JPH0687807B2 - Tape rubber for shoes - Google Patents
Tape rubber for shoesInfo
- Publication number
- JPH0687807B2 JPH0687807B2 JP62173932A JP17393287A JPH0687807B2 JP H0687807 B2 JPH0687807 B2 JP H0687807B2 JP 62173932 A JP62173932 A JP 62173932A JP 17393287 A JP17393287 A JP 17393287A JP H0687807 B2 JPH0687807 B2 JP H0687807B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- tape
- shoes
- parts
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- Compositions Of Macromolecular Compounds (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明はムーニー粘度（ML）が低いために作業性に優
れ、かつ加硫温度付近での引張応力，引張強度が大きい
ために、加硫時に変形を伴なわず、さらに製品の表面が
良好な靴用のテープゴムに関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention is excellent in workability due to its low Mooney viscosity (ML), and has high tensile stress and tensile strength near the vulcanization temperature. The present invention relates to a tape rubber for shoes which is not deformed at all and has a good surface.
［従来の技術及びその問題点］ 従来、甲布の下辺にゴムのりを塗布し、テープゴム，底
ゴム，爪先ゴムなどを順次はり付け成型した後に加硫か
んに入れて加硫して布靴を製造する際に、テープゴムの
はり付け作業は、テープゴムに一定の張力を加える必要
があるために加硫かん中に入れ、テープの温度が上昇し
た時に、テープの引張応力あるいは引張強度が低い場合
にはテープが伸びるかあるいは切れてしまい不良品とな
る事が多かった。このため、現状ではテープ配合物の引
張応力あるいは引張強度をあげるために多量の充填剤あ
るいは短繊維等を配合するなり、あるいはテープ部分に
補強層を裏打ちするなどの手段が取られている。[Prior art and its problems] Conventionally, rubber glue is applied to the lower side of the upper cloth, and tape rubber, bottom rubber, toe rubber, etc. are sequentially glued and molded, and then put into a vulcanizer and vulcanized to make cloth shoes. At the time of manufacturing, the tape rubber sticking work is put in a vulcanizer because it is necessary to apply a certain tension to the tape rubber, and when the tape temperature rises, the tensile stress or tensile strength of the tape is low. The tape was often stretched or cut, resulting in a defective product. For this reason, at present, in order to increase the tensile stress or tensile strength of the tape compound, a large amount of filler, short fibers, or the like must be compounded, or a tape layer is lined with a reinforcing layer.
しかし、多量の充填剤を配合した場合には、引張応力に
若干の改善は認められるものの、ML粘度が増大し作業性
が悪くなる。However, when a large amount of the filler is blended, although the tensile stress is slightly improved, the ML viscosity increases and the workability deteriorates.
さらに、短繊維を配合した場合には、その平均直径が太
い場合には、繊維の分散が悪く引張強度が大幅に低下
し、さらに製品の表面が悪くなる等の問題点が生じてい
る。Further, when short fibers are blended, if the average diameter is large, the dispersion of the fibers is poor, the tensile strength is significantly reduced, and the surface of the product is further deteriorated.
また、テープ部分の補強層を裏打ちする方法では、かな
り不良品の率は低くなるが、多くの労力を要し、生産性
が悪い。Further, the method of lining the reinforcing layer of the tape portion considerably lowers the rate of defective products, but it requires a lot of labor and productivity is poor.
［本発明が解決しようとする問題点］ 本発明の目的は、上述の従来技術の問題点、すなわち作
業性，引張応力，引張強度など、製品の表面状態が改良
され、生産性の優れた靴用のテープゴムを提供すること
にある。[Problems to be Solved by the Present Invention] An object of the present invention is to improve the productivity of shoes by improving the surface conditions of the products such as the above-mentioned problems of the prior art, that is, workability, tensile stress, and tensile strength. To provide tape rubber for.
［問題点を解決するための手段］ 本発明は、甲布の下辺にゴムのりを塗布し、テープゴ
ム，底ゴム，爪先ゴムなどを順次はり付け成型した後に
加硫かんに入れて加硫して布靴を製造する際に、加硫可
能なゴム100重量部に繊維形成可能なポリアミドの平均
繊維直径（以下、平均繊維径ともいう）が0.05〜0.8μ
ｍの短繊維１〜20重量部が埋封されており、かつ、加硫
可能なゴムとポリアミドとがシランカップリング剤を介
して結合されたものを少なくとも一部含有し、末加硫状
態での120℃における100％引張応力（M100）が40〜102K
g/cm2、また引張強度（TB）が140〜190Kg/cm2である、
靴用のテープゴムに関する。[Means for Solving the Problems] In the present invention, rubber glue is applied to the lower side of the upper cloth, and tape rubber, bottom rubber, toe rubber, etc. are sequentially bonded and molded, and then put into a vulcanizer and vulcanized. When manufacturing cloth shoes, the average fiber diameter (hereinafter also referred to as the average fiber diameter) of polyamide capable of forming fibers in 100 parts by weight of vulcanizable rubber is 0.05 to 0.8μ.
1 to 20 parts by weight of m short fibers are embedded, and at least a part of vulcanizable rubber and polyamide bonded via a silane coupling agent is contained, and in a non-vulcanized state. 100% tensile stress (M 100 ) at 120 ℃ is 40 to 102K
g / cm 2 , and the tensile strength (T B ) is 140 to 190 Kg / cm 2 ,
Tape rubber for shoes.
靴用のテープゴムに使用される加硫可能なゴムとして
は、天然ゴム，シス−1,4ポリブタジエン，ポリイソプ
レン，スチレン−ブタジエン共重合体ゴム，イソブレン
−イソブチレン共重合体，エチレン−プロピレン−ジエ
ン三元共重合体などを挙げることができ、これらのゴム
の中でも天然ゴムが好ましい。The vulcanizable rubber used for the tape rubber for shoes includes natural rubber, cis-1,4 polybutadiene, polyisoprene, styrene-butadiene copolymer rubber, isobrene-isobutylene copolymer, ethylene-propylene-diene terephthalate. Examples of the rubber include natural copolymers, and natural rubber is preferable.
また、前記強化ゴム組成物に用いられるポリアミドは、
繊維形成可能なもので、融点が150〜260℃、好ましくは
190〜235℃の、ナイロン6,ナイロン610,ナイロン12,ナ
イロン611,ナイロン612,ナイロン66等を挙げることがで
きる。また、このポリアミドとしては繊維形成能があれ
ば特に制限はないが、数平均分子量5,000以上、好まし
くは8,000以上である。分子量があまりに低いと繊維形
成能が悪く強度も低い。Further, the polyamide used in the reinforced rubber composition,
It is capable of forming fibers and has a melting point of 150 to 260 ° C, preferably
Nylon 6, nylon 610, nylon 12, nylon 611, nylon 612, nylon 66 and the like at 190 to 235 ° C. can be mentioned. The polyamide is not particularly limited as long as it has a fiber-forming ability, but has a number average molecular weight of 5,000 or more, preferably 8,000 or more. If the molecular weight is too low, the fiber-forming ability is poor and the strength is low.
本発明における強化ゴム組成物に用いられる短繊維は、
上記のポリアミドの微細な短繊維で、この短繊維は、繊
維軸方向に分子が配列された形態のもので、その平均繊
維直径0.05〜0.8μｍ、特に断面円形で最短繊維長が１
μｍ以上のものが好ましい。平均繊維直径が0.8μｍよ
り大きくなると分散性が悪く、表面状態も悪くなる。ま
た強度面でもよくない。Short fibers used in the reinforced rubber composition of the present invention,
The above-mentioned polyamide fine short fibers, in which molecules are arranged in the fiber axial direction, and the average fiber diameter thereof is 0.05 to 0.8 μm, and particularly the circular cross section has the shortest fiber length of 1
It is preferably μm or more. If the average fiber diameter exceeds 0.8 μm, the dispersibility is poor and the surface condition is poor. It is also not good in terms of strength.
また、シランカップリング剤として構造式Y-R1SiX3、あ
るいはY-R1SiX2X2で示される化合物が使用される。Further, as the silane coupling agent, a compound represented by the structural formula YR 1 SiX 3 or YR 1 SiX 2 X 2 is used.
ここで、上記構造式におけるY,R1,R2,Xは、各々、下記
の基を示す。Here, Y, R 1 , R 2 and X in the above structural formulas respectively represent the following groups.
Y:H2N-,CH2＝CH-, C1-,HS-,C6H5‐， R1:ApCnH2n BqCmH2m BqClH2l 〔A:C6H4,B:O,NH ｐ＝０〜2,n＝０〜5,q＝０〜2, ｍ＝０〜5,l＝０〜５ 〕 R2:CnH2n+1〔ｎ＝１〜４〕 X:DrCnH2n EsCmH2m+1 〔D;O,C1,E:O ｒ＝０〜2,n＝０〜5,s＝１〜2, ｍ＝１〜５ 〕 従って、シランカップリング剤としては、具体的には、
γ−アミノプロピルトリメトキシシラン，γ−アミノプ
ロピルトリエトキシシラン,N−β（アミノエチル）γ−
アミノプロピルトリメトキシシラン,N−β（アミノエチ
ル）γ−アミノプロピルメチルジメトキシシラン，γ−
（ジエチレントリアミノ）プロピルトリメトキシシラン
−γ−ウレイド−プロピルトリエトキシシラン−ビニル
トリエトキシシラン，ビニルトリメトキシシラン，ビニ
ルトリス（βメトキシエトキシ）シラン，γ−グリシド
キシプロピルメチルジエトキシシラン，γ−グリシドキ
シプロピルトリメトキシシラン，β−（3,4エポキシシ
クロヘキシル）エチルトリメトキシシラン，γ−メタク
リロキシプロピルトリメトキシシラン，γ−クロロプロ
ピルトリメトキシシラン，γ−メルカプトプロピルトリ
メトキシシラン,N−フェニル−γ−アミノプロピルトリ
エトキシシラン,N−β（Ｎ−ビニルベンジルアミノエチ
ル）−γ−アミノプロピルトリメトキシシラン塩酸塩な
どを挙げることができる。Y: H 2 N-, CH 2 ＝ CH-, C1-, HS-, C 6 H 5- , R 1 : ApCnH 2 n BqCmH 2 m BqC l H 2l (A: C 6 H 4 ,, B: O, NH p = 0-2, n = 0-5, q = 0~2, m = 0~5, l = 0~5 ] R 2: CnH 2n + 1 [n = 1 to 4] X: DrCnH 2 n EsCmH 2m + 1 [D; O, C1, E: O r = 0 to 2, n = 0 to 5, s = 1 to 2, m = 1 to 5] Therefore, as the silane coupling agent, specifically,
γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-
Aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-
(Diethylenetriamino) propyltrimethoxysilane-γ-ureido-propyltriethoxysilane-vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (βmethoxyethoxy) silane, γ-glycidoxypropylmethyldiethoxysilane, γ-glyce Sidoxypropyltrimethoxysilane, β- (3,4epoxycyclohexyl) ethyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, N-phenyl- γ-aminopropyltriethoxysilane, N-β (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride and the like can be mentioned.
而して、本発明に用いられる靴用のテープゴムは、前記
の加硫可能なゴム100重量部に、前記のポリアミドの微
細な短繊維１〜20重量部、好ましくは３〜15重量部が埋
封されており、かつ、前記ポリアミドと前記ゴムとがシ
ランカップリング剤を介して結合しているもので、前記
短繊維の界面において前記ポリアミドと前記ゴムとが前
記シランカップリング剤を介して結合しているものを少
なくとも一部含有するものである。Thus, in the tape rubber for shoes used in the present invention, 100 parts by weight of the vulcanizable rubber is filled with 1 to 20 parts by weight, preferably 3 to 15 parts by weight, of the fine polyamide microfibers. It is sealed, and the polyamide and the rubber are bound via a silane coupling agent, and the polyamide and the rubber are bound at the interface of the short fibers via the silane coupling agent. It contains at least part of what is done.
加硫可能なゴムに埋封されている短繊維の割合が前記下
限より少ないと、これを配合してなるテープゴムの引張
応力が改善されず、加硫可能なゴムに埋封されている短
繊維の割合が前記上限より多いと、繊維の分散が悪くな
り、製品の表面状態が悪くなる。When the ratio of the short fibers embedded in the vulcanizable rubber is less than the lower limit, the tensile stress of the tape rubber prepared by blending this is not improved, and the short fibers embedded in the vulcanizable rubber are not improved. If the ratio is more than the above upper limit, the dispersion of fibers becomes poor and the surface condition of the product becomes poor.
本発明の靴用のテープゴムは強化ゴム組成物（マスター
バッチ）と希釈用の加硫可能なゴム組成物とを用いて調
製することができる。その強化ゴム組成物（マスターバ
ッチ）は、例えば加硫可能なゴム、該加硫可能なゴム10
0重量部当り約20〜100重量部のポリアミド、及び該ポリ
アミド100重量部当りシランカップリング剤0.1〜5.5重
量部を、前記ポリアミドの融点以上の温度で混練し、得
られた混練物を前記ポリアミドの融点以上の温度で押し
出すことにより、或いは更に、適宜前記押出物を前記ポ
リアミドの融点より高い温度で又は前記ポリアミドの融
点より低い温度で延伸することにより得られる。更に、
前記押出物を前記ポリアミドの融点より高い温度で延伸
し且つ前記押出物を前記ポリアミドの融点より低い温度
で延伸することによっても得られる（以下強化ゴム組成
物と言う）。The tape rubber for shoes of the present invention can be prepared using a reinforced rubber composition (masterbatch) and a vulcanizable rubber composition for dilution. The reinforced rubber composition (masterbatch) is, for example, a vulcanizable rubber, the vulcanizable rubber 10
About 20 to 100 parts by weight of polyamide per 0 parts by weight, and 0.1 to 5.5 parts by weight of a silane coupling agent per 100 parts by weight of the polyamide are kneaded at a temperature equal to or higher than the melting point of the polyamide, and the resulting kneaded product is the polyamide. By extruding at a temperature equal to or higher than the melting point of, or further, by appropriately stretching the extrudate at a temperature higher than the melting point of the polyamide or lower than the melting point of the polyamide. Furthermore,
It can also be obtained by stretching the extrudate at a temperature higher than the melting point of the polyamide and stretching the extrudate at a temperature lower than the melting point of the polyamide (hereinafter referred to as a reinforced rubber composition).
なお、靴用のテープゴムの成型に用いられる強化ゴム組
成物は、加硫可能なゴム、該加硫可能なゴム100重量部
当たり１〜20重量部のポリアミド、及び該加硫可能なゴ
ム100重量部当りシランカップリング剤0.1〜5.5重量部
を前記ポリアミドの融点以上の温度で混練して、得られ
た混練物（加硫可能なゴム100重量部に対してポリアミ
ド１〜20重量部含有する組成物）を用いたほかは、前述
と同様にして押し出し延伸することにより、本発明にお
ける靴用のテープゴムの成型に用いることができる強化
ゴム組成物を直接に得ることもできる。The reinforced rubber composition used for molding tape rubber for shoes is a vulcanizable rubber, 1 to 20 parts by weight of polyamide per 100 parts by weight of the vulcanizable rubber, and 100 parts by weight of the vulcanizable rubber. A kneaded product obtained by kneading 0.1 to 5.5 parts by weight of a silane coupling agent per part at a temperature not lower than the melting point of the polyamide (a composition containing 1 to 20 parts by weight of polyamide with respect to 100 parts by weight of vulcanizable rubber). Other than the above, a reinforced rubber composition that can be used for molding the tape rubber for shoes according to the present invention can be directly obtained by extruding and stretching in the same manner as described above.
本発明の靴用のテープゴムは、上記強化ゴム組成物、又
は、これらに加硫可能なゴムを添加してバンバリーミキ
サー，ロールなどの混練機を用い50〜180℃で１〜60分
間程度混練し、その後ロール或はゴム押出機等によりテ
ープ状に成型することによって得られる。The tape rubber for shoes of the present invention is kneaded at 50 to 180 ° C. for about 1 to 60 minutes using the above-mentioned reinforced rubber composition, or a vulcanizable rubber added thereto and a kneading machine such as a Banbury mixer or a roll. After that, it is obtained by molding into a tape shape by a roll or a rubber extruder.
本発明の靴用のテープゴムには、加硫剤などの添加剤が
配合される。The tape rubber for shoes of the present invention contains an additive such as a vulcanizing agent.
加硫剤としては、公知の加硫剤、たとえばイオウ，有機
過酸化剤，含イオウ化合物などを使用することができ
る。加硫剤をゴム組成物に配合する方法については特に
制限はなく、それ自体公知の配合方法を採用することが
できる。As the vulcanizing agent, known vulcanizing agents such as sulfur, organic peroxides, and sulfur-containing compounds can be used. The method of compounding the vulcanizing agent with the rubber composition is not particularly limited, and a compounding method known per se can be adopted.
また、本発明のテープゴム組成物には、加硫剤と共に、
カーボンブラック，熱硬化性樹脂，ホワイトカーボン，
活性化炭酸カルシウム，超微粉けい酸マグネシウム，ハ
イスチレン樹脂，クマロンインデン樹脂，フェノール樹
脂，リグニン，変性メラミン樹脂，石油樹脂などの補強
剤、各種グレードの炭酸カルシウム，塩基性炭酸マグネ
シウム，クレー，亜鉛華，けいそう土，再生ゴム，粉末
ゴム，エボナイト粉末などの充填剤、アルデヒド，アン
モニア類，アルデヒド・アミン類，グアニジン類，チオ
ウレア類，チアゾール類，チウラム類，ジチオカーバメ
ート類，キサンテート類などの加硫促進剤、金属酸化
物，脂肪酸などの加硫促進助剤、アミン・アルデヒド
類，アミン・ケトン類，アミン類，フェノール類，イミ
ダゾール類，含イオウ系あるいは含リン系老化防止剤、
ナフテン系やアロマティック系のプロセス油等を、本発
明の効果を損なわない範囲で配合することができる。Further, the tape rubber composition of the present invention, together with the vulcanizing agent,
Carbon black, thermosetting resin, white carbon,
Activated calcium carbonate, ultrafine magnesium silicate, high styrene resin, coumarone indene resin, phenol resin, lignin, modified melamine resin, petroleum resin and other reinforcing agents, various grades of calcium carbonate, basic magnesium carbonate, clay, zinc Additives such as flower, diatomaceous earth, reclaimed rubber, powdered rubber, ebonite powder, aldehydes, ammonia, aldehydes / amines, guanidines, thioureas, thiazoles, thiurams, dithiocarbamates, xanthates. Sulfurization accelerators, vulcanization accelerators such as metal oxides and fatty acids, amines / aldehydes, amines / ketones, amines, phenols, imidazoles, sulfur-containing or phosphorus-containing antioxidants,
A naphthene type or aromatic type process oil or the like can be added within a range not impairing the effects of the present invention.
［実施例］ 以下に実施例及び比較例を示す。以下の記載において部
は重量部を示す。[Examples] Examples and comparative examples are shown below. In the following description, “part” means “part by weight”.
また、靴用のテープゴムのムーニー粘度ML1+4（100℃）
はJIS K6300に従って測定し、末加硫物の引張応力，引
張強度はJIS K6301に従って測定した。さらに靴用のテ
ープゴムの状態は目視により行った。In addition, Mooney viscosity ML 1 + 4 (100 ℃) of tape rubber for shoes
Was measured according to JIS K6300, and the tensile stress and tensile strength of the unvulcanized product were measured according to JIS K6301. Further, the state of the tape rubber for shoes was visually observed.
以下、下記実施例１〜11及び比較例１〜４における強化
ゴム組成物（マスターバッチ）の配合割合、本発明の靴
用のテープゴム配合割合、物性等については、後記第１
表および第2,第３表にまとめて記載した。Hereinafter, the compounding ratio of the reinforced rubber composition (masterbatch) in Examples 1 to 11 and Comparative Examples 1 to 4 below, the compounding ratio of the tape rubber for the shoe of the present invention, and the physical properties will be described in the first section below.
It is described collectively in the table and Tables 2 and 3.
実施例１ 220℃、50r.p.m.にセットしたブラベンダーブラストグ
ラフ中に、粘度が１×106ポイズの天然ゴム（NR）100
部、及び老化防止剤としてＮ−（３−メタクリロイルオ
キシ−２−ヒドロキシプロピル）−Ｎ′−フェニル−ｐ
−フェニレンジアミン〔商品名ノクラックＧ−１、大内
新興化学工業（株）製〕1.0部を投入し、これらを30秒
間混練後、ナイロン６（商品名1030B、宇部興産（株）
製、融点221℃、分子量30,000）100重量部当たり２重量
部のＮ−β（アミノエチル）γ−アミノプロピルトリメ
トキシシラン（商品名KBM603、信越化学工業（株）製、
以下シランＡ）をあらかじめ練り込んだペレット51部を
投入し、13分間混練し（この間、ブラベンダー内の温度
は230℃まで上昇）、混練物を得た。得られた混練物
を、ノズルの内径2mm、ノズルの長さと内径との比（L/
D）が２の円形ダイを有する20mmφ押出機（Haake社製）
を用いてダイ設定温度235℃で紐状に押出し、次いで、
押出物をノズル直下3mに設置したガイドロールを経て、
ボビンにドラフト比10（38.8m/分の速度）で巻取った。
この巻取物約500本を束ねてシート状（厚さ約2mm、巾約
150mm）とし、このシート状物をロール間隙0.2mm、温度
60℃の一対の圧延ロールで約10倍に圧延して、強化ゴム
組成物（マスターバッチ）（試料１）を得た。Example 1 In a Brabender blast graph set at 220 ° C. and 50 rpm, a natural rubber (NR) 100 having a viscosity of 1 × 10 6 poise
Parts and N- (3-methacryloyloxy-2-hydroxypropyl) -N'-phenyl-p as an antioxidant
-Phenylenediamine (trade name: Nocrac G-1, manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) 1.0 part was added, and after kneading these for 30 seconds, nylon 6 (trade name 1030B, Ube Industries, Ltd.)
Made, melting point 221 ° C., molecular weight 30,000) 2 parts by weight per 100 parts by weight of N-β (aminoethyl) γ-aminopropyltrimethoxysilane (trade name KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.,
51 parts of pellets in which silane A) was previously kneaded were introduced and kneaded for 13 minutes (while the temperature inside the Brabender increased to 230 ° C.) to obtain a kneaded product. The resulting kneaded product was measured for the nozzle inner diameter of 2 mm and the ratio of the nozzle length to the inner diameter (L /
D) 20mmφ extruder (Haake) with 2 circular dies
Extruded into a string at a die set temperature of 235 ° C using
The extrudate passed through a guide roll installed 3 m directly below the nozzle,
It was wound on a bobbin at a draft ratio of 10 (speed of 38.8 m / min).
Approximately 500 rolls are bundled into a sheet (thickness 2 mm, width approx.
150 mm), and this sheet-like material with a roll gap of 0.2 mm and temperature
A pair of rolling rolls at 60 ° C. rolled about 10 times to obtain a reinforced rubber composition (masterbatch) (Sample 1).
次に、90℃、77r.p.m.にセットしたバンバリーにより、
前述のようにして配合・混練し押出された強化ゴム組成
物（試料１のマスターバッチ）、並びに、第２表に示す
配合剤〔後述する（注１）〜（注３）も参照〕のうち加
硫促進剤及びイオウを除く各配合成分（天然ゴム、カー
ボンブラック:C/B、その他の配合剤等）を混練して混練
物Ａを得て、次いで、この混練物Ａに10インチロール上
で加硫促進剤及びイオウを追加して混練し、第２表に示
す配合割合の混練物Ｂ（テープゴムの成型用の強化ゴム
組成物）を得、最後に、その混練物Ｂをテープ状にロー
ル出して靴用のテープゴム（未加硫物）を得た後、得ら
れた未加硫の靴用のテープゴムの物性を測定すると共
に、その未加硫の靴用のテープゴムを用いて公知の手段
によって靴を成型して、120℃の空気中で60分間の加硫
を行った。前述の未加硫の靴用のテープゴムの物性、及
び、成型・加硫後の製品面の状況を、第２表に示す。Next, with Banbury set at 90 ° C and 77 rpm,
Of the reinforced rubber composition (masterbatch of sample 1) compounded / kneaded and extruded as described above, and the compounding agent shown in Table 2 [see also (Note 1) to (Note 3) described below] Each compounding component (natural rubber, carbon black: C / B, other compounding agents, etc.) except the vulcanization accelerator and sulfur is kneaded to obtain a kneaded product A, which is then rolled on a 10 inch roll. With the addition of a vulcanization accelerator and sulfur, kneading is performed to obtain a kneaded material B (reinforced rubber composition for molding tape rubber) having a compounding ratio shown in Table 2. Finally, the kneaded material B is formed into a tape. After roll-out to obtain tape rubber for shoes (unvulcanized product), the physical properties of the obtained unvulcanized tape rubber for shoes are measured, and the unvulcanized shoe tape rubber is used to The shoe was molded by means and vulcanized in air at 120 ° C. for 60 minutes. Table 2 shows the physical properties of the unvulcanized tape rubber for shoes and the condition of the product surface after molding and vulcanization.
実施例２ シランＡに代えてビニルトリス（β−メトキシエトキ
シ）シラン（商品名KBC1003、信越化学工業（株）製、
シランＢ）を用いた他は実施例１と同様にして強化ゴム
組成物（試料２）を得、この試料２を強化ゴム組成物と
して使用した他は実施例１と同様にして行った。Example 2 Instead of silane A, vinyltris (β-methoxyethoxy) silane (trade name KBC1003, manufactured by Shin-Etsu Chemical Co., Ltd.,
A reinforced rubber composition (sample 2) was obtained in the same manner as in Example 1 except that silane B) was used, and the same procedure as in Example 1 was carried out except that this sample 2 was used as the reinforced rubber composition.
実施例３ シランＡに代えてγ−メタクリロキシプロピルトリメト
キシシラン（商品名KBM503、信越化学工業（株）製、シ
ランＣ）を用いた他は実施例１と同様にして強化ゴム組
成物（試料３）を得、この試料３を強化ゴム組成物とし
て使用した他は実施例１と同様にして行った。Example 3 In place of silane A, γ-methacryloxypropyltrimethoxysilane (trade name KBM503, manufactured by Shin-Etsu Chemical Co., Ltd., silane C) was used in the same manner as in Example 1 except that a reinforced rubber composition (sample) was used. 3) was obtained, and this sample 3 was used in the same manner as in Example 1 except that it was used as a reinforced rubber composition.
実施例４ シランＡに代えてγ−メルカプトプロピルトリメトキシ
シラン（商品名KBM803、信越化学工業（株）製、シラン
Ｄ）を用いた他は実施例１と同様にして強化ゴム組成物
（試料４）を得、この試料４を強化ゴム組成物として使
用した他は実施例１と同様にして行った。Example 4 A reinforced rubber composition (Sample 4) was prepared in the same manner as in Example 1 except that γ-mercaptopropyltrimethoxysilane (trade name KBM803, manufactured by Shin-Etsu Chemical Co., Ltd., Silane D) was used instead of silane A. 2) was used, and this sample 4 was used as a reinforced rubber composition.
実施例５ シランＡに代えてβ−（3,4−エポキシシクロヘキシ
ル）エチルトリメトキシシラン（商品名KBM303、信越化
学工業（株）製、シランＥ）を用いた他は実施例１と同
様にして強化ゴム組成物（試料５）を得、この試料５を
強化ゴム組成物として使用した他は実施例１と同様にし
て行った。Example 5 In the same manner as in Example 1 except that β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (trade name KBM303, Shin-Etsu Chemical Co., Ltd., Silane E) was used in place of silane A. A reinforced rubber composition (Sample 5) was obtained, and the same procedure as in Example 1 was carried out except that this Sample 5 was used as the reinforced rubber composition.
実施例６ ナイロン６（商品名1013B、宇部興産（株）製、融点221
℃、分子量13,000）100重量部当り４重量部のシランＡ
をあらかじめ練り込んだペレット52部を使用した他は実
施例１と同様に実施して強化ゴム組成物（試料６）を
得、この試料６を強化ゴム組成物として使用した他は実
施例１と同様にして行った。Example 6 Nylon 6 (trade name: 1013B, manufactured by Ube Industries, Ltd., melting point 221)
℃, molecular weight 13,000) 4 parts by weight of silane A per 100 parts by weight
Was carried out in the same manner as in Example 1 except that 52 parts of pellets which had been kneaded in advance were used to obtain a reinforced rubber composition (Sample 6), and this Sample 6 was used as a reinforced rubber composition. The same was done.
実施例７ 天然ゴムに投入する６−ナイロンの量を100部に代えた
他は実施例１と同様にして強化ゴム組成物（試料７）を
得、この試料７を強化ゴム組成物として使用した他は実
施例１と同様にして行った。Example 7 A reinforced rubber composition (Sample 7) was obtained in the same manner as in Example 1 except that the amount of 6-nylon added to natural rubber was changed to 100 parts, and this Sample 7 was used as the reinforced rubber composition. Others were the same as in Example 1.
実施例８ 天然ゴムに投入する６−ナイロンの量を20部に代えた他
は実施例１と同様にして強化ゴム組成物（試料８）を
得、この試料８を強化ゴム組成物として使用した他は実
施例１と同様にして行った。Example 8 A reinforced rubber composition (Sample 8) was obtained in the same manner as in Example 1 except that the amount of 6-nylon added to natural rubber was changed to 20 parts, and this Sample 8 was used as the reinforced rubber composition. Others were the same as in Example 1.
実施例２〜８における未加硫の靴用のテープゴムの物性
及び成型・加硫後の製品面の状況を第２表に示す。Table 2 shows the physical properties of the unvulcanized tape rubber for shoes and the condition of the product surface after molding and vulcanization in Examples 2 to 8.
実施例9,10 各成分の組成（配合割合）を第３表に示すように代えた
他は実施例１と同様にして行った。Examples 9 and 10 Examples 9 and 10 were carried out in the same manner as in Example 1 except that the composition (blending ratio) of each component was changed as shown in Table 3.
実施例11 カーボンブラックに代えてホワイトカーボンを使用した
他は実施例１と同様にして行った。Example 11 Example 11 was carried out in the same manner as in Example 1 except that white carbon was used instead of carbon black.
比較例１ 強化ゴム組成物を使用しないで各成分の使用割合（組
成）を第３表に示すように代えた他は実施例１と同様に
して行った。Comparative Example 1 The same procedure as in Example 1 was carried out except that the reinforcing rubber composition was not used and the ratio (composition) of each component was changed as shown in Table 3.
比較例２〜５ 各成分の組成（配合割合）を第３表に示すように代えた
他は実施例１と同様にして行った。Comparative Examples 2 to 5 Comparative Examples 2 to 5 were carried out in the same manner as in Example 1 except that the composition (blending ratio) of each component was changed as shown in Table 3.
実施例９〜11および比較例１〜５における未加硫の靴用
のテープゴムの物性及び成型・加硫後の製品面の状況を
第３表に示す。Table 3 shows the physical properties of the unvulcanized tape rubber for shoes in Examples 9 to 11 and Comparative Examples 1 to 5 and the condition of the product surface after molding and vulcanization.
なお、第１表に示す各試料１〜８（強化ゴム組成物）に
おける結合ゴム量の測定は、次のようにして行った。The amount of bound rubber in each of Samples 1 to 8 (reinforced rubber composition) shown in Table 1 was measured as follows.
［結合ゴム量測定］ 強化ゴム組成物2gをそれぞれトルエン200mlに80℃で添
加し、強化ゴム組成物中のゴム分を溶解させ、得られた
スラリーを室温で遠心分離して溶液部分と沈澱部分とに
分けた。沈澱部分について前記の操作を７回繰り返し行
った後、沈澱部分を乾燥してナイロン繊維を得た。この
ナイロン繊維をフェノールとオルソジクロルベンゼンの
混合溶媒に溶解させて、1Hの核磁気共鳴スペクトル（NM
R）で分析（内部標準テトラメチルシラン）し、NMRチャ
ートからゴムに起因するメチル基及びメチレン基、６−
ナイロンに起因するCO基に隣接したメチレン基、NH基に
隣接したメチレン基、及び他の３個のメチレン基の各々
のピークについて、切り取り面積法により６−ナイロン
と天然ゴムとのモル比をもとめて、結合ゴム量を算出し
た。また、前記のナイロン繊維の形状を、繊維約200本
について10,000倍の倍率で走査型顕微鏡を用いて測定し
た。繊維は断面円形の極めて細い短繊維であった。[Measurement of bound rubber amount] 2 g of the reinforced rubber composition was added to 200 ml of toluene at 80 ° C to dissolve the rubber component in the reinforced rubber composition, and the resulting slurry was centrifuged at room temperature to separate the solution part and the precipitated part. Divided into The above operation was repeated 7 times for the precipitated portion, and then the precipitated portion was dried to obtain a nylon fiber. This nylon fiber was dissolved in a mixed solvent of phenol and orthodichlorobenzene, and the 1 H nuclear magnetic resonance spectrum (NM
R) (internal standard tetramethylsilane), and from the NMR chart, methyl group and methylene group derived from rubber, 6-
Determine the molar ratio of 6-nylon and natural rubber by the cut area method for each peak of the methylene group adjacent to the CO group, the methylene group adjacent to the NH group, and the other three methylene groups originating from nylon. Then, the amount of bound rubber was calculated. The shape of the nylon fiber was measured for about 200 fibers at a magnification of 10,000 times using a scanning microscope. The fibers were very fine short fibers with a circular cross section.
また、第３表における（注１）〜（注３）は次の通りで
ある。Further, (Note 1) to (Note 3) in Table 3 are as follows.
（注１）Ｎ−330:HAF、粒子径30mμ、DBP吸油量110ml/1
00g （注２）他の配合剤 芳香族系プロセスオイル、エッソ110:10部、亜鉛華:5
部、ステアリン酸:2部、老化防止剤 Ｎ−フェニル−
Ｎ′−イソプロピル−ｐ−フェニレンジアミン １部、
加硫促進剤 Ｎ−オキシジエチレンベンゾチアジル−２
−スルフェンアミド 0.8部、イオウ 1.5部 （注３）カットファイバー：ナイロン短繊維 直径20μｍ、平均長さ2mm ［本発明の効果］ 本発明により、ML粘度が低いために作業性に優れ、かつ
加硫温度付近での引張応力，引張強度が大きいために加
硫時の変形がない生産性のよい靴用のテープゴムが得ら
れた。(Note 1) N-330: HAF, particle size 30mμ, DBP oil absorption 110ml / 1
00g (Note 2) Other compounding agents Aromatic process oil, Esso 110: 10 parts, zinc white: 5
Parts, stearic acid: 2 parts, anti-aging agent N-phenyl-
1 part of N'-isopropyl-p-phenylenediamine,
Vulcanization accelerator N-oxydiethylene benzothiazyl-2
-Sulfenamide 0.8 part, sulfur 1.5 part (Note 3) Cut fiber: Nylon short fiber Diameter 20 μm, average length 2 mm [Effect of the present invention] According to the present invention, ML viscosity is low and workability is excellent and Because of the large tensile stress and tensile strength near the vulcanization temperature, there was no deformation during vulcanization, and a highly productive tape rubber for shoes was obtained.
Claims (1)
能なポリアミドの平均繊維直径が0.05〜0.8μｍの短繊
維１〜20重量部が埋封されており、かつ、加硫可能なゴ
ムとポリアミドとがシランカップリング剤を介して結合
されたものを少なくとも一部含有し、未加硫状態での12
0℃における100％引張応力（M100）が40〜102Kg/cm2、
また引張強度（TB）が140〜190Kg/cm2である靴用のテー
プゴム。1. 100 parts by weight of vulcanizable rubber are embedded with 1 to 20 parts by weight of short fibers having an average fiber diameter of 0.05 to 0.8 μm of a fiber-forming polyamide and are vulcanizable. It contains at least a part of rubber and polyamide bonded via a silane coupling agent, and is 12 in the unvulcanized state.
100% tensile stress (M 100 ) at 0 ℃ is 40 to 102Kg / cm 2 ,
Tape rubber for shoes with a tensile strength (T B ) of 140-190 Kg / cm 2 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62173932A JPH0687807B2 (en) | 1987-07-14 | 1987-07-14 | Tape rubber for shoes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62173932A JPH0687807B2 (en) | 1987-07-14 | 1987-07-14 | Tape rubber for shoes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6417604A JPS6417604A (en) | 1989-01-20 |
| JPH0687807B2 true JPH0687807B2 (en) | 1994-11-09 |
Family
ID=15969741
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62173932A Expired - Lifetime JPH0687807B2 (en) | 1987-07-14 | 1987-07-14 | Tape rubber for shoes |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0687807B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109431002A (en) * | 2018-10-31 | 2019-03-08 | 际华三五三七制鞋有限责任公司 | Blended 1X1 camouflage color plain cloth hot vulcanized rubber boots adherend of polyester-cotton blend and preparation method and application |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6958815B2 (en) * | 2016-01-26 | 2021-11-02 | 学校法人神奈川大学 | Aromatic polyamide surface modifier for silica sol |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5879037A (en) * | 1981-11-05 | 1983-05-12 | Ube Ind Ltd | Reinforced rubber composition and its preparation |
| JPH0433300A (en) * | 1990-05-28 | 1992-02-04 | Matsushita Electric Works Ltd | Turn-on device for discharge lamp |
-
1987
- 1987-07-14 JP JP62173932A patent/JPH0687807B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109431002A (en) * | 2018-10-31 | 2019-03-08 | 际华三五三七制鞋有限责任公司 | Blended 1X1 camouflage color plain cloth hot vulcanized rubber boots adherend of polyester-cotton blend and preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6417604A (en) | 1989-01-20 |
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