って、歯間ブラシには、特有の不快な臭いも付かず、色も付かないことから気持ち良く使用できることになる。また、細菌やカビが付着していないことから歯間ブラシを歯間空隙に挿入して使用しても、口臭や口内炎の原因にならず、不適当な歯間ブラシの取り扱い方によってブラシ毛で歯間の歯肉を痛めたりしても、細菌やカビによって炎症を起こしたりする等といった恐れがない。
前記金属ワイヤーは、Ｎｉ６６．５重量％、Ｃｕ３１．５重量％、Ｆｅ１．２重量％を含有する合金に例示される抗菌性のＮｉ−Ｃｕ系合金、少なくともＣｕ１．５重量％、Ｃｒ１７重量％含有するステンレスに例示される抗菌性のステンレス等の抗菌性合金からなるものであってもよく、これによれば、ワイヤーにも細菌、カビ等の微生物が増殖することがなく無菌状態を維持することができることになる。
そして、抗菌性を付与した歯間ブラシにおいて、柄部材を少なくとも金属接着性ポリオレフィンからなる熱可塑性合成樹脂とすると、ブラシ部材の柄部材に埋設された所定長さのワイヤー部が金属接着性ポリオレフィンによって接着されることから、柄部材に埋め込み固定するためのワイヤー部の一部をコの字形やくの字形に折曲げたりするといった細かく、面倒で困難な作業をする必要がなく、折曲げ加工工程を省略することができる等から安価な歯間ブラシを提供することができる。
【図面の簡単な説明】
【図１】本発明の歯間ブラシの一例を示し、（ａ）は平面図、（ｂ）はブラシ毛の拡大断面図、（ｃ）は柄部材の拡大断面図である。
【図２】本発明の歯間ブラシの他の例を示す平面図である。
【図３】従来の歯間ブラシの平面図である。
【符号の説明】
１ 歯間ブラシ
２ ブラシ部材
３ 柄部材[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an antibacterial interdental brush. More particularly, the present invention relates to an interdental brush used for insertion into an interdental space to remove plaque or the like in the interdental space or to massage the gums in the interdental region.
[0002]
[Prior art]
Plaque is a glucan produced by Streptococcus mutans, a resident bacterium that lives in the oral cavity, using sugar in the food as a nutrient source, and this is attached to the surface of the tooth, and is caused by lime in the saliva. When calcified, it becomes tartar that is difficult to peel off and is fixed to the surface of the tooth. In addition, anaerobic and aerobic bacteria with nutrients such as food residue are inhabited in plaque and calculus. About 70% of dental plaque is formed by microorganisms, including a mass of filamentous fungi, many gram-positive cocci, bacilli, and a few gram-negative bacteria, and the remaining 30% is mostly bacterial polysaccharides. It consists of exopolysaccharide dextran, mutan, levan and the like. It is said that periodontal diseases such as caries, gingivitis, or alveolar pyorrhea are caused by acids, toxins, etc. produced by bacteria in dental plaque. If plaque and calculus are left as they are, a pocket is formed between the teeth and gums and pus accumulates, and the accumulated pus melts the alveolar bone supporting the teeth and progresses to alveolar pus leakage. In order to prevent gingivitis and alveolar pyorrhea, the plaque is removed with a toothbrush to clean the surface of the teeth, prevent the development of calculus, and massage the gingiva to reduce gingival blood circulation. It is necessary to increase, promote metabolism, eliminate pockets and secure teeth.
[0003]
The interdental brush is positioned as an auxiliary tool for the toothbrush, and removes plaque and the like of the interdental space that cannot be removed by a normal toothbrush, and prevents the occurrence of dental caries on the teeth facing the interdental part. It is used to prevent the occurrence of periodontal disease in the interdental region and massage the gums in the interdental region. The interdental brush (20) is bent, for example, as shown in FIG. 3, in a brush portion (22) in which brush hair (21) is twisted into a metal wire made of stainless steel or the like, and in a U shape or a U shape. And a handle member (24) having a predetermined length of embedded metal wire portion (23). For the bristles (21), a thermoplastic synthetic resin such as polyamide or polybutylene terephthalate is used. The handle member (24) is made of a soft thermoplastic synthetic resin such as low-density polyethylene (LDPE) or other soft polyethylene, polypropylene (PP), EVA (ethylene-vinyl acetate copolymer), or a polymer blend. in use. The wire portion (23) protrudes from the leading tip (25) of the handle member (24), and it is necessary to bend the interdental brush (20) in order to brush the interdental space of the back teeth. In some cases, by bending the tip (25), the metal wire can be bent without reducing the radius of curvature, and the wire portion (23) can be prevented from being bent. The interdental brush (20) is attached to the tooth surface by the brush portion (22) when the brush portion (22) is inserted into the interdental space from a direction substantially perpendicular to the teeth and moved in that direction. It is possible to remove residual plaque or food residue accumulated in the interdental space, clean the tooth surface of the interdental space, and the brush part (22) massages the gingival part appropriately. It is often used because it stimulates gingival metabolism, trains gingiva, and makes gingiva healthy.
[0004]
Plaque or the like removed by the interdental brush adheres to the surface of the bristle (21) or between the bristle (21). Dental plaque is sticky, and the bristle (21) is made of a material that is thinner than an ordinary toothbrush, and the bristle (21) is close to each other, and is attached to the surface of the bristle (21). It is very difficult to completely remove dirt and the like with tap water. If the interdental brush (20) with plaque or the like attached to the brush hair (21) is left unattended, bacteria and mold will grow in the plaque and the like. That is, the interdental brush in which bacteria and fungi have grown has a peculiar unpleasant odor, and in some cases, it may be colored and may be reluctant to continue to use. When the interdental brush (20) with bacteria and molds attached is inserted into the interdental space and used, bacteria and mold remain in the oral cavity, which may cause bad breath and stomatitis. Moreover, if the gingiva between teeth is damaged by the brush hair (21) of the interdental brush (20), inflammation will be caused by bacteria and mold. In some cases, it may cause harm to the body, such as gastrointestinal disorders.
[0005]
[Problems to be solved by the invention]
The present invention was devised as a result of intensive studies in view of the above circumstances, and an object thereof is to provide an interdental brush in which harmful microorganisms such as bacteria and mold do not grow.
[0006]
[Means for Solving the Problems]
In order to solve the above-mentioned problem, the interdental brush of the present invention is a predetermined brush from the end of the wire part of a brush member comprising a brush part and a wire part in which the bristle is twisted into a metal wire over a predetermined length from the tip. In the interdental brush whose length is embedded in the handle member, the brush hair contains 0.1 to 5.0% by weight of an inorganic antibacterial agent with respect to the thermoplastic synthetic resin.
This makes it possible to sterilize bacteria in plaque and the like attached to the brush hair by the inorganic antibacterial agent, and microorganisms such as bacteria and mold grow even if the interdental brush to which plaque adheres is left. The sterility can be maintained without the need to do so.
The handle member may contain 0.1 to 5.0% by weight of an inorganic antibacterial agent relative to the thermoplastic synthetic resin. According to this, microorganisms such as bacteria and mold are present on the brush hair and the handle member. Aseptic conditions can be maintained without proliferation.
Further, the interdental brush of the present invention is a brush member composed of a brush portion and a wire portion in which the brush bristles are twisted into a metal wire over a predetermined length from the tip, and the predetermined length from the end of the wire portion to the handle member In the interdental brush embedded, the brush hair may contain 0.1 to 5.0% by weight of antibacterial zeolite with respect to the thermoplastic synthetic resin.
According to this, bacteria in the plaque etc. attached to the brush hair can be sterilized by the antibacterial zeolite, and microorganisms such as bacteria, mold and the like grow even if the interdental brush attached with the plaque etc. is left. Aseptic conditions can be maintained.
The handle member may contain 0.1 to 5.0% by weight of antibacterial zeolite with respect to the thermoplastic synthetic resin. According to this, microorganisms such as bacteria and mold grow on the brush hair and the handle member. The sterility can be maintained without the need to do so.
As the antibacterial zeolite, it is preferable to use an antibacterial zeolite excellent in discoloration resistance as described later. Such antibacterial zeolite excellent in discoloration resistance is not only mixed in the interstitial brush bristles and the thermoplastic synthetic resin for the handle member, but also mixed in the interstitial brush sleeve thermoplastic synthetic resin. It is also possible. Mixing antibacterial zeolite with excellent discoloration resistance is preferable because even if it is used for a long period of time, the thermoplastic synthetic resin is less discolored and the commercial value can be maintained over a long period of time.
As the metal wire, stainless steel, titanium, titanium alloy, cobalt chrome, nickel chrome, iron, copper, aluminum, etc. can be used, but stainless steel has good corrosion resistance, sufficient mechanical strength, and is inexpensive. It is preferable from the point.
Further, the metal wire may be made of an antibacterial alloy, and according to this, a sterilized state can be maintained without microorganisms such as bacteria and mold growing on the wire. As the antibacterial alloy, an antibacterial Ni—Cu alloy, an antibacterial stainless steel or the like can be adopted.
Examples of the antibacterial Ni—Cu alloy include an alloy containing 66.5 wt% Ni, 31.5 wt% Cu, and 1.2 wt% Fe.
Examples of the antibacterial stainless steel include an antibacterial stainless steel (trade name: NSS AM1: manufactured by Nisshin Steel Co., Ltd.) containing at least 1.5 wt% Cu and 17 wt% Cr.
It is preferable that the thermoplastic synthetic resin constituting the handle member is made of at least a metal-adhesive polyolefin because the wire portion of the brush member can be embedded and fixed in a straight line, and the metal-adhesive polyolefin at that time is an ultra-low density polyethylene. It is desirable that a carboxylic acid is introduced into the resin by a graft reaction. The metal-adhesive polyolefin can be used alone or in a polymer blend with other thermoplastic synthetic resins. For the polymer blend, a thermoplastic synthetic resin as described later can be used, and the metal wire does not easily come out of the handle member when the metal adhesive polyolefin is 5.6 parts by weight or more in 100 parts by weight of the thermoplastic synthetic resin. It is preferable for obtaining a sufficient adhesive force. If the metal-adhesive polyolefin is less than 5.6 parts by weight in 100 parts by weight of the thermoplastic synthetic resin, the adhesive force between the metal wire surface and the pattern member is inferior, which is not preferable. In particular, the polymer blend is preferably a combination of metal-adhesive polyolefin, EVA and soft polyethylene, preferably 5 to 55 parts by weight of the metal-adhesive polyolefin, 55 to 25 parts by weight of EVA, and 10 to 35 parts by weight of soft polyethylene. .
[0007]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments will be shown and the present invention will be described in more detail. Of course, the present invention is not limited to the following embodiments.
Fig.1 (a) is a top view which shows an example of the interdental brush of this invention, (b) is an expanded sectional view of a bristle, (c) is an expanded sectional view of a handle member. Here, it demonstrates as what uses antimicrobial zeolite as an inorganic type antimicrobial agent.
As shown in FIG. 1, the interdental brush (1) includes a brush member (2) and a handle member (3). In the brush member (2), the bristles (5) formed by molding a thermoplastic synthetic resin mixed and kneaded with the antibacterial zeolite (4) were twisted into the stainless wire over a predetermined length from the tip thereof. It consists of a brush part (6) and a wire part (7). And the predetermined length from the terminal of the said wire part (7) is embed | buried under the handle member (3) of the thermoplastic synthetic resin in which the antimicrobial zeolite (4) was mixed and kneaded. When the thermoplastic synthetic resin containing the metal-adhesive polyolefin described later in the handle member (3) is not used, the wire portion (7) embedded in the handle member (3) is usually a dogleg shape, Or use the one folded in a U shape Just do it. From the head part (3a) of the handle member (3), a tapered detail (8) enveloping the wire part (7) protrudes, and a pinch is provided between the trunk part (3b) and the tail part (3c). The part (9) is provided in an annular shape. The outer diameter of the trunk portion (3b) and the tail portion (3c) is the same, and can be connected by being inserted into a sleeve (not shown) if necessary. Accordingly, the interdental brush (1) can be stored by inserting the sleeve (6) into the sleeve from the direction of the brush (6) and fitting the body (3b), and the tail (3c) is fitted to the sleeve. Thus, the interdental brush can be used in a state extended from the sleeve.
[0008]
As the thermoplastic synthetic resin used for the brush hair, for example, polyamide, polybutylene terephthalate, or the like can be used. These may be used alone or in combination of two or more.
[0009]
Examples of the thermoplastic synthetic resin used for the handle member include soft polyethylene such as low density polyethylene (LDPE), polypropylene (PP), EVA (ethylene-vinyl acetate copolymer), polyacetal (POM), and the like. These may be used alone or in combination of two or more. Further, as will be described later, a metal-adhesive polyolefin alone or a polymer blend with another thermoplastic synthetic resin may be used.
[0010]
Antibacterial zeolite is an ion-exchangeable ion in natural zeolite or synthetic zeolite, such as sodium ion, calcium ion, potassium ion, magnesium ion, iron ion, etc., part or all of antibacterial metal ion such as silver, What was obtained by exchanging with one or more metal ions selected from copper, zinc, bismuth, and thallium can be employed. Preferably, it is substituted with ammonium ions and the antibacterial metal ions. Of the silver, copper, zinc, bismuth and thallium ions as antibacterial metal ions, silver, copper or zinc ions are preferred from the standpoint of antibacterial properties, economic efficiency, biological harm and the like.
Zeolite is generally an aluminosilicate having a three-dimensional framework structure, and has the general formula: XM _Z / _n O ・ Al ₂ O _Three ・ YSiO ₂ ・ ZH ₂ Represented by O. Here, M represents an ion-exchangeable ion and is usually a monovalent or divalent metal ion, n is a valence of a (metal) ion, X is a coefficient of a metal oxide, Y is a coefficient of silica, and Z is a crystal The number of water molecules. Specific examples of the zeolite include, for example, A-type zeolite, X-type zeolite, Y-type zeolite, T-type zeolite, high silica zeolite, sodalite, mordenite, analcym, clinoptilolite, chabasite, Although erionite etc. can be mentioned, it is not limited to this. The ion exchange capacities of these exemplified zeolites are: A-type zeolite 7 meq / g, X-type zeolite 6.4 meq / g, Y-type zeolite 5 meq / g, T-type zeolite 3.4 meq / g, Sodalite 11. 5 meq / g, mordenite 2.6 meq / g, analsim 5 meq / g, clinoptilolite 2.6 meq / g, chabasite 5 meq / g, erionite 3.8 meq / g, all of which are antibacterial metal ions Sufficient capacity for ion exchange.
[0011]
From the viewpoint of antibacterial properties, the antibacterial metal ions in the zeolite should be contained in an amount of 0.1 to 25% by weight (on the basis of drying at 110 ° C.). It is more preferable to contain 0.1 to 8% by weight of silver ions and 0.1 to 20% by weight of zinc ions. In addition, it is necessary to prevent discoloration of the zeolite that the ammonium ion in the zeolite is contained in an amount of 0.5 to 5% by weight, preferably 0.5 to 2% by weight (based on a drying temperature of 110 ° C.). .
Examples of the antibacterial zeolite excellent in discoloration resistance described above include antibacterial zeolite based on the production method described in JP-A-6-247816 and antibacterial zeolite based on the production method described in JP-A-7-247113. . The antibacterial zeolite based on the production method described in JP-A-6-247816 is obtained by treating a zeolite carrying an antibacterial metal with hydroxy or alkoxysilane or a low condensate thereof. Further, the antibacterial zeolite based on the production method described in JP-A-7-247113 is an alkoxysilane containing 0.05 part by weight or more of ethylenically unsaturated bond with respect to 1000 parts by weight of zeolite carrying an antibacterial metal. Copolymer comprising at least 9.95 parts by weight of ethylenically unsaturated monomer and 10 to 200 parts by weight of the sum of the alkoxysilane monomer and ethylenically unsaturated monomer It is obtained by subjecting the above zeolite to surface treatment by coalescence. Of these, the antibacterial zeolite described in JP-A-7-247113 is preferred because of its excellent dispersibility and compatibility with low molecular weight organic polymers.
In addition, it is also possible to use an antibacterial polyolefin composition excellent in discoloration resistance mixed with an antibacterial zeolite. Examples of such antibacterial polyolefins include those described in JP-B-7-21091 and JP-B-6-23274. The antibacterial polyolefin composition described in JP-B-7-21091 is a kind selected from the group consisting of (a) copper, silver, zinc, and tin with respect to 100 parts by weight of a polyolefin resin containing a chlorine compound. Or 0.1 to 5.0 parts by weight of an antibacterial agent obtained by holding two or more kinds of metals in a porous zeolite, (b) 0.01 to 0.5 parts by weight of a phosphorus-based antioxidant, and (c) Containing 0.01 to 0.3 parts by weight of a phenolic antioxidant and (d) 0.01 to 0.5 parts by weight of a neutralizing agent for chlorine composed of hydrotalcites and / or magnesium oxide. It is a feature. The antibacterial polyolefin composition described in JP-B-6-23274 is a kind selected from the group consisting of (a) silver, copper, zinc, and tin with respect to 100 parts by weight of a polyolefin resin containing a chlorine compound. Or 0.1 to 5.0 parts by weight of an antibacterial agent obtained by holding two or more kinds of metals in a porous zeolite, (b) 0.01 to 0.5 parts by weight of a hindered amine-based polysiloxane compound, and (c) 0.01 to 0.5 parts by weight of one or more neutralizers selected from the group consisting of hydrotalcites, calcium aluminum silicate, Group II metal oxides and hydroxides It is characterized by containing.
The antibacterial antibacterial zeolite excellent in discoloration resistance and the antibacterial polyolefin composition excellent in discoloration resistance mixed with the antibacterial zeolite are appropriately selected and used.
Such antibacterial zeolite exhibits permanent antibacterial properties.
[0012]
The antibacterial zeolite is preferably contained in an amount of 0.1 to 5.0% by weight based on the thermoplastic synthetic resin for brush hair. If the antibacterial zeolite is less than 0.1% by weight, it is insufficient to uniformly expose the fine particles of the antibacterial zeolite on the surface of the brush hair, and sufficient antibacterial properties cannot be exhibited. If it exceeds 1, the mechanical properties such as the bristle strength, elastic modulus, heat resistance and the like are inferior, and the influence of the color of the antibacterial zeolite is strong, which is not preferable. The thermoplastic synthetic resin for brush bristles is made into a molten state, mixed with finely divided antibacterial zeolite, and then kneaded, and then brush bristles are obtained by extrusion molding or the like. The average particle size of the antibacterial zeolite is 1.5-2 μm, and the maximum particle size is 10 μm or less, so that the antibacterial zeolite is uniformly dispersed in the thermoplastic synthetic resin and does not hinder molding, and has good antibacterial properties From the viewpoint of expressing
[0013]
Moreover, it is preferable to contain the said antimicrobial zeolite 0.1 to 5.0weight% with respect to the thermoplastic synthetic resin of a handle member. If the antibacterial zeolite is less than 0.1% by weight, it is insufficient to expose the microparticles of the antibacterial zeolite uniformly on the surface of the handle member, and sufficient antibacterial properties cannot be exhibited. On the other hand, if it exceeds 5.0% by weight, mechanical properties such as the strength, elastic modulus, heat resistance and the like of the handle member will be inferior, and the influence of the color of the antibacterial zeolite will be strong, which is not preferable. The thermoplastic synthetic resin for the handle member is made into a molten state, and the particulate antibacterial zeolite is mixed and kneaded, and then molded to obtain the handle member. The average particle size of the antibacterial zeolite is 1.5 to 2 μm, and the maximum particle size is 10 μm or less in order to achieve uniform dispersion of the antibacterial zeolite in the thermoplastic synthetic resin, good molding, and good antibacterial properties. Is preferable. For forming the handle member, an insert molding method in which the wire portion of the brush member is inserted and molded in a mold is employed.
[0014]
A thermoplastic synthetic resin containing at least a metal-adhesive polyolefin is used as the handle member. Because As shown in FIG. 2, the wire part (10) is formed into a handle member (10) by insert molding in which a predetermined length is embedded in the handle member (3) from the end of the linear wire part (10) of the brush member (2). 3) Since it is sufficiently bonded to the pattern member (3), operations such as bending of the wire part (10) embedded in the handle member (3), application of an adhesive to the wire part (10), or application of a primer are required. It is preferable because it does not.
[0015]
As a metal-adhesive polyolefin, it is a metal-adhesive polyolefin in which carboxylic acid is introduced into ultra-low-density polyethylene by a graft reaction. Adhesiveness with embedded linear wire part, molding processability, use of pattern members It is desirable from the point of time flexibility. The adhesion mechanism between the metal-adhesive polyolefin and the metal is not clear, but causes a chemical bond or a hydrogen bond between the carboxylic acid introduced by the graft reaction and the oxide film on the metal surface or the —OH group in the sorption water. This is probably due to this. The metal-adhesive polyolefin may be a single polymer blend or a polymer blend containing the metal-adhesive polyolefin.
In the case of the metal adhesive polyolefin alone, it is preferable to apply a release agent to the mold in order to improve the release property after molding. In order to prevent sink marks during molding, the injection speed may be lowered.
Examples of the metal adhesive polyolefin include those described in JP-B-54-18297, JP-B-58-12299, JP-B-4-60140, and JP-A-2-6513. Japanese Patent Publication No. 54-18297 discloses a polyolefin grafted with an unsaturated carboxylic acid or its anhydride or a polyolefin A blended with the grafted polyolefin in an amount of 0.01 to 2% by weight of phosphoric acid. It contains a composition having a good adhesion persistence with respect to a metal characterized by containing salt B. The one described in Japanese Patent Publication No. 58-12299 is composed of 70 to 95 parts by weight of polyethylene partially or completely modified with unsaturated carboxylic acid or its anhydride and 5 to 30 parts by weight of polypropylene, and is contained by modification. The amount of unsaturated carboxylic acid or anhydride obtained is 1 × 10 as carbonyl groups per gram of composition. ^-Four 1x10 ^-1 A polyolefin composition having excellent metal adhesion, characterized by being in the range of millimolar equivalent. Japanese Patent Publication No. 4-60140 discloses an ultrahigh molecular weight polyolefin having an ultimate clay [η] measured in decalin at 135 ° C. of 10 dl / g or more, an unsaturated carboxylic acid, its acid anhydride, A modified ultra-high molecular weight polyolefin powder obtained by graft copolymerization of unsaturated carboxylic acid derivative component units comprising a salt or an ester thereof, wherein at least 20% by weight or more passes through a 350 mesh sieve and has an average particle size of 1 to 80 μm. The content of the modified ultra-high molecular weight polyolefin powder in the range. JP-A-2-6513 discloses that an unsaturated carboxylic acid or a derivative thereof is randomly added to a polyolefin copolymer derived from propylene, ethylene, and an α-olefin having 4 to 20 carbon atoms. 01 to 10% by weight of a modified polymer graft-polymerized, wherein the polyolefin copolymer has a propylene component of 40 to 90 mol%, an ethylene component of 2 to 40 mol%, and an α-olefin component of 10 to 40 mol%. Is in range,
And this α-olefin component / (ethylene component + the α-olefin component)
The polyolefin-modified polymer is characterized in that the relevant molar ratio is in the range of 0.1 to 0.9.
The metal-adhesive polyolefin is appropriately selected and used.
[0016]
When using a polymer blend, the thermoplastic synthetic resin other than the metal-adhesive polyolefin may be a high pressure low density polyethylene (HPLDPE), a very low density polyethylene (VLDPE), a linear low density polyethylene (LLDPE), or the like. Soft polyethylene, medium density polyethylene (MDPE), high density polyethylene (HDPE), ethylene vinyl alcohol copolymer (PVOH), ethylene-vinyl acetate copolymer (EVA), polypropylene (PP), ethylene ionomer, etc. can be used. . These thermoplastic synthetic resins other than the metal-adhesive polyolefin can be polymer-blended with one or more kinds of the metal-adhesive polyolefin. The combination of thermoplastic synthetic resin in the polymer blend does not exclude the adhesion of the metal adhesive polyolefin to the metal wire. Considering the compatibility and miscibility of the resins, the bending strength of the resulting pattern member, etc. It is determined in consideration of the mechanical properties, biocompatibility, mold release properties, moldability such as anti-sink properties, and manufacturing cost. As for the mixing ratio, it is necessary to select a range in which sufficient adhesion with the metal wire can be secured. As described above, when a metal-adhesive polyolefin obtained by introducing a carboxylic acid into ultra-low density polyethylene by graft reaction and another thermoplastic synthetic resin are used as a polymer blend, the metal-adhesive polyolefin is a thermoplastic synthetic resin 100. It is preferable that the amount is 5.6 parts by weight or more in parts by weight in order to obtain a sufficient adhesive force that the metal wire does not easily come out of the handle member. If the metal-adhesive polyolefin is less than 5.6 parts by weight in 100 parts by weight of the thermoplastic synthetic resin, the adhesive force between the metal wire surface and the pattern member is inferior, which is not preferable.
[0017]
As a polymer blend, combining metal-adhesive polyolefin, EVA, and soft polyolefin has sufficient adhesion to metal wires, and can be molded without using a mold release agent. Is preferable, and an appropriate flexibility is obtained for the handle member. And the compounding ratio of 5-55 weight part of metal-adhesive polyolefin, 55-25 weight part of EVA, and 10-35 weight part of soft polyethylene is preferable. If the metal-adhesive polyolefin is less than 5 parts by weight, the adhesive strength with the metal wire is insufficient, and if it exceeds 55 parts by weight, the adhesive strength with the metal wire is sufficient, but a mold release agent is used during molding. It becomes necessary to do. In this case, when the metal-adhesive polyolefin is 5 parts by weight or more and less than 10 parts by weight, the metal wire has an adhesive force with the metal wire and the releasability is particularly good. With excellent adhesive strength, releasability and moldability are particularly good. When the amount exceeds 20 parts by weight, the balance between adhesion to metal wires, releasability, moldability, and flexibility of the pattern member is further improved. be able to. Among these, the most preferable blending ratio is 30 parts by weight of metal adhesive polyolefin, 45 parts by weight of EVA, and 25 parts by weight of soft polyethylene.
[0018]
Various methods such as a physical blending method by melting and a reactive processing method can be adopted for the polymer blend, but the physical blending method by melting is preferable from the viewpoint of uniform dispersion. In physical blending by melting, when the softening temperature, melt viscosity, etc. of the thermoplastic synthetic resin to be blended are close, it is preferable to use a single screw extruder, etc., the difference in softening temperature is large, and the melt viscosity is also high. If they differ greatly, it is preferable to use a twin screw extruder. The material that has been polymer blended and extruded from the extruder is in the form of pellets, and in insert molding, the pellets are melted and mixed with antibacterial zeolite fine particles for use in molding. According to such a polymer blend, the amount of expensive metal-adhesive polyolefin used can be reduced, and a cheaper antibacterial interdental brush handle can be provided.
[0019]
Not only antibacterial zeolite but also other antibacterial zeolite, for example, one or two or more kinds of antibacterial substances selected from antibacterial zirconium phosphate, antibacterial calcium phosphate and antibacterial glass are used. Of course, you may. At that time, the total content of the thermoplastic synthetic resin containing antibacterial zeolite and one or more kinds selected from antibacterial zirconium phosphate, antibacterial calcium phosphate and antibacterial glass is 0.00. It is preferable to set it as 1 to 5.0 weight%.
As the antibacterial zirconium phosphate, silver zirconium phosphate (trade name; Novalon: manufactured by Toa Gosei Co., Ltd., average particle size: 0.3 to 1.5 μm), and as the antibacterial calcium phosphate, silver apatite (trade name; apasider) A: Sangi Co., Ltd., average particle size of 1 to 10 μm), and antibacterial glass, silver glass (trade name; Ion Pure: manufactured by Ishizuka Glass Co., Ltd., average particle size of 1 to 20 μm) can be used. Needless to say, the antibacterial zirconium phosphate, the antibacterial calcium phosphate, and the antibacterial substance carried on the antibacterial glass are not limited to the above-described silver but may be copper or zinc.
Needless to say, an inorganic antibacterial agent other than the antibacterial substances as described above can be used. In short, the thermoplastic resin used for the bristles of the interdental brush or the thermoplastic resin used for the handle member. It can be mixed and kneaded uniformly and can exhibit sufficient antibacterial properties, and as such, titanium oxide can be further exemplified. Of course, the various antibacterial agents described above can be used alone or in combination of two or more.
[0020]
In forming the pattern member, inorganic pigment colorants, auxiliaries, stabilizers and the like can be added as appropriate. The addition amount of the inorganic pigment-based colorant is preferably 2% by weight or less with respect to the thermoplastic synthetic resin constituting the handle member.
[0021]
【Example】
Examples of interdental brushes using antibacterial zeolite Along with reference examples This will be described in more detail.
<1> Prior to the examples, the antibacterial performance test of the antibacterial zeolite was performed as follows.
[I] Brush hair sample
A-type antibacterial zeolite (trade name; Zeomic: manufactured by Sinanen Zeomic Co., Ltd.) is melt-mixed with polyamide (trade name; TYEX612 NYLON: manufactured by DuPont Co., Ltd.) in an amount of 1.0% by weight. A nylon filament for hair was produced. The average particle diameter of the antibacterial zeolite is 1.5 μm, and A-type zeolite (Na ₂ O ・ Al ₂ O ₃ ・ 1.9SiO ₂ ・ XH ₂ O) Na ions are ion-exchanged with Ag ions and Zn ions. This A-type antibacterial zeolite has a structural formula: 0.05 Ag ₂ O.0.85ZnO.0.1Na ₂ O ・ Al ₂ O ₃ ・ 2SiO ₂ ・ 5H ₂ It can be expressed by O. The content of Ag ions in this antibacterial zeolite is 2.5% by weight and Zn ions are 14% by weight. Two types of nylon filaments, M size with a diameter of 0.076 mm and S size with 0.064 mm, are manufactured. For comparison, M and S size nylon filaments (blank products) that do not contain the antibacterial zeolite are also available. Manufactured. 1.5 g of each of these nylon filaments was added to the following sample No. Samples were prepared in the following order.
No. 1 M for Zeomic containing 1.0% by weight
No. 2 M blank
No. 3S Zeomic 1.0 wt% product
No. 4 S blank product
Sample No. 1-No. Four antibacterial tests were performed on S. aureus and E. coli. In the antibacterial test against Staphylococcus aureus, 70 ml of Ringer's solution was placed in an Erlenmeyer flask, sterilized by moist heat, and then the Erlenmeyer flask was separately prepared with a suspension of Staphylococcus aureus (5.4 × 10). ⁵ Add 5 ml to the test solution, add the sample to this, shake at 25 ° C. and about 150 rpm, and count the number of surviving bacteria (individuals / ml) in the test solution after 24 hours on a standard agar medium. It was measured by the pour plate method (agar plate culture method; 35 ° C., 48 hours). In the antibacterial test against E. coli, 70 ml of Ringer's solution was placed in an Erlenmeyer flask, sterilized with moist heat, and then the Escherichia coli suspension (1.0 × 10 ⁵ Add 5 ml to the test solution, add the sample to this, shake at 25 ° C. and about 150 rpm, and count the number of surviving bacteria (individuals / ml) in the test solution after 24 hours on a standard agar medium. It was measured by the pour plate method (agar plate culture method; 35 ° C., 48 hours).
As a control, a test using only the bacterial solution was also performed. This is a test for confirming whether the active state of Staphylococcus aureus and Escherichia coli used in the antibacterial test is good, and the same operation as the antibacterial test described above is performed except that a brush hair sample is not used. It is.
The results are as shown in Table 1.
[0022]
[Table 1]

[0023]
[II] Resin sample for pattern member
The A-type antibacterial zeolite used in the above [I] is 0.5% by weight and 1.0% by weight, respectively, with respect to low density polyethylene (trade name; MIRASON 401: manufactured by Mitsui Petrochemical Co., Ltd.). Prepared by melt mixing, this was injected into a molding die, molded at a molding temperature of 170 ° C. and molding time of 10 seconds, and a resin plate containing 0.5% by weight of antibacterial zeolite having a thickness of 3 mm; A resin plate containing 1.0% by weight of antibacterial zeolite was molded. Further, only the low density polyethylene was injected into a molding die and molded at a molding temperature of 170 ° C. and a molding time of 10 seconds to form a resin plate (blank product) having a thickness of 3 mm. These resin plates are referred to as Sample No. below. Samples were prepared in the following order.
No. 5 Product containing 0.5% by weight of Zeomic
No. 6 Product containing 1.0% by weight of Zeomic
No. 7 Blank product
Sample No. 5-No. 7 was cut into 50 mm × 50 mm, and the antibacterial test was performed on S. aureus and E. coli. Antibacterial activity test against Staphylococcus aureus was carried out using a Staphylococcus aureus suspension (5.4 × 10 5) prepared with Ringer's solution. ^Five 0.5 ml of the solution / ml) was dropped onto a sample in a sterilized petri dish, and the sample was covered with a polyethylene film of approximately the same size as the sample sterilized with UV light, and cultured in an atmosphere of 35 ° C. and humidity of 93% or more for 24 hours . After incubation, the surface of the sample was washed out with 10 ml of sterilized Ringer's solution. The number of viable cells (cells / ml) in the washed out solution was measured by the pour plate method (agar plate culture method; 35 ° C., 48 hours) using a standard agar medium. The antibacterial test against E. coli was carried out using an E. coli suspension (1.0 × 10 ^Five 0.5 ml / ml) was dropped onto a sample in a petri dish, and the sample was covered with the same polyethylene film as described above, and cultured in an atmosphere of 35 ° C. and a humidity of 93% or more for 24 hours. After incubation, the surface of the sample was washed out with 10 ml of sterilized Ringer's solution. The number of viable cells (cells / ml) in the washed out solution was measured by the pour plate method (agar plate culture method; 35 ° C., 48 hours) using a standard agar medium.
As a control, a test using only the bacterial solution was also performed. In the control test, 0.5 ml of the bacterial solution was dropped into a sterilized petri dish without using the handle member resin sample, and the same operation as the above-described antibacterial test was performed.
The results are as shown in Table 2.
The Ringer's solution in the antibacterial test of [I] and [II] used was treated in an autoclave at 120 ° C. for 20 minutes prior to the test.
[0024]
[Table 2]

[0025]
( Reference example 1 )
Sample [I] of the above [I]. 1 Nylon filament is used as brush hair, and it is sandwiched in order from a bent portion of a 0.3 mm diameter stainless steel wire that is folded in half at the center and crushed, and is radially planted at a twist number of 22 times / cm. Was made. Next, the wire part was bent into a U shape for embedding in the handle member, and this was subjected to insert molding. Sample No. in [II] above. What was melt-mixed to the same composition as No. 6 was injected into a pattern member molding die into which the wire portion of the brush member was inserted, and insert molding was performed at a molding temperature of 170 ° C. and a molding time of 10 seconds to produce an interdental brush. The antibacterial properties of the obtained interdental brush were monitored as follows.
That is, the obtained interdental brush was passed to a monitor, used as usual after dinner every morning, and washed with running water for 10 seconds. After repeating this for one week, it was inserted into a sleeve for storing an interdental brush, sealed in a polyethylene bag, and stored at 37 ° C. for one week. One week later, the polyethylene bag was opened, the interdental brush was taken out of the sleeve, and the smell and appearance of the interdental brush at that time were observed. For comparison, a similar monitor test was performed on a commercially available interdental brush (manufactured by Healthtech Co., Ltd.). The test results are as shown in Table 3.
[0026]
( Reference example 2 )
Reference example 1 Except that the amount of antibacterial zeolite is 5.0% by weight for both the bristle and the handle member. Reference example 1 An interdental brush was produced in the same manner as described above.
Effect of antibacterial activity of the obtained interdental brush Reference example 1 The same monitoring test was conducted. The test results are as shown in Table 3.
[0027]
( Reference example 3 )
The A-type antibacterial zeolite used in [I] is 0.1% by weight melt-mixed with polybutylene terephthalate (trade name; LUMICON 1101G-30: manufactured by Toray Industries, Inc.), and an M size brush is formed by extrusion molding. A filament for hair was produced. Using this, Reference example 1 A brush member was produced in the same manner as described above. Next, the wire part was bent into a U shape for embedding in the handle member, and this was subjected to insert molding.
Inserted the wire part of the brush member into polypropylene (trade name; GRAND POLYPRO E101: made by Grand Polymer Co., Ltd.) with 0.1% by weight of A-type antibacterial zeolite used in [I]. It was injected into the pattern member molding die and insert molded at a molding temperature of 230 ° C. and a molding time of 10 seconds to produce an interdental brush.
Effect of antibacterial activity of the obtained interdental brush Reference example 1 The same monitoring test was conducted. The test results are as shown in Table 3.
[0028]
( Reference example 4 )
Reference example 3 Except that the amount of antibacterial zeolite is 3.5% by weight for both the bristle and the handle member. Reference example 1 An interdental brush was produced in the same manner as described above.
Effect of antibacterial activity of the obtained interdental brush Reference example 1 The same monitoring test was conducted. The test results are as shown in Table 3.
[0029]
( Reference Example 5 )
As a brush member Reference example 3 The same one was used. As a handle member, a brush member obtained by melting and mixing 1.0% by weight of A-type antibacterial zeolite used in [I] with polypropylene (trade name: GRAND POLYPRO E101: manufactured by Grand Polymer Co., Ltd.) The interdental brush was manufactured by injection molding into a pattern member molding die into which the wire part was inserted and insert molding at a molding temperature of 230 ° C. and a molding time of 10 seconds.
Effect of antibacterial activity of the obtained interdental brush Reference example 1 The same monitoring test was conducted. The test results are as shown in Table 3.
[0030]
(Example 1, 2 )
The A-type antibacterial zeolite used in [I] was melt-mixed with 2.5% by weight of the polyamide used in [I], and a filament for M-size bristles was produced by extrusion molding. Using this, Reference example 1 A brush member was produced in the same manner as described above.
30 weight by weight of metal-adhesive polyolefin (trade name; Admer Grade XE-070: Mitsui Petrochemical Co., Ltd.) obtained by grafting carboxylic acid into ultra-low density polyethylene as a thermoplastic synthetic resin used for the pattern member Part, EVA (trade name; EVAFLEX P-1407: Mitsui DuPont Chemical Co., Ltd.) 45 parts by weight, soft polyethylene (trade name; ULTZEX 20200J: Mitsui Petrochemical Co., Ltd.) 25 parts by weight, [I The A-type antibacterial zeolite used in the above is used in an amount of 0.5% by weight and 1.0% by weight based on the total amount of the thermoplastic synthetic resin, and these are melted and kneaded at 230 ° C. for 2 hours 30 minutes, A polymer blend containing 0.5% by weight of antibacterial zeolite and a polymer blend containing 1.0% by weight were obtained.
After degreasing the surface of the linear wire part of the produced brush member with ethyl alcohol, the wire part is inserted into a mold, and a polymer blend obtained at a molding temperature of 180 ° C. and a molding time of 10 seconds is injected. At the same time as the molding of the handle member, the wire part and the handle member are bonded to obtain an interdental brush I containing 0.5% by weight of antibacterial zeolite and an interdental brush II containing 1.0% by weight. It was. The embedding distance of the wire part in the handle member was set to 18.5 mm.
Examples of interdental brushes I and II obtained 1, 2 As an antibacterial effect Reference example 1 The same monitoring test was conducted. The test results are as shown in Table 3.
[0031]
[Table 3]

[0032]
In addition, an interdental brush having a handle member using a polymer blend not mixed with antibacterial zeolite was produced as follows.
30 parts by weight of the metal adhesive polyolefin, 45 parts by weight of EVA and 25 parts by weight of soft polyethylene were melted and kneaded at 230 ° C. for 2 hours and 30 minutes to obtain a polymer blend.
After degreasing the surface of the linear wire part of the produced brush member with ethyl alcohol, the wire part is inserted into a mold, and a polymer blend obtained at a molding temperature of 180 ° C. and a molding time of 10 seconds is injected. Insert molding was performed, and at the same time as the pattern member was molded, the wire part and the pattern member were bonded to obtain an interdental brush III containing no antibacterial zeolite. The embedding distance in the handle member of the wire part was set to 18.5 mm and 16.5 mm.
[0033]
The adhesion between the wire portions of the interdental brushes I, II, and III and the handle member was evaluated by the pulling resistance of the wire portion from the handle member. The drawing resistance was measured by a tensile test using an autograph AGS-500D (manufactured by Shimadzu Corporation) at a crosshead speed of 10 mm / min. The interdental brush used was stored under the storage conditions shown in Table 4 after molding. Here, it was said that the adhesion of the metal-adhesive polyolefin to the metal was improved over time, and the actual use of the interdental brush went through the market after molding, This is because it takes a predetermined period of time for the consumer to use it, so that it is stored at 60 ° C. to promote its effect, and the pull-out resistance test is made more realistic.
The results are as shown in Table 4.
[0034]
[Table 4]

[0035]
If the pulling resistance value shown in Table 4 is used, even if an external force that rotates or pulls out the wire portion embedded in the handle member of the interdental brush is applied by using the interdental brush, it can be easily applied. The wire part does not come off from the handle member, can be used for a long period of time, and can sufficiently be used as an interdental brush. Therefore, it is not necessary to perform a fine, troublesome and difficult work such as bending a part of the wire portion embedded in the handle member into a U shape or a U shape, and the bending process can be omitted. Furthermore, in insert molding, it is only necessary to insert a linear wire portion into a mold, so that the work is easy, work efficiency can be improved, and an inexpensive interdental brush is provided. become. Moreover, even when using a linear wire part like the prior art, the process of apply | coating an adhesive agent to this wire part, or the process of applying a primer to a wire part becomes unnecessary. Moreover, since it is only necessary to degrease the metal wire, clean the surface, and use it for molding, the work is safe and easy, and the manufacturing cost of the interdental brush is not increased. In order to enable normal use without the stainless wire coming out of the interdental brush, the embedment distance by the insert is preferably 16.5 mm or more in this composition.
The mechanism by which the stainless steel wire is bonded to the handle is not clear, but hydrogen bonding between the carboxylic acid introduced by the graft reaction in the metal-adhesive polyolefin and the passive layer on the stainless steel surface plays a major role. It is considered a thing.
In addition, as is apparent from Table 4, when the resin mixed with antibacterial zeolite is used for the handle member, there is a large difference in the resistance to pulling out the wire from the handle member as compared with the case where no antibacterial zeolite is mixed. Not. In general, the storage conditions after molding are considered to correspond to one day at 60 ° C. left for one month at room temperature, which is based on the results of A and B of interdental brush III. Is also obvious.
[0036]
(Example 3 )
The metal-adhesive polyolefin was melted and kneaded at 230 ° C. for 2 hours and 30 minutes using 2.5% by weight of the A-type antibacterial zeolite used in [I] to obtain a mixture.
Example 1 Using the same brush member, after degreasing the surface of the linear wire portion with ethyl alcohol, the wire portion is inserted into a mold, and the mixture obtained at a molding temperature of 180 ° C. and a molding time of 20 seconds is injected. Then, insert molding was performed, and at the same time as the pattern member was formed, the wire part and the pattern member were bonded to obtain an interdental brush. Prior to molding, a fluorine-based non-silicon type release agent was applied in the mold. Moreover, the embedding distance in the handle member of the wire part was set to 18.5 mm.
Effect of antibacterial activity of the obtained interdental brush Reference example 1 The same monitoring test was conducted. The test results are as shown in Table 3.
In addition, the adhesion between the wire portion of the obtained interdental brush and the handle member was evaluated by performing a pull-out test similar to the previous period after storage at 60 ° C. for 1 day and evaluating it. It was 5 cm.
[0037]
Next, an example using an antibacterial metal wire as an interdental brush metal wire using antibacterial zeolite Along with reference examples It will be further explained.
Prior to the examples, antibacterial performance tests of antibacterial metal wires were performed as follows.
[0038]
[III] Antibacterial alloy sample
As an antibacterial metal wire alloy, a Ni—Cu alloy containing 66.5 wt% Ni, 31.5 wt% Cu, 1.2 wt% Fe as shown in Table 5 (trade name; MONEL alloy 400: Daido Special Steel Co., Ltd.) was used. For comparison, three types of austenitic stainless steel were used: Sus304, Sus316, and SusXM7. These compositions (% by weight) are as shown in Table 5. Samples were prepared in the following order.
No. 8 Ni-Cu alloy
No. 9 Sus304
No. 10 Sus316
No. 11 SusXM7
[0039]
[Table 5]

[0040]
All the samples were 50 mm × 50 mm, and the antibacterial test was performed on S. aureus and E. coli as follows.
1) Test strain
Staphylococcus aureus IFO 12732 (Staphylococcus aureus)
Escherichia coli IFO 3972 (E. coli)
2) Test medium
NA medium: Ordinary agar medium (Eiken Chemical Co., Ltd.)
1/50 NB medium: Normal bouillon (Eiken Chemical Co., Ltd.) supplemented with 0.2% meat extract diluted 50 times with purified water and adjusted to pH 7.0 ± 0.2
SCDLP medium: SCDLP medium (Nippon Pharmaceutical Co., Ltd.)
SA medium: Standard agar medium (Eiken Chemical Co., Ltd.)
3) Preparation of bacterial solution
The test strains pre-cultured in NA medium at 37 ° C. for 16 to 24 hours were re-inoculated into NA medium and cells cultured at 37 ° C. for 16 to 20 hours were uniformly dispersed in 1/50 NB medium, and the number of bacteria per ml Is 1.0 × 10 ⁶ ~ 5.0 × 10 ⁶ It prepared so that it might become.
4) Sample preparation
Prior to the antibacterial test, the sample was lightly wiped with absorbent cotton soaked with 99.5% (V / V) ethanol, and then air-dried.
5) Test operation
Antibacterial test against Staphylococcus aureus was performed by dropping 0.1 ml of the bacterial solution onto the sample and sterilizing the sample with ultraviolet light at 50 x 50 mm. ² The same polyethylene film as used in [II] above was covered and adhered, and cultured in an atmosphere at 35 ° C. and a relative humidity of 90% or more for 24 hours. After culturing, the surviving bacteria were washed out from the sample with the SCDLP medium, and the number of viable bacteria in the washed liquid was measured by the agar plate culture method (35 ° C., 48 hours) using the SA medium, and converted per sample. did. Moreover, it tested similarly using a plastic petri dish as a control sample. In addition, the measurement immediately after inoculation is performed on the control sample, and 2.9 × 10 per plastic petri dish. ^Five It was a piece.
The antibacterial test against E. coli is 50 x 50 mm in which 0.1 ml of bacterial solution is dropped onto the sample and UV sterilized on the sample. ² The same polyethylene film as used in [II] above was covered and adhered, and cultured in an atmosphere at 35 ° C. and a relative humidity of 90% or more for 24 hours. After culturing, the surviving bacteria were washed out from the sample with the SCDLP medium, and the number of viable bacteria in the washed liquid was measured by the agar plate culture method (35 ° C., 48 hours) using the SA medium, and converted per sample. did. Moreover, it tested similarly using a plastic petri dish as a control sample. In addition, the measurement immediately after inoculation is performed on a control sample, and 1.5 × 10 5 per plastic petri dish. ^Five It was a piece.
The results are as shown in Table 6. Sample No. The Ni—Cu alloy of No. 8 exhibits good antibacterial properties as compared with the stainless steels of Samples 9 to 11. In addition, Sample No. The Ni—Cu alloy of No. 8 has good corrosion resistance as a wire compared to a stainless steel wire, and is excellent in toughness and hardly breaks and breaks the wire.
[0041]
[Table 6]

[0042]
( Reference Example 6 )
As brush hair Reference example 1 Using a Ni-Cu alloy (trade name; MONEL alloy 400: manufactured by Daido Special Steel Co., Ltd.) with a diameter of 0.3 mm, folded in half at the center and made into a pine needle. This was sandwiched, and hair was radially planted at a twist number of 22 times / cm to produce a brush member. Next, the wire part was bent into a U shape for embedding in the handle member, and this was subjected to insert molding. For the handle member, the sample No. What was melt-mixed to the same composition as No. 6 was injected into a pattern member molding die into which the wire portion of the brush member was inserted, and insert molding was performed at a molding temperature of 170 ° C. and a molding time of 10 seconds to produce an interdental brush.
Effect of antibacterial activity of the obtained interdental brush Reference example 1 The same monitoring test was conducted. The test results are as shown in Table 7.
[0043]
( Reference Example 7 )
Reference Example 6 Except that the amount of antibacterial zeolite is 5.0% by weight for both the bristle and the handle member. Reference Example 6 An interdental brush was produced in the same manner as described above.
Effect of antibacterial activity of the obtained interdental brush Reference example 1 The same monitoring test was conducted. The test results are as shown in Table 7.
[0044]
( Reference Example 8 )
As brush hair Reference example 3 Use the same as Reference Example 6 Using the same Ni-Cu alloy wire used in Reference Example 6 A brush member was manufactured in the same manner as described above. Next, the wire part was bent into a U shape for embedding in the handle member, and this was subjected to insert molding.
As a pattern member Reference example 3 Were used and injected into a pattern member molding die into which the wire portion of the brush member was inserted, and insert molding was performed at a molding temperature of 230 ° C. and a molding time of 10 seconds to produce an interdental brush.
Effect of antibacterial activity of the obtained interdental brush Reference example 1 The same monitoring test was conducted. The test results are as shown in Table 7.
[0045]
(Example 4, 5 )
Example as brush hair 1 Use the same as Reference Example 6 Using Ni-Cu alloy wire used in Reference Example 6 A brush member was manufactured in the same manner as described above.
Examples of thermoplastic synthetic resins used for pattern members 1 In the same manner as above, a metal-adhesive polyolefin (trade name; Admer Grade XE-070: manufactured by Mitsui Petrochemical Co., Ltd.) obtained by introducing a carboxylic acid into ultra-low density polyethylene by a graft reaction, EVA (trade name; EVAFLEX P-1407: Mitsui DuPont Chemical Co., Ltd.) 45 parts by weight, soft polyethylene (trade name; ULTZEX 20200J: Mitsui Petrochemical Co., Ltd.) 25 parts by weight, A-type used in [I] These antibacterial zeolites were used in an amount of 0.5% by weight and 1.0% by weight with respect to the total amount of the thermoplastic synthetic resin. A polymer blend containing 1% by weight and a polymer blend containing 1.0% by weight were obtained.
After degreasing the surface of the linear wire part of the produced brush member with ethyl alcohol, the wire part is inserted into a mold, and a polymer blend obtained at a molding temperature of 180 ° C. and a molding time of 10 seconds is injected. Insert molding was performed, and the wire part and the pattern member were bonded simultaneously with the molding of the handle member, and an interdental brush IV containing 0.5% by weight of antibacterial zeolite and an interdental brush V containing 1.0% by weight were obtained. . The embedding distance of the wire part in the handle member was set to 18.5 mm.
Examples of interdental brushes IV and V obtained 4, 5 As an antibacterial effect Reference example 1 The same monitoring test was conducted. The test results are as shown in Table 7.
[0046]
[Table 7]

[0047]
In addition, an interdental brush having a handle member using a polymer blend not mixed with antibacterial zeolite was produced as follows.
30 parts by weight of the metal adhesive polyolefin, 45 parts by weight of EVA and 25 parts by weight of soft polyethylene were melted and kneaded at 230 ° C. for 2 hours and 30 minutes to obtain a polymer blend.
After degreasing the surface of the wire portion made of the linear Ni—Cu alloy wire of the produced brush member with ethyl alcohol, the wire portion is inserted into a mold and obtained at a molding temperature of 180 ° C. and a molding time of 10 seconds. The obtained polymer blend was injected and insert-molded, and at the same time as forming the handle member, the wire part and the handle member were bonded together to obtain an interdental brush VI containing no antibacterial zeolite. The embedding distance in the handle member of the wire part was set to 18.5 mm and 16.5 mm.
[0048]
The adhesion between the interdental brush IV, V, VI wire part and the handle member, Example 1 In the same manner as described above, the wire part was pulled out from the handle member and evaluated.
The results are as shown in Table 8.
[0049]
[Table 8]

[0050]
As shown in Table 8, even in the case of a linear Ni—Cu alloy wire, 1-3 The pulling resistance value is almost the same as the straight stainless steel wire used in the above, and by using the interdental brush, the antibacterial wire part embedded in the handle member of the interdental brush is rotated or pulled out. Even if an external force is applied, the wire part does not easily come off from the handle member, and can be used for a long period of time, and can sufficiently be used as an interdental brush. Therefore, it is not necessary to perform a fine, troublesome and difficult work such as bending a part of the wire portion embedded in the handle member into a U shape or a U shape, and the bending process can be omitted. Furthermore, even in insert molding, it is easy to work because it is only necessary to insert a linear wire part into the mold, and work efficiency can be improved, so the wire part is also inexpensive with antibacterial properties. Provide an interdental brush. Moreover, even when using a linear wire part like the prior art, the process of apply | coating an adhesive agent to this wire part, or the process of applying a primer to a wire part becomes unnecessary. Moreover, since it is only necessary to degrease the metal wire, clean the surface, and use it for molding, the work is safe and easy, and the manufacturing cost of the interdental brush is not increased. In addition, in order to enable normal use without the Ni—Cu-based alloy wire coming out of the interdental brush, the embedment distance by the insert is preferably 16.5 mm or more in this composition.
The mechanism by which the Ni-Cu alloy wire is bonded to the handle member is not clear, but the carboxylic acid introduced by the graft reaction in the metal-adhesive polyolefin and the passive layer on the Ni-Cu alloy surface. Hydrogen bonds are thought to play a major role.
In addition, as is apparent from Table 8, when the resin mixed with antibacterial zeolite is used for the handle member, there is a large difference in resistance to pulling out the wire from the handle member as compared with the case where no antibacterial zeolite is mixed. Not. Also, in general, the storage conditions after molding are considered to correspond to one day at 60 ° C. left for one month at room temperature, which is based on the results of E and F of the interdental brush VI. Is also obvious.
[0051]
(Example 6 )
The metal-adhesive polyolefin was melted and kneaded at 230 ° C. for 2 hours and 30 minutes using 2.5% by weight of the A-type antibacterial zeolite used in [I] to obtain a mixture.
Example 4 Using the same brush member, after degreasing the surface of the wire portion made of a linear Ni—Cu alloy wire with ethyl alcohol, the wire portion is inserted into a mold, a molding temperature of 180 ° C., and a molding time of 20 seconds. The mixture obtained was injected and molded, and at the same time as forming the handle member, the wire part and the handle member were bonded together to obtain an interdental brush. Prior to molding, a fluorine-based non-silicon type release agent was applied in the mold. Moreover, the embedding distance in the handle member of the wire part was set to 18.5 mm.
Effect of antibacterial activity of the obtained interdental brush Reference example 1 The same monitoring test was conducted. The test results are as shown in Table 7.
Further, the adhesion between the wire part of the obtained interdental brush and the handle member was evaluated by conducting a pull-out test similar to the previous period after storing it at 60 ° C. for one day and evaluating it. It was 5 cm.
[0052]
<2> Further, examples of interdental brushes using antibacterial zeolite excellent in discoloration resistance as antibacterial zeolite will be described in detail below.
Prior to the examples, an antibacterial performance test and a discoloration resistance test of an antibacterial zeolite excellent in discoloration resistance were performed as follows.
[IV] Discoloration-resistant resin sample
As thermoplastic synthetic resin, metal adhesive polyolefin (trade name; Admer Grade XE-070: manufactured by Mitsui Petrochemical Co., Ltd.) obtained by grafting carboxylic acid into ultra-low density polyethylene by graft reaction, EVA ( Trade name: EVAFLEX P-1407: Mitsui DuPont Chemical Co., Ltd. 45 parts by weight, soft polyethylene (trade name: ULTZEX 20200J: Mitsui Petrochemical Co., Ltd.) 25 parts by weight were used. Antibacterial with excellent discoloration resistance by adding 1.6% by weight of white pigment containing titanium oxide, carbon black, titanium yellow and iron oxide to the total amount of the thermoplastic synthetic resin. A-type antibacterial zeolite (trade name; Bactekiller BM-102GSK: manufactured by Kanebo Kasei Co., Ltd.) carrying Ag and Zn ions as the functional zeolite is 0.5% by weight based on the total amount of the thermoplastic synthetic resin, and 1.0 wt%, these were melted and kneaded at 230 ° C. for 2 hours and 30 minutes, injected into a molding die, molded at a molding temperature of 180 ° C. and a molding time of 10 seconds, and antibacterial having a thickness of 3 mm Resin plates containing 0.5% by weight and 1.0% by weight of zeolite were molded. The average particle diameter of the antibacterial zeolite excellent in the color fastness was 1.7 μm. Also, the thermoplastic synthetic resin mixed with the same weight% of the pigment is injected into a molding die, molded at a molding temperature of 180 ° C. and a molding time of 10 seconds, and a resin plate (blank product) having a thickness of 3 mm. ). These resin plates are referred to as Sample No. below. Samples were prepared in the following order.
No. 12 Bactekiller BM-102GSK 0.5 wt% product
No. 13 Bactekiller BM-102GSK containing 1.0% by weight
No. 14 Blank product
In addition, polypropylene (trade name; Novatec MA3M: manufactured by Nippon Polytem Co., Ltd.) was used as the thermoplastic synthetic resin. Antibacterial zeolite with excellent discoloration resistance obtained by mixing 2.0% by weight of a cream pigment containing titanium oxide, calcined pigment yellow, calcined pigment green, and ultramarine blue with respect to the polypropylene. A-type antibacterial zeolite (trade name; Bactekiller BM-102GSK: manufactured by Kanebo Kasei Co., Ltd.) supporting Ag and Zn ions as described above is melted and kneaded in 1.0% by weight with respect to the polypropylene, and then molded metal The resin plate was injected into a mold and molded at a molding temperature of 230 ° C. and a molding time of 10 seconds to mold a resin plate containing 1.0% by weight of antibacterial zeolite having a thickness of 3 mm. In addition, the polypropylene mixed with the same weight% of the pigment is injected into a molding die and molded at a molding temperature of 230 ° C. and a molding time of 10 seconds to form a 3 mm thick resin plate (blank product). did. These resin plates are referred to as Sample No. below. Samples were prepared in the following order.
No. 15 Bacteria BM-102GSK 1.0 wt%
No. 16 Blank product
[0053]
(A) Antibacterial test
Sample No. 12-No. 16 was cut into 50 mm × 50 mm, and the antibacterial test was performed on S. aureus and E. coli as follows.
1) Test strain
Staphylococcus aureus IFO 12732 (Staphylococcus aureus)
Escherichia coli IFO 3972 (E. coli)
2) Test medium
NA medium: Ordinary agar medium (Eiken Chemical Co., Ltd.)
1/500 NB medium: Normal bouillon (Eiken Chemical Co., Ltd.) supplemented with meat extract 0.2% diluted with purified water 500 times and adjusted to pH 7.0 ± 0.2
SCDLP medium: SCDLP medium (Nippon Pharmaceutical Co., Ltd.)
SA medium: Standard agar medium (Eiken Chemical Co., Ltd.)
3) Preparation of bacterial solution
The test strains pre-cultured in NA medium at 37 ° C. for 16 to 24 hours were re-inoculated into NA medium and cells cultured at 37 ° C. for 16 to 20 hours were uniformly dispersed in 1/500 NB medium, and the number of bacteria per ml Is 2.0 × 10 ^Five ~ 1.0 × 10 ⁶ It prepared so that it might become.
4) Sample preparation
Prior to the antibacterial test, the sample was lightly wiped with absorbent cotton soaked with 99.5% (V / V) ethanol, and then air-dried.
5) Test operation
In the antibacterial test against Staphylococcus aureus, 0.5 ml of the bacterial solution was dropped onto the sample, and the sample was covered with a polyethylene film sterilized with ultraviolet light, and cultured for 24 hours in an atmosphere of 35 ° C. and a relative humidity of 90% or more. After culturing, the surviving bacteria were washed out from the sample with the SCDLP medium, and the number of viable bacteria in the washed liquid was measured by the agar plate culture method (35 ° C., 48 hours) using the SA medium, and converted per sample. did. Moreover, it tested similarly using a plastic petri dish as a control sample. In addition, the measurement immediately after inoculation is performed on the control sample, and 2.9 × 10 per plastic petri dish. ^Five It was a piece.
In the antibacterial test against Escherichia coli, 0.5 ml of the bacterial solution was dropped onto the sample, and the sample was covered with a polyethylene film sterilized with ultraviolet light, and cultured in an atmosphere of 35 ° C. and a relative humidity of 90% or more for 24 hours. After culturing, the surviving bacteria were washed out from the sample with the SCDLP medium, and the number of viable bacteria in the washed liquid was measured by the agar plate culture method (35 ° C., 48 hours) using the SA medium, and converted per sample. did. Moreover, it tested similarly using a plastic petri dish as a control sample. In addition, the measurement immediately after inoculation is performed on a control sample, and 4.1 × 10 4 per plastic petri dish. ^Five It was a piece.
The results are as shown in Table 9.
[0054]
[Table 9]

[0055]
(B) Discoloration resistance test
Sample No. 12-No. No. 16 was exposed to sunlight, and the sample color tone (L ^* ・ A ^* ・ B ^* ) Was measured using a color computer (Σ80 COLOR MEASURING SYSTEM: manufactured by NIPON DENSHOKU IN. CO. LTD), and the color difference (ΔE) was determined from the result of the color tone. The color difference (ΔE) is the initial color tone (L ^* ・ A ^* ・ B ^* ) Color tone every week (L ^* ・ A ^* ・ B ^* ) Is squared and the square root of the sum is taken.
The results are as shown in Table 10.
When a discoloration-resistant resin material mixed with a red pigment, a yellow pigment, and the like was produced in the same manner as described above, and a similar discoloration resistance test was performed, good results were obtained.
[0056]
[Table 10]

[0057]
(Example 7 )
As a brush member Reference example 1 The same one was used. For the handle member, the sample No. The one having the same composition as 13 was melt mixed and subjected to insert molding. When manufacturing the interdental brush, the surface of the linear wire part of the brush member is degreased with ethyl alcohol, and then the wire part is inserted into the pattern member molding die and melted at a molding temperature of 180 ° C. and a molding time of 10 seconds. The mixture was injected and insert molded, and at the same time as forming the handle member, the wire part and the handle member were bonded to obtain an interdental brush.
The embedding distance of the wire part in the handle member was set to 18.5 mm. In addition, after storage at 60 ° C. for 7 days, Example 1 When the pull-out resistance was measured in the same manner as described above, it was 7.68 (kgf).
And about the effect of antibacterial power of the obtained interdental brush, Reference example 1 When the same monitor test was conducted, no odor or appearance was found, and no discoloration was observed.
[0058]
【The invention's effect】
Since the present invention is configured as described in detail above, the following effects can be obtained.
In the interdental brush in which a predetermined length is embedded in the handle member from the end of the wire portion of the brush member consisting of the brush portion and the wire portion in which the brush hair is twisted into the metal wire over a predetermined length from the tip, Brush bristles can sterilize bacteria in plaque etc. adhering to brush hairs by containing inorganic antibacterial agent in an amount of 0.1 to 5.0% by weight with respect to thermoplastic synthetic resin. In addition, even if the interdental brush to which plaque or the like is attached is left unattended, microorganisms such as bacteria and mold do not grow, and a sterile condition can be maintained.
Further, the handle member may contain 0.1 to 5.0% by weight of an inorganic antibacterial agent with respect to the thermoplastic synthetic resin. According to this, the brush hair and the handle member are free of bacteria, mold, etc. Aseptic conditions can be maintained without the growth of microorganisms.
By providing antibacterial properties with an inorganic antibacterial agent that exhibits permanent antibacterial properties, the interdental brush is hygienic, and even if it is left with plaque etc. attached by use, bacteria and mold will remain. There is no proliferation. Therefore, the interdental brush does not have a specific unpleasant odor and does not have a color, so that it can be used comfortably. Also, since bacteria and mold do not adhere, even if an interdental brush is inserted into the interdental space, it does not cause bad breath or stomatitis. Even if the gums between teeth are hurt, there is no fear of inflammation caused by bacteria or mold.
And in the interdental brush by which predetermined length is embed | buried in the pattern member from the terminal of the wire part of the brush member which consists of the brush part and wire part which the bristle was twisted into the metal wire over the predetermined length from the front-end | tip By adding 0.1 to 5.0% by weight of the antibacterial zeolite to the brush bristles with respect to the thermoplastic synthetic resin, bacteria in the plaque and the like attached to the bristles can be killed by the antibacterial zeolite. In addition, even if the interdental brush to which plaque or the like is attached is left unattended, microorganisms such as bacteria and mold do not grow, and a sterile condition can be maintained. And the handle member is aseptic without containing microorganisms such as bacteria and mold on the bristles and handle member by containing 0.1 to 5.0% by weight of antibacterial zeolite with respect to the thermoplastic synthetic resin. The state can be maintained.
By providing antibacterial properties with an antibacterial zeolite that exhibits permanent antibacterial properties, the interdental brush is hygienic, and bacteria and mold grow even if it is left with plaque attached by use. There is nothing to do. Therefore, the interdental brush does not have a specific unpleasant odor and does not have a color, so that it can be used comfortably. Also, since bacteria and mold do not adhere, even if an interdental brush is inserted into the interdental space, it does not cause bad breath or stomatitis. Even if the gums between teeth are hurt, there is no fear of inflammation caused by bacteria or mold.
The metal wire has an antibacterial Ni-Cu alloy exemplified by an alloy containing 66.5 wt% Ni, 31.5 wt% Cu, 1.2 wt% Fe, at least 1.5 wt% Cu and 17 wt% Cr It may be made of an antibacterial alloy such as antibacterial stainless steel exemplified by stainless steel, and according to this, a sterilized state is maintained without the growth of microorganisms such as bacteria and mold on the wire. Will be able to.
In the interdental brush imparted with antibacterial properties, when the handle member is a thermoplastic synthetic resin made of at least a metal-adhesive polyolefin, the wire portion of a predetermined length embedded in the handle member of the brush member is made of the metal-adhesive polyolefin. Because it is bonded, there is no need to perform a detailed, tedious and difficult work such as folding a part of the wire part to be embedded and fixed in the handle member into a U shape or a U shape, and the bending process is not necessary. Since it can be omitted, an inexpensive interdental brush can be provided.
[Brief description of the drawings]
1A and 1B show an example of an interdental brush according to the present invention, in which FIG. 1A is a plan view, FIG. 1B is an enlarged cross-sectional view of brush bristles, and FIG.
FIG. 2 is a plan view showing another example of an interdental brush according to the present invention.
FIG. 3 is a plan view of a conventional interdental brush.
[Explanation of symbols]
1 Interdental brush
2 Brush members
3 Pattern members

Claims (9)

In an interdental brush in which a predetermined length is embedded in a handle member from the end of a wire part of a brush member consisting of a brush part and a straight wire part in which a bristle is twisted into a metal wire over a predetermined length from the tip ,
The brush hair contains 0.1 to 5.0% by weight of an inorganic antibacterial agent with respect to the thermoplastic synthetic resin, and the handle member contains 0.1 to 5 % of the inorganic antibacterial agent with respect to the thermoplastic synthetic resin. An interdental brush comprising 0% by weight of a thermoplastic synthetic resin constituting a handle member and comprising at least a metal-adhesive polyolefin . In an interdental brush in which a predetermined length is embedded in a handle member from the end of a wire part of a brush member consisting of a brush part and a straight wire part in which a bristle is twisted into a metal wire over a predetermined length from the tip ,
The brush bristles contain 0.1 to 5.0 wt% of antibacterial zeolite with respect to the thermoplastic synthetic resin, and the handle member has 0.1 to 5.0 wt% of antibacterial zeolite with respect to the thermoplastic synthetic resin. An interdental brush characterized in that the thermoplastic synthetic resin contained in the composition and constituting the handle member comprises at least a metal-adhesive polyolefin . The interdental brush according to claim 1 or 2, wherein the metal-adhesive polyolefin is obtained by introducing carboxylic acid into ultra-low density polyethylene by a graft reaction. The interdental brush according to claim 3 , wherein the metal-adhesive polyolefin is 5.6 parts by weight or more in 100 parts by weight of the thermoplastic synthetic resin. 4. The interdental brush according to claim 3, wherein the thermoplastic synthetic resin constituting the handle member comprises a polymer blend of 5 to 55 parts by weight of metal-adhesive polyolefin, 55 to 25 parts by weight of EVA, and 10 to 35 parts by weight of soft polyethylene. The interdental brush characterized by being. The interdental brush according to claim 1, 2, 3, 4, or 5 , wherein the metal wire is made of an antibacterial alloy. The interdental brush according to claim 6 , wherein the metal wire is made of an antibacterial Ni-Cu alloy. The interdental brush according to claim 7, wherein the antibacterial Ni-Cu alloy is an alloy containing 66.5 wt% Ni, 31.5 wt% Cu, and 1.2 wt% Fe. The interdental brush according to claim 6 , wherein the metal wire is stainless steel containing at least 1.5 wt% Cu and 17 wt% Cr.

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