JP4438435B2 - Laminated body of thermoplastic sheet and elastomer adherend - Google Patents
Laminated body of thermoplastic sheet and elastomer adherend Download PDFInfo
- Publication number
- JP4438435B2 JP4438435B2 JP2004025782A JP2004025782A JP4438435B2 JP 4438435 B2 JP4438435 B2 JP 4438435B2 JP 2004025782 A JP2004025782 A JP 2004025782A JP 2004025782 A JP2004025782 A JP 2004025782A JP 4438435 B2 JP4438435 B2 JP 4438435B2
- Authority
- JP
- Japan
- Prior art keywords
- adherend
- elastomer
- resin
- value
- adhesive polymer
- 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 - Fee Related
Links
- 229920001971 elastomer Polymers 0.000 title claims description 35
- 239000000806 elastomer Substances 0.000 title claims description 27
- 229920001169 thermoplastic Polymers 0.000 title claims description 8
- 239000004416 thermosoftening plastic Substances 0.000 title claims description 8
- 229920005989 resin Polymers 0.000 claims description 35
- 239000011347 resin Substances 0.000 claims description 35
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 23
- 229920000642 polymer Polymers 0.000 claims description 16
- 239000002998 adhesive polymer Substances 0.000 claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 239000005060 rubber Substances 0.000 claims description 8
- 150000003505 terpenes Chemical class 0.000 claims description 6
- 235000007586 terpenes Nutrition 0.000 claims description 6
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 claims description 3
- 229920001194 natural rubber Polymers 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- 244000043261 Hevea brasiliensis Species 0.000 claims description 2
- 229920003052 natural elastomer Polymers 0.000 claims description 2
- 238000003475 lamination Methods 0.000 claims 1
- 229920001195 polyisoprene Polymers 0.000 claims 1
- 229920002725 thermoplastic elastomer Polymers 0.000 claims 1
- 239000000853 adhesive Substances 0.000 description 28
- 230000001070 adhesive effect Effects 0.000 description 27
- 239000000654 additive Substances 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002788 crimping Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 229920006465 Styrenic thermoplastic elastomer Polymers 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 230000000181 anti-adherent effect Effects 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003911 antiadherent Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000019241 carbon black Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 229920006132 styrene block copolymer Polymers 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Tires In General (AREA)
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は粘着剤ポリマーを介して熱可塑性シートとエラストマー被着体とを接合した積層体に関し、更に詳しくは粘着剤の自着性を抑えて積層作業性を高めた積層体及びそれを用いた空気入りタイヤに関する。 The present invention relates to a laminate in which a thermoplastic sheet and an elastomer adherend are bonded via an adhesive polymer, and more specifically, a laminate that suppresses self-adhesiveness of the adhesive and improves the laminating workability, and the same. Related to pneumatic tires.
粘接着剤に配合する粘着付与樹脂は、通常ポリマーとの相容性が近いものを選ぶのが常識である（例えば非特許文献１参照）。しかしながらこうして得られた粘着剤はタックが非常に大きくなるため、フィルムなどに塗布して用いると、粘着剤部分同士が貼りついた場合にはなかなか剥がせず、時には片方の粘着剤が基材から剥がれてしまうといたったトラブルの発生原因となっていた。更に被着体がエラストマーなどの柔らかい材料であると、表面にフィルムなどを貼りつける場合に貼りつけにくいという問題があった。しかし、相容性に劣る粘着付与樹脂を使用すると、タックが落ちて成形後に積層体が剥がれてしまうという問題が発生する場合があった。 It is common sense to select a tackifier resin to be blended in an adhesive, usually having a compatibility with a polymer (see Non-Patent Document 1, for example). However, the pressure-sensitive adhesive thus obtained has a very large tack, so when applied to a film or the like, it does not readily peel off when the pressure-sensitive adhesive parts stick together, and sometimes one of the pressure-sensitive adhesives is removed from the substrate. If it peeled off, it was a cause of trouble. Further, when the adherend is a soft material such as an elastomer, there is a problem that it is difficult to attach a film or the like on the surface. However, when a tackifying resin having inferior compatibility is used, there is a case in which tack is dropped and the laminate is peeled off after molding.
従って、本発明は熱可塑性シートとエラストマー被着体との積層性に問題を生ずることなく積層作業性を改良することを目的とする。 Accordingly, an object of the present invention is to improve the laminating workability without causing a problem in the laminating properties of the thermoplastic sheet and the elastomer adherend.
本発明に従えば、（ｉ）粘着剤ポリマーＡと熱可塑性のシートＣとを貼り合わせたフィルム積層体と、（ｉｉ）そのフィルム積層体の粘着剤ポリマーＡと接するように積層されたエラストマー被着体Ｂとの積層体において、前記粘着剤ポリマーＡのＳｐ値がエラストマー被着体ＢのＳｐ値から少なくとも１．０（Ｐａ 1/2 ）以上離れたものであり、該粘着剤ポリマーＡに、エラストマー被着体ＢのＳｐ値±０．５の範囲のものに相容性を示す粘着付与樹脂Ｄを配合し、該エラストマー被着体Ｂに、粘着剤ポリマーＡのＳｐ値±０．５の範囲のものに相容性を示す粘着付与樹脂Ｅを配合し、そして、前記粘着剤ポリマーＡがスチレン系熱可塑性エラストマーもしくはその変性物であり、エラストマー被着体Ｂが天然ゴム、ポリイソプレンゴム、スチレン−ブタジエンゴム又はポリブタジエンゴムから選ばれるゴムであり、粘着剤ポリマーＡに配合される粘着付与樹脂Ｄがテルペン樹脂及び／又はピネン樹脂であり、エラストマー被着体Ｂに配合される粘着付与樹脂Ｅが変性テルペン樹脂、テルペン−フェノール樹脂、クマロン−インデン樹脂及びスチレン樹脂から選ばれる少なくとも１種であることを特徴とする積層体が提供される。 According to the present invention, ( i) a film laminate in which an adhesive polymer A and a thermoplastic sheet C are bonded together, and (ii) an elastomer coating laminated so as to be in contact with the adhesive polymer A of the film laminate. In the laminate with the adherend B, the Sp value of the pressure-sensitive adhesive polymer A is at least 1.0 (Pa 1/2 ) or more away from the Sp value of the elastomer adherend B. In addition, the tackifier resin D exhibiting compatibility is blended with the elastomer adherend B having an Sp value in the range of ± 0.5, and the elastomer adherend B has an Sp value ± 0.5 of the adhesive polymer A. A tackifying resin E having compatibility with the above-mentioned range, and the pressure-sensitive adhesive polymer A is a styrenic thermoplastic elastomer or a modified product thereof, and the elastomer adherend B is natural rubber or polyisoprene rubber. , Su A tackifier resin E which is a rubber selected from tylene-butadiene rubber or polybutadiene rubber, the tackifier resin D blended with the adhesive polymer A is a terpene resin and / or pinene resin, and blended with the elastomer adherend B. Is a at least one member selected from a modified terpene resin, a terpene-phenol resin, a coumarone-indene resin, and a styrene resin .
本発明は、通常両立が困難な粘着剤のタックと作業性が、被着体がエラストマーの場合、粘着付与樹脂の相容性を規定することで両立が可能となることを見出したものである。すなわち、被着体がエラストマーの場合、粘着剤と被着体のそれぞれのポリマーを選択する際、相容性の悪い組み合わせ（Ｓｐ値が離れている）を選び、粘着剤ポリマーＡに配合する粘着付与樹脂を、被着体ポリマーＢに相容性の高い（Ａには低い）ものとすることで、粘着剤自身のタックは低く抑えられ作業性が向上しつつ、被着体Ｂと貼りあわせたときには十分なタックを示すことを見出し、本発明を完成させた。更に被着体に粘着剤に相容する樹脂を配合すると、更に良いタックを示す。特に被着体をタイヤの未加硫部材とし、スチレン系ブロック共重合体の粘着剤を用いると、ゴムに対する十分なタックを示しつつ、高い作業性でフィルム状部材を積層させることができる。 In the present invention, it has been found that tackiness and workability of a pressure-sensitive adhesive, which are usually difficult to be compatible, can be compatible by defining the compatibility of the tackifier resin when the adherend is an elastomer. . That is, when the adherend is an elastomer, when selecting the respective polymers of the pressure-sensitive adhesive and the adherend, an incompatible combination (Sp value is separated) is selected, and the pressure-sensitive adhesive blended into the pressure-sensitive adhesive polymer A By making the imparting resin highly compatible with the adherend polymer B (low for A), the tack of the pressure sensitive adhesive itself is kept low and the workability is improved, and the adherend B is bonded. As a result, the present invention was completed. Furthermore, when a resin compatible with the adhesive is added to the adherend, a better tack is exhibited. In particular, when the adherend is an unvulcanized member of a tire and an adhesive of a styrene block copolymer is used, the film-like member can be laminated with high workability while showing sufficient tack against rubber.
本発明に従えば、前記粘着剤ポリマーＡとエラストマー被着体Ｂとの組合せにおいて、エラストマー被着体Ｂに、粘着剤ポリマーＡのＳｐ値±０．５の範囲のものに相容性を示す粘着付与樹脂Ｄを更に配合した前記積層体が提供される。 According to the present invention, in the combination of the pressure-sensitive adhesive polymer A and the elastomer adherend B, the elastomer adherend B is compatible with the pressure-sensitive adhesive polymer A having an Sp value in the range of ± 0.5. The laminate is further provided with a tackifier resin D.
本発明で用いる粘着剤ポリマーＡとしては、例えばスチレン−ブタジエンブロック共重合体又はスチレン−イソプレンブロック共重合体（の変成物）、アクリルゴム、エチレン−酢酸ビニル共重合体（の変成物）、エチレン−エチルアクリレート共重合体（の変成物）などをあげることができる。また、エラストマー被着体ＢとしてはＮＲ，ＩＲ，ＢＲ，ＳＢＲなどをあげることができる。更に本発明で用いる粘着付与樹脂Ｄとしてはテルペン樹脂、ピネン樹脂が、また、粘着付与樹脂Ｅとしては変性テルペン樹脂、テルペン−フェノール樹脂、クマロン−インデン樹脂、スチレン樹脂などをあげることができる。 Examples of the pressure-sensitive adhesive polymer A used in the present invention include a styrene-butadiene block copolymer or a styrene-isoprene block copolymer (modified product thereof), an acrylic rubber, an ethylene-vinyl acetate copolymer (modified product thereof), and ethylene. -Ethyl acrylate copolymer (modified product thereof) and the like. Examples of the elastomer adherend B include NR, IR, BR, SBR and the like . Furthermore, examples of the tackifier resin D used in the present invention include terpene resins and pinene resins, and examples of the tackifier resin E include modified terpene resins, terpene-phenol resins, coumarone-indene resins, and styrene resins .
本発明に従えば粘着剤ポリマーＡのＳｐ値とエラストマー被着体ＢのＳｐ値との差が少なくとも１．０Ｐａ1/2以上、好ましくは１．２〜２．０Ｐａ1/2でなければならない。Ｓｐ値の差が１．０Ｐａ1/2未満ではポリマーＡへの相容性を下げつつエラストマー被着体Ｂには相容してタックを付与することが困難であるので好ましくない。ここでＳｐ値はポリマーの極性を表す指標で、分子の凝集エネルギー密度の平方根で表され、Ｓｐ値が大きいほど極性が大きい。Ｓｐ値は、たとえば日本ゴム協会編、新版ゴム技術の基礎Ｐ１０１に記載されている。 The difference between Sp value of Sp value and elastomer adherend B of follow if the adhesive polymer A in the present invention is at least 1.0 Pa 1/2 or more, preferably should be 1.2 to 2.0 Pa 1/2 . If the difference in Sp value is less than 1.0 Pa 1/2 , it is difficult to compatibilize the elastomer adherend B while imparting tack to the elastomer adherend B while lowering the compatibility with the polymer A, which is not preferable. Here, the Sp value is an index representing the polarity of the polymer, and is represented by the square root of the cohesive energy density of the molecule. The greater the Sp value, the greater the polarity. The Sp value is described in, for example, the edition of Japan Rubber Association, Basic P101 of New Edition Rubber Technology.
本発明に従えば、更に、前記粘着剤ポリマーＡに、エラストマー被着体ＢのＳｐ値±０．５の範囲、好ましくは被着体ＢのＳｐ値±０．３の範囲のＳｐ値に相容性を示す粘着付与剤Ｄを配合しなければならない。この値が大き過ぎると、粘着剤Ａのタックが下がらなかったり、エラストマー被着体Ｂへのタックが不足するので好ましくない。粘着付与剤Ｄの配合量には特に制限はないが、コストや粘着剤の物性の観点からポリマーＡに対し２０〜２００重量部配合するのが好ましい。 According to the present invention, the pressure-sensitive adhesive polymer A further has an Sp value in the range of Sp value ± 0.5 of the elastomer adherend B, preferably in the range of Sp value ± 0.3 of the adherend B. A tackifier D exhibiting capacity must be blended. If this value is too large, the tackiness of the pressure-sensitive adhesive A does not decrease, or the tackiness to the elastomer adherend B is insufficient, which is not preferable. The amount of the tackifier D is not particularly limited, but it is preferably 20 to 200 parts by weight based on the polymer A from the viewpoint of cost and physical properties of the adhesive.
本発明の好ましい態様によれば、エラストマー被着体Ｂに、粘着剤ポリマーＡのＳｐ値±０．５に相容性を示す粘着付与樹脂Ｅを配合することによりＡとＢを貼りあわせた時のタックをさらに向上させることができるという効果が得られるので好ましい。 According to a preferred embodiment of the present invention, when A and B are bonded to the elastomer adherend B by blending a tackifier resin E exhibiting compatibility with the Sp value ± 0.5 of the adhesive polymer A. This is preferable because the effect of further improving the tack can be obtained.
本発明において使用する熱可塑性シートＣとしては、特に制限はないが例えばポリエチレン、ポリプロピレン、ポリエステル、ポリアミド、ポリスチレン、およびこれらを連続層とし、他のポリマーを分散させたものなどを用いることができる。 The thermoplastic sheet C used in the present invention is not particularly limited, and for example, polyethylene, polypropylene, polyester, polyamide, polystyrene, and the like in which these are continuous layers and other polymers are dispersed can be used.
本発明に係る積層体の熱可塑性シート、粘着剤、被着体には、更に常用の添加剤、例えば可塑剤、架橋剤、老化防止剤、加硫促進剤、着色剤、各種カーボンブラック、各種シリカなどの補強剤および充填剤などの各種添加剤を必要に応じ配合することができる。これらの添加剤の配合量は本発明の目的に反しない限り、従来の一般的な配合量とすることができる。 For the thermoplastic sheet, pressure-sensitive adhesive, and adherend of the laminate according to the present invention, conventional additives such as plasticizers, crosslinking agents, anti-aging agents, vulcanization accelerators, colorants, various carbon blacks, various types Various additives such as a reinforcing agent such as silica and a filler can be blended as necessary. As long as the amount of these additives is not contrary to the object of the present invention, a conventional general amount can be used.
以下、実施例によって本発明を更に説明するが、本発明の範囲をこれらの実施例に限定するものでないことはいうまでもない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further, it cannot be overemphasized that the scope of the present invention is not limited to these Examples.
従来例１、実施例１〜３及び比較例１
サンプルの調製
表Ｉに示す各成分（重量部）を２５mmφの単軸混練押出機によって混合し、防着液を含んだ水中でカットし、粘着剤Ａのペレットを得た。
Conventional Example 1, Examples 1 to 3 and Comparative Example 1
Sample preparation Each component (parts by weight) shown in Table I was mixed by a single screw kneading extruder with a diameter of 25 mm and cut in water containing an anti-adhesion solution to obtain a pellet of adhesive A.
次に表ＩＩに示す各成分（重量部）を１．７リットルのバンバリーミキサーによって混合し、被着体Ｂのシートを得た。 Next, each component (parts by weight) shown in Table II was mixed with a 1.7 liter Banbury mixer to obtain an adherend B sheet.
上で得た粘着剤Ａ及び被着体Ｂを用いて熱可塑性シートＣ（幅４００mm、厚さ０．２mmのポリエステルの押出シートを使用）に対し、粘着剤Ａを積層し、更にその粘着剤Ａに接するようにして被着体Ｂを積層した。 The pressure-sensitive adhesive A and the adherend B obtained above are used to laminate the pressure-sensitive adhesive A on the thermoplastic sheet C (using a polyester extruded sheet having a width of 400 mm and a thickness of 0.2 mm), and then the pressure-sensitive adhesive. The adherend B was laminated so as to be in contact with A.
次に得られた積層体を以下に示す試験法で評価した。結果は表ＩＩＩに示す。 Next, the obtained laminate was evaluated by the following test method. The results are shown in Table III.
評価試験法
１）タック試験
厚さ０．２mmのポリエステルシート上に、Ｔダイを用いて表Ｉに示す配合の粘接着剤を厚さ０．０５mmの厚さに均一に塗布した。これを幅１cmの帯状に切断し、タックテスターのリング部に取り付け、自着のタックの場合は１０cm四方に切った同じシートに、対被着体Ｂタックの場合は布で裏打した被着体Ｂのシートに垂直に押し付け、それを引き剥がす際の力を測定した。測定は（株）東洋精機製作所製 ＰＩＣＭＡタックテスターを用いて下記条件で測定した。
測定条件 上部試料寸法 ：１２．７mm×１５２mm
圧着荷重 ：４．９０N
剥離速度 ：１２０mm／min.
圧着時間 ：０sec.
温度 ：２０℃
湿度 ：６５％
Evaluation test method
1) Tack test An adhesive having the composition shown in Table I was uniformly applied to a thickness of 0.05 mm on a polyester sheet having a thickness of 0.2 mm using a T-die. This is cut into a 1cm wide band and attached to the ring of the tack tester. In the case of self-adhesive tack, the same sheet cut into 10cm squares, and in the case of anti-adherent B tack, the substrate is lined with cloth. The force when pressing the sheet B vertically and peeling it off was measured. The measurement was performed under the following conditions using a PICMA tack tester manufactured by Toyo Seiki Seisakusho.
Measurement conditions Upper sample size: 12.7 mm x 152 mm
Crimping load: 4.90N
Peeling speed: 120mm / min.
Crimping time: 0 sec.
Temperature: 20 ° C
Humidity: 65%
２）粘着剤Ａ同士のタック（判定基準）
◎：粘着剤同士をくっつけても、簡単に剥がせる
○：粘着剤同士をくっつけても、勢い良く剥がせば粘着剤の剥がれがなく剥がせる
×：粘着剤同士をくっつけると剥がせず、無理に剥がすと粘着剤がシートＣから剥がれたり、シートが伸びてしまう
2) Tack between adhesives A (determination criteria)
◎: Even if the adhesives are attached to each other, they can be easily peeled off ○: Even if the adhesives are attached to each other, if they are peeled off vigorously, the adhesive can be removed without peeling. The adhesive will peel off from the sheet C or the sheet will stretch
３）粘着剤Ａと被着体Ｂのタック（判定基準）
○：粘着剤Ａと被着体Ｂがしっかりついており、剥がすと粘着剤が材料破壊となる
×：粘着剤Ａと被着体Ｂがついておらず、剥がすときれいに粘着剤が剥がせる
3) Tack between adhesive A and adherend B (determination criteria)
○: Adhesive A and adherend B are firmly attached, and the adhesive is destroyed when peeled off. ×: Adhesive A and adherend B are not attached, and when peeled off, the adhesive can be removed cleanly.
表ＩＩＩに示す通り、従来例１は、粘着剤Ａと被着体ＢのＳｐ値を近い組み合わせで、Ａに相溶性の高い粘着付与樹脂を配合した例で、両者のタックは良好であるが、粘着剤Ａ同士でくっつくと剥がせない（粘着剤の材料破壊）。比較例１は、粘着剤ＡのＳｐ値を被着体と１．０Ｐａ １／２ 以上離した場合で被着体Ｂとのタックが落ちる。一方、参照例１は、粘着剤Ａに被着体Ｂに相溶する粘着付与樹脂Ｄを配合した例で、被着体Ｂとのタックを維持しつつ、粘着剤同士のタックを下げ、粘着剤の扱いがしやすくなった。また参照例２は、粘着剤ＡのポリマーのＳｐ値を被着体とさらに離し、被着体Ｂに相溶する粘着付与樹Ｄ脂を配合した例で、被着体とのタックを保ったまま、粘着剤Ａ同士のタックをさらに下げ、非常に扱いやすくなった。実施例１は、被着体Ｂに、粘着剤Ａに相溶する粘着付与樹脂Ｅを配合した例で、粘着剤と被着体のタックが更に向上した。 As shown in Table III, Conventional Example 1 is an example in which the Sp value of the adhesive A and the adherend B is close to each other, and a highly compatible tackifying resin is blended with A, and the tack of both is good. If the adhesives A stick together, they cannot be removed (material destruction of the adhesive). In Comparative Example 1, when the Sp value of the adhesive A is separated from the adherend by 1.0 Pa 1/2 or more, the tack with the adherend B falls. On the other hand, Reference Example 1 is an example in which a tackifier resin D that is compatible with the adherend B is blended with the adhesive A, while maintaining the tack with the adherend B, the tack between the adhesives is lowered, and the adhesive It became easier to handle the agent. Reference Example 2 is an example in which the Sp value of the polymer of the pressure-sensitive adhesive A is further separated from the adherend, and a tackified tree D fat that is compatible with the adherend B is blended, and the tack with the adherend is maintained. The tack between the adhesives A was further lowered, and it became very easy to handle. Example 1 is an example in which a tackifier resin E compatible with the adhesive A is blended with the adherend B, and the tack of the adhesive and the adherend is further improved.
以上の通り、本発明に従えば粘着剤Ａ同士のタックを抑えて粘着剤Ａと被着体Ｂとのタックに優れるので、作業性の改良と積層接着性の維持の両性能を達成することができ、ホース、空気式防舷材、タイヤのサイドプリントやインナーライナー、靴底などとして使用するのに有用である。 As described above, according to the present invention, since the tack between the pressure-sensitive adhesives A is suppressed and the tack between the pressure-sensitive adhesive A and the adherend B is excellent, both performance of improving workability and maintaining laminated adhesiveness are achieved. It is useful for use as hoses, pneumatic fenders, tire side prints, inner liners, and shoe soles.
Claims (2)
前記粘着剤ポリマーＡのＳｐ値がエラストマー被着体ＢのＳｐ値から少なくとも１．０（Ｐａ 1/2 ）以上離れたものであり、該粘着剤ポリマーＡに、エラストマー被着体ＢのＳｐ値±０．５の範囲のものに相容性を示す粘着付与樹脂Ｄを配合し、該エラストマー被着体Ｂに、粘着剤ポリマーＡのＳｐ値±０．５の範囲のものに相容性を示す粘着付与樹脂Ｅを配合し、そして、
前記粘着剤ポリマーＡがスチレン系熱可塑性エラストマーもしくはその変性物であり、エラストマー被着体Ｂが天然ゴム、ポリイソプレンゴム、スチレン−ブタジエンゴム又はポリブタジエンゴムから選ばれるゴムであり、粘着剤ポリマーＡに配合される粘着付与樹脂Ｄがテルペン樹脂及び／又はピネン樹脂であり、エラストマー被着体Ｂに配合される粘着付与樹脂Ｅが変性テルペン樹脂、テルペン−フェノール樹脂、クマロン−インデン樹脂及びスチレン樹脂から選ばれる少なくとも１種であること
を特徴とする積層体。 (I) Lamination of a film laminate in which an adhesive polymer A and a thermoplastic sheet C are bonded together, and (ii) an elastomer adherend B laminated so as to be in contact with the adhesive polymer A of the film laminate. In the body,
The Sp value of the adhesive polymer A is at least 1.0 (Pa 1/2 ) or more away from the Sp value of the elastomer adherend B, and the Sp value of the elastomer adherend B is included in the adhesive polymer A. In the range of ± 0.5, a tackifying resin D showing compatibility is blended, and the elastomer adherend B is compatible with the adhesive polymer A having an Sp value of ± 0.5. Formulating the tackifying resin E shown, and
The pressure-sensitive adhesive polymer A is a styrene-based thermoplastic elastomer or a modified product thereof, and the elastomer adherend B is a rubber selected from natural rubber, polyisoprene rubber, styrene-butadiene rubber, or polybutadiene rubber. The tackifying resin D to be blended is a terpene resin and / or pinene resin, and the tackifying resin E to be blended with the elastomer adherend B is selected from a modified terpene resin, a terpene-phenol resin, a coumarone-indene resin, and a styrene resin. Be at least one kind
A laminate characterized by the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004025782A JP4438435B2 (en) | 2004-02-02 | 2004-02-02 | Laminated body of thermoplastic sheet and elastomer adherend |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004025782A JP4438435B2 (en) | 2004-02-02 | 2004-02-02 | Laminated body of thermoplastic sheet and elastomer adherend |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005212452A JP2005212452A (en) | 2005-08-11 |
| JP4438435B2 true JP4438435B2 (en) | 2010-03-24 |
Family
ID=34908058
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004025782A Expired - Fee Related JP4438435B2 (en) | 2004-02-02 | 2004-02-02 | Laminated body of thermoplastic sheet and elastomer adherend |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4438435B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007099146A (en) * | 2005-10-06 | 2007-04-19 | Yokohama Rubber Co Ltd:The | Layered material, and pneumatic tire using the same |
| JP5754092B2 (en) | 2010-07-15 | 2015-07-22 | 横浜ゴム株式会社 | Laminated body and pneumatic tire using the same |
-
2004
- 2004-02-02 JP JP2004025782A patent/JP4438435B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005212452A (en) | 2005-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100340394C (en) | Reusable packaging seal, method of manufacture and application thereof | |
| US6183862B1 (en) | Multilayer PSA construction exhibiting reduced tackifier migration | |
| JP4983922B2 (en) | Pneumatic tire | |
| AU2017216394B2 (en) | Improved pressure sensitive adhesive compositions | |
| KR102162852B1 (en) | Olefin block copolymer based pressure sensitive adhesives | |
| CN101111584B (en) | Adhesive composition | |
| JP2019508536A (en) | Film backing for peel removal installation | |
| EP3265527A1 (en) | Double coated tape | |
| CN108690540B (en) | Ultra-removable hot melt adhesive and labels containing it | |
| EP3622031A1 (en) | Adhesive tapes | |
| JP2001260262A (en) | Composite base and adhesive film | |
| JP4438435B2 (en) | Laminated body of thermoplastic sheet and elastomer adherend | |
| CN101198670A (en) | pressure sensitive adhesive | |
| JP2003292918A (en) | Adhesive composition for lapping use | |
| JP3994510B2 (en) | Adhesive composition for adhesive bonding of rubber and thermoplastic elastomer and adhesive sheet | |
| JP5097795B2 (en) | Stretch release tape | |
| JP2001294824A (en) | Adhesive tape for fixing goods | |
| JP2002097432A (en) | Adhesive composition | |
| CN119654378A (en) | Stabilized hot melt pressure sensitive adhesive | |
| JP3434399B2 (en) | Stretch film for food packaging | |
| JP2002030156A (en) | Resin molded product with adhesive sheet attached | |
| JPH10183082A (en) | Hot-melt adhesive composition for rubber bonding and bonding method | |
| JPH0711205A (en) | Adhesive composition and adhesive tape | |
| JP6760749B2 (en) | Chloroprene rubber latex adhesive composition | |
| JP3159940U (en) | Adhesive note |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20061207 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20090618 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090630 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090827 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20091215 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20091228 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130115 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4438435 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130115 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130115 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130115 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140115 Year of fee payment: 4 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |