JPS63207875A - Hot-melt tacky adhesive composition for sanitary material - Google Patents
Hot-melt tacky adhesive composition for sanitary materialInfo
- Publication number
- JPS63207875A JPS63207875A JP4019087A JP4019087A JPS63207875A JP S63207875 A JPS63207875 A JP S63207875A JP 4019087 A JP4019087 A JP 4019087A JP 4019087 A JP4019087 A JP 4019087A JP S63207875 A JPS63207875 A JP S63207875A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- butadiene
- vinyl aromatic
- weight
- vinyl
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 title claims description 10
- 230000001070 adhesive effect Effects 0.000 title abstract description 26
- 239000000853 adhesive Substances 0.000 title abstract description 24
- 239000012943 hotmelt Substances 0.000 title description 3
- 239000011347 resin Substances 0.000 claims abstract description 46
- 229920005989 resin Polymers 0.000 claims abstract description 46
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 29
- -1 vinyl aromatic hydrocarbon Chemical class 0.000 claims abstract description 22
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 21
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 19
- 239000003208 petroleum Substances 0.000 claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 150000003505 terpenes Chemical class 0.000 claims abstract description 6
- 235000007586 terpenes Nutrition 0.000 claims abstract description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 5
- 239000004831 Hot glue Substances 0.000 claims description 5
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 5
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 abstract description 14
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 150000002430 hydrocarbons Chemical class 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 15
- 230000014759 maintenance of location Effects 0.000 description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 9
- 238000002845 discoloration Methods 0.000 description 9
- 239000002390 adhesive tape Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 125000001741 organic sulfur group Chemical group 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- 239000004902 Softening Agent Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- HBGPNLPABVUVKZ-POTXQNELSA-N (1r,3as,4s,5ar,5br,7r,7ar,11ar,11br,13as,13br)-4,7-dihydroxy-3a,5a,5b,8,8,11a-hexamethyl-1-prop-1-en-2-yl-2,3,4,5,6,7,7a,10,11,11b,12,13,13a,13b-tetradecahydro-1h-cyclopenta[a]chrysen-9-one Chemical compound C([C@@]12C)CC(=O)C(C)(C)[C@@H]1[C@H](O)C[C@]([C@]1(C)C[C@@H]3O)(C)[C@@H]2CC[C@H]1[C@@H]1[C@]3(C)CC[C@H]1C(=C)C HBGPNLPABVUVKZ-POTXQNELSA-N 0.000 description 1
- PFRGGOIBYLYVKM-UHFFFAOYSA-N 15alpha-hydroxylup-20(29)-en-3-one Natural products CC(=C)C1CCC2(C)CC(O)C3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 PFRGGOIBYLYVKM-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 244000147058 Derris elliptica Species 0.000 description 1
- 241000628997 Flos Species 0.000 description 1
- SOKRNBGSNZXYIO-UHFFFAOYSA-N Resinone Natural products CC(=C)C1CCC2(C)C(O)CC3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 SOKRNBGSNZXYIO-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、初期積層性と剥離強さのバランスに優れ、か
つ、粘着剤自身の保油性、耐共気、耐熱変色特性に優れ
た粘着剤組成物に関し、特に衛生材料用に好適なホット
メルト粘ＳＩＩ剤組成物ン提供する。[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides an adhesive which has an excellent balance between initial lamination properties and peel strength, and which has excellent oil retention properties, synergism resistance, and heat discoloration resistance properties of the adhesive itself. The present invention relates to a hot melt viscous SII agent composition particularly suitable for sanitary materials.
衛生材料用ホットメルト粘着剤用途としてはナプキン固
定用両面テープが代赤的であり友。最近では、これに加
え紙おむつ用テープが急速な伸び′ンみせ、非常に太さ
なＮ蒙倉となっている。When it comes to hot melt adhesives for sanitary materials, double-sided tape for fixing napkins is the best choice. Recently, in addition to this, tape for disposable diapers has been growing rapidly and has become extremely thick.
従来、衛生材料用ホットメルト粘着剤は、共役ジエンと
ビニル芳香族系炭化水素から成ゐブロック共］Ｌ＠体乞
ベースに粘潰付与剤樹脂及び軟化剤等の配合＠が使用さ
れている。ブロック共１台体の具体例としては、ポリス
チレンーボリブタジェンブロック共Ｎ曾体あるいはポリ
スチレン−ポリインプレンブロック共重合体等が使用さ
れている。Conventionally, hot-melt adhesives for sanitary materials have been formulated with a block consisting of a conjugated diene and a vinyl aromatic hydrocarbon, and a base containing a viscosity-imparting resin, a softener, and the like. Specific examples of the block copolymer include a polystyrene-volibutadiene block copolymer or a polystyrene-polyinprene block copolymer.
粘着付与剤樹脂としては、ロジン系樹脂、テルペン系樹
脂、脂肪族系石油樹脂、芳香族系石油樹脂、脂環族系石
油樹脂等が使用されている。軟化剤としては、石油系軟
化剤、液状ゴム等が使用されていゐＯ
〔発明が解決しようとする間購点〕
衛生材料用帖着剤に要求される物性としては、初期粘着
性と剥離強さのバランスに優れ、保持力特性に唆れるご
と。ま几、粘着剤配付物に含まれている軟化剤＠−が接
層界面に移行し、剥離強さを低″Ｆさせ、紙おむつの場
合には、テープす゛れン起したりする場合がある。この
ため、粘着剤配付物自身の保油性が良く、軟化剤等の接
層界面への耐移行性に優れることが′必安である。ま几
、衛生用品に対する商品価値からＶ３漕剤配合物の耐熱
変色性、耐臭気特性にも優れることが必要とされている
。As the tackifier resin, rosin resin, terpene resin, aliphatic petroleum resin, aromatic petroleum resin, alicyclic petroleum resin, etc. are used. As the softening agent, petroleum-based softeners, liquid rubber, etc. are used. Excellent balance of strength and holding power. Otherwise, the softener contained in the adhesive may migrate to the contact interface, lowering the peel strength and causing tape smearing in the case of disposable diapers. For this reason, it is essential that the adhesive itself has good oil retention properties and excellent migration resistance of softeners, etc. to the contact interface. It is also necessary to have excellent heat resistance to discoloration and odor resistance.
しかしながら、従来のスチレンとブタジェンから成るブ
ロック共″Ｎ合体配＠物では、これらの性能（初期粘着
性、剥離強さ、保油性、耐熱変色性、耐臭気特性）乞同
時に満足しうるものは存在しなかった。However, conventional block co-N complexes made of styrene and butadiene cannot satisfy these properties (initial adhesion, peel strength, oil retention, heat discoloration resistance, and odor resistance) at the same time. I didn't.
また、スチレンとインプレンから凧るブロック共Ｘ台体
配合物についての試みもされてい、６が、初期粘着性と
剥＃＆強さのバランスは良いものの、保油性、耐熱変色
性、耐臭気性の点では者しく不充分なものであり九〇
以上の様に現状では、初期＃６漕性と剥離強さのバラン
スに優れ、かつ、粘着剤自身の保油性、臭気、耐熱変色
に優れた特性ン十分に満足するものはない。In addition, attempts have been made to develop a block co-X-base compound made from styrene and imprene, and although 6 has a good balance of initial adhesion, peel strength and strength, it has poor oil retention, heat discoloration resistance, and odor resistance. Currently, as shown in 90 and above, the adhesive has an excellent balance between initial #6 peeling properties and peel strength, and has excellent oil retention, odor, and heat discoloration resistance of the adhesive itself. None of the characteristics are completely satisfactory.
〔問題点Ｙ：解決するための：Ｐ段及び作用〕かかる現
状に鑑み、本発明者らはブタジェンとビニル芳香族炭化
水素からなるブロック共重合体と粘着付与剤樹脂及び酸
化防止剤ン配合しｔ帖増剤組成物の初期粘着性と剥離強
さのバランス、粘着剤自身の保油性、耐英気、１ａＩｔ
熱変色物性の改良について鋭意検討しｆｃ粕来、ビニル
芳香族炭化水素の含有量及びブタジェン部のビニル袖付
含有量かも定範囲であり、しかもそれらの関係が特定化
されたブタジェンとビニル芳香族炭化水素からなるブロ
ック共重合体及び特定の粘着付与剤樹脂さらに、特定の
酸化防止剤乞使用することにより七の目的が達成される
ことン見い出し、本発明ンな丁に至った。[Problem Y: To solve: P step and action] In view of the current situation, the present inventors have formulated a block copolymer consisting of butadiene and a vinyl aromatic hydrocarbon, a tackifier resin, and an antioxidant. Balance of initial tackiness and peel strength of T-sheet thickener composition, oil retention property of adhesive itself, resistance to corrosion, 1aIt
The improvement of the thermochromic physical properties was thoroughly studied, and the content of fc lees, vinyl aromatic hydrocarbon content, and vinyl sleeve content of the butadiene part were also within a certain range, and the relationship between them was specified.Butadiene and vinyl aromatic carbonization It has been discovered that the seven objects can be achieved by using a block copolymer consisting of hydrogen, a specific tackifier resin, and a specific antioxidant, and the present invention has been achieved.
即ち、本発明は、
ｔａｌ 少なくとも１つのビニル芳香族炭化水素Ｙ主
とする１＠体ブロックと少なくとも１つのブタジェンχ
主とする重合体ブロックから成り、（イ） ビニル芳香
族炭化水素の含有量〔Ｓ〕が１０〜３０１童係
（ロ） ブタジェン部のビニル結付含有量〔Ｖ）が２０
〜５０％
Ｈ上記のビニル芳香族炭化水系の含有量〔８〕とブタジ
ェンｂのビニル結合金有量〔Ｖ〕との関係が下式を満足
する
４０≦ＣＥ３］ ＋ （Ｖ’ｌ≦ｑＯ
ブロック共重曾体 弁型 １００！重都（ｂ）水添ロ
ジン系樹脂、テルペン系樹脂 Ｃ５・ｃ９系脂肪族芳香
族系共重合石油樹脂、脂環族系石油樹脂の一櫨又は二種
以上ン含む粘着付与剤樹脂
４０へ２ＣＪＯ重１１部ｔｃ＋ 少なくとも２
個以上の芳香族＃Ｌン頁するフェノール系一次酸化防止
剤 ０．３〜３．５ｍｔ部からなる衛生材料用ホット
メルト粘漕剤組底物に閑する。That is, the present invention provides tal at least one vinyl aromatic hydrocarbon Y-based 1@ block and at least one butadiene χ
(a) The vinyl aromatic hydrocarbon content [S] is 10 to 301 (b) The vinyl bond content [V] of the butadiene moiety is 20
~50% H The relationship between the above vinyl aromatic hydrocarbon content [8] and the vinyl bond content [V] of butadiene b satisfies the following formula 40≦CE3] + (V'l≦qO block Copolymer Valve type 100! Juto (b) Hydrogenated rosin resin, terpene resin C5/C9 aliphatic aromatic copolymerized petroleum resin, alicyclic petroleum resin one or more types Contains tackifier resin
40 to 2CJO weight 11 parts tc+ at least 2
A hot-melt viscosifier for sanitary materials consisting of 0.3 to 3.5 mt of a phenolic primary antioxidant containing at least 100 aromatic compounds is used.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明で使用する成分（ａｌのブロック共重合体は、少
なくとも１つ、好ましくは２個以上のビニル芳香族炭化
水素を主とする重合体ブロックと少なくとも１つのブタ
ジェン乞主とする重合体ブロックから成る。ビニル芳香
秩炭化水木ン主とて６１合体ブロックとはビニル芳香族
炭化水系ン５ｏ重賃係以上含有するビニル芳香族炭化水
素とブタジェンとの共１合体ブロック及び／又はビニル
芳香族炭化水素単独重合体ブロックを示し、ブタジェン
部主とする重合体ブロックとはブタジェン’２５０Ｂｉ
ｔ％ケ超える童で官有するブタジェンとビニル芳香族炭
化水素との共重合体ブロック及び／又はブタジェン単独
重合体ブロックン示す。共１！合体ブロック中のビニル
芳香族炭化水素は均一に分布していても、又テーパー状
に分布していてもよい。The component (Al block copolymer) used in the present invention is composed of at least one, preferably two or more vinyl aromatic hydrocarbon-based polymer blocks and at least one butadiene-based polymer block. Vinyl aromatic hydrocarbons mainly consist of a 61-unit block, which is a co-unit block of vinyl aromatic hydrocarbons and butadiene containing 50% or more of vinyl aromatic hydrocarbons, and/or vinyl aromatic hydrocarbons. It shows a homopolymer block, and the polymer block mainly consisting of butadiene moieties is Butadiene '250Bi.
Indicates a copolymer block of butadiene and a vinyl aromatic hydrocarbon and/or a butadiene homopolymer block containing more than t%. 1 together! The vinyl aromatic hydrocarbons in the combined block may be uniformly distributed or tapered.
均一に分布し７１ｉＨ）分及び／又はテーパー状に分布
したｂ分は谷ブロック中に！！数個共存してもよい。Uniformly distributed 71iH) minutes and/or tapered distributed b minutes in the valley block! ! Several may coexist.
本発明のポリマーの特徴は１．成分子ａｔのブロック共
重合体のビニル芳香族炭化水素の含有量〔１３）が１０
〜６０重′ｊｔ％、好ましくは１５〜２５憲１ｉ％テア
リ、ブタジェン部のビニル結合含有量〔Ｖ］が２０〜５
０％、好ましくは２５〜４５％、東に好ましくは６０〜
４０％であり、かつ［８）と（Ｖ〕との関係が下式
％式％
の関係χ満足するブロック共重合体であることである。The features of the polymer of the present invention are 1. The vinyl aromatic hydrocarbon content [13) of the block copolymer of component element at is 10
~60 wt%, preferably 15-25 wt%, and the vinyl bond content [V] of the butadiene moiety is 20-5
0%, preferably 25-45%, preferably 60-45%
40%, and the relationship between [8] and (V) satisfies the relationship χ of the following formula %.
（８〕及び（Ｖ） Ｏ含有量、Ｃ８〕＋ ＥＶ） ノｙ
Ｍ９Ｆ。(8] and (V) O content, C8] + EV) Noy
M9F.
が上記の記載の範囲ン満足しないときは初Ｘｊｌ＋増性
、接着力、耐クリープ特性のバランスに浚れ几組底物か
得られない。ま六、保油性も良くない。If the above-mentioned range is not satisfied, it is not possible to obtain a dredged and assembled bottom product with a balance of initial Xjl + increase strength, adhesive strength, and creep resistance properties. Maroku, oil retention is also not good.
本発明で用いるビニル芳香族炭化水素としてはスチレン
、０−メチルスチレン、ｐ−メチルスチレン、α−メチ
ルスチレン、などがあるが、物に一般的なものとしては
スチレンか挙げられる。これらは１種のみならず２種以
上乞混合して使用してもよい。Vinyl aromatic hydrocarbons used in the present invention include styrene, 0-methylstyrene, p-methylstyrene, α-methylstyrene, and the most commonly used one is styrene. These may be used not only alone, but also as a mixture of two or more.
本発明においては、ポリマー構造が、−齢式、（Ａ−Ｂ
）ｎ＋ ＊＋Ｂ−Ａ）ｎ＊ Ｂ＋Ａ−Ｃ３）ｎ（上
式において、Ａはビニル芳香族炭化水素χ主とする１１
合体ブロックであり、Ｂは共役ジエン馨主とする＊＠体
デブロックある。Ａブロックとブロックとの境界は必す
しも明瞭に区別される必安はない。又、ｎは１以上の整
叡である。〕で表される＆状ブロック共ｎｏ体、或いは
一斂式、Ｃ（＝Ｂ−Ａ）→−−−ｘ、〔（Ａ−Ｂ）ｎ→
ｍ＋２ ｘｎ ｍ＋２
（（Ｂ−Ａ−）−ＨＢ十ｍ＋２ ｘ’
Ｃ（Ａ−ＢガＡ＋ｉ丁Ｘ。In the present invention, the polymer structure has the -age formula, (A-B
)n+ *+B-A)n*B+A-C3)n (In the above formula, A is mainly vinyl aromatic hydrocarbon χ11
It is a combined block, and B is a *@body deblock where B is the conjugate diene master. The boundary between the A block and the block does not necessarily need to be clearly distinguished. Further, n is an integer of 1 or more. ] An &-shaped block conjugate, or a single convergence expression, C(=B-A)→---x, [(A-B)n→
m+2 xn m+2 ((B-A-)-HB10m+2 x' C(A-BgaA+i-choX.
（上式において、Ａ、Ｂは前記と同じであり、Ｘは多官
能有機リチウム化付物等の開始剤ン示す。ｍ及びｎは１
以上の整数である。〕で表すれるラジアルブロック共重
合体乞使用することができる。本発明で使用するブロッ
ク共Ｎ、合体は上記一般式で表されるブロック共重合体
の任意の混／＠物でもよい。(In the above formula, A and B are the same as above, and X represents an initiator such as a polyfunctional organic lithiated adduct. m and n are 1
is an integer greater than or equal to ] can be used. The block copolymer used in the present invention may be any mixture of block copolymers represented by the above general formula.
本発明で使用されるブロック共重合体の好適なものはメ
ルトフロー（温度２ＬｌＯ℃、加重５榴）が０．５〜５
０ｇ７１０ｍ１ｎ％好ましくは１１−３ｔ）／１０ｍ１
ｎのものである。メルトフローが０．５ｇ／ｌＱｍｉｎ
未鷹になると粘層剤組成物の粘度が高くなりテープ等へ
の塗布性能が低下する傾向がみられる。又メルトフロー
が５Ｌ）ｇ／１０ｍ１ｎ乞超えると耐クリープ特性が低
下する傾向がみられる。A preferable block copolymer used in the present invention has a melt flow (temperature of 2LIO℃, weight of 50℃) of 0.5 to 5.
0g710m1n% preferably 11-3t)/10m1
It is of n. Melt flow is 0.5g/lQmin
When it becomes too thick, the viscosity of the thickening agent composition tends to increase and the coating performance on tapes etc. tends to deteriorate. Furthermore, when the melt flow exceeds 5 L) g/10 ml, the creep resistance tends to deteriorate.
本発明で使用する成分（ｔ）ｌの粘着付与剤樹脂は、水
添ロジン系樹脂、テルペン系樹脂、Ｃ５・Ｃ９系脂肪族
芳香族系共蔦合石油樹脂、側塊族系石油樹脂である。こ
れらの具体例としては、水冷ロジン系樹脂では、Ｆｏｒ
ａｌ ８５ （Ｈｅｒｃｕｌｅｓ社製〕、テルペン系樹
脂では、ＹＳレジンＴｏ−１０５（安原油脂社製）、Ｃ
５・Ｃ９系脂肪族芳香族系共１合石油樹ｊ＆では１．エ
スコレツツ２１０１ （エツソ化学社製）、フィントン
Ｇ−１００・フィントンＵ−１８５（日本ゼオン社シ）
、側塊族系石油樹脂では、アルコンｕ−９０（荒用化学
社製）等が挙げられ、いずれも初期粘着性と剥離強さと
のバランスに優れ、かつ、保油性、臭気に悪ｔｅ＊Ｙ及
ぼさない組成物が得られる。これらは１ｍのみならず２
′！ａ以上ン混合して使用しても良い。ごのうち、脣に
好ましくはＣｌ５− Ｃ，、系脂肪族芳香族系共′３１
＠石油樹脂であり、例えはフィントンＵ−１８５は初期
粘着性と剥離強さのバランスに優れ、かつ、保油性、耐
熱色物性、臭気にも優れ九組成物が得られる。The tackifier resin of component (t)l used in the present invention is a hydrogenated rosin resin, a terpene resin, a C5/C9 aliphatic aromatic co-polymerized petroleum resin, or a side block petroleum resin. . Specific examples of these include water-cooled rosin resins such as For
al 85 (manufactured by Hercules), terpene-based resins include YS resin To-105 (manufactured by Yasuyu Co., Ltd.), C
5/C9 aliphatic aromatic type oil tree j & 1. Escorets 2101 (manufactured by Etsuo Kagaku Co., Ltd.), Finton G-100/Finton U-185 (manufactured by Zeon Corporation)
, Alcon U-90 (manufactured by Arayo Kagaku Co., Ltd.) is an example of side block type petroleum resins, and all of them have an excellent balance between initial adhesion and peel strength, and have good oil retention and odor. A composition is obtained that does not affect These are not only 1m but also 2m
′! You may use a mixture of more than a. Of these, Cl5-C, aliphatic, aromatic, and
@Petroleum resin, for example Finton U-185, has an excellent balance between initial tackiness and peel strength, and also has excellent oil retention, heat-resistant color properties, and odor, resulting in a composition.
上記以外の粘着付与剤樹脂、例えは０５糸脂肪族系石油
樹脂、Ｃ９糸芳香族石油樹脂では、初期粘着性、剥離強
さに劣り、好ましくない。Tackifier resins other than those mentioned above, such as 05 thread aliphatic petroleum resin and C9 thread aromatic petroleum resin, are not preferred because they have poor initial tackiness and peel strength.
本発明において成分子ｔ）ｌの粘着付与剤樹脂は、成分
ｔａ）のブロック共重合体１００重Ｊｌｆｔｌｉに対し
て、４０〜２００盲童部、好ましくは６０〜１５０の範
囲で使用される。粘着付与剤樹脂の配＠量がごの範囲外
であると得られる粘接着剤ｍ成＠ン用いた衛生材料の粘
＊Ｗ性が悪く好ましくない。In the present invention, the tackifier resin of component t)l is used in an amount of 40 to 200 parts, preferably 60 to 150 parts per 100 parts of the block copolymer of component ta). If the amount of the tackifier resin is outside the specified range, the viscosity of the resulting sanitary material using the adhesive agent will be poor, which is undesirable.
本発明で使用する成分ｔｃｌの欧化防止剤は粘着剤配合
物に漕色しないごとが必要で少なくとも２個以上の芳香
族環ン有するフェノール系−吹酸化防止剤が必女であり
、又、必要に応じて有機イオク系二送酸化防止剤ン併用
しても艮い。有機イオウ糸二送酸化防止剤ン併用する場
合は、成分子＆ｌのブロック共貞曾体１ｏｏｘｉｉｍに
対して、フェノール系−吹酸化防止剤は（Ｊ、３１Ｋｔ
部以上、有機イオウ系二次酸化防止剤は２．５１童部以
下・、かつ、フェノール系−吹酸化防止剤と有機イオウ
糸二次酸化防止剤の＠耐ｆｉが６．５重量部身心の範囲
で使用される。具体的には、フェノール系−吹酸化防止
剤としては、ペンタエリチリトルーテトラキス−（６，
５−シーｔ、ｅｒｔ−ブナルー４−ハイドロキシハイド
ロンンナメート）、２ｔａｒｔ−ブチル−６−（３’−
ｔ、ｅｒｔ−ブチル−５′−メチル−２′−ハイドロキ
シベンジ／ｌ／ ） −４−メチルフェニルアクリレー
ト等であり、π機イオウ系二次酸化防止剤としては、ペ
ンタエリチリトルーテトラキス−（β−ラウリル−チオ
プロピオネート）、ジステアリル、−３、３’−チオジ
プロぎオネート等であり、これらの級化防止剤ン使用し
た粘着剤組成物は溶融状態に於て、長時間加熱によって
も、粘度及び゛性能の安定性に優れ、かつ、臭気が殆ど
なく、変色も見られない。本発明以外の酸化防止剤、例
えは、２，６−シーｔｅｒｔ−ブチル−４−メテルーフ
ェノールン使用した粘着剤組成物では、始融状懇に於て
、短時間で変色し、刺激臭があり、好ましくない。The TCL component used in the present invention is required to prevent color discoloration in the adhesive formulation, and a phenolic-blown antioxidant having at least two or more aromatic rings is required. Depending on the situation, it may also be used in combination with organic ion-based antioxidants. When using an organic sulfur-based antioxidant in combination, the phenolic-based antioxidant is (J, 31Kt) for each block of the component &l.
The organic sulfur-based secondary antioxidant is 2.51 parts by weight or less, and the phenolic-blown antioxidant and the organic sulfur thread secondary antioxidant have a fi of 6.5 parts by weight. used in range. Specifically, as a phenolic-blown antioxidant, pentaerythritol-tetrakis-(6,
5-sheet t, ert-bunaru-4-hydroxyhydronnamate), 2t-butyl-6-(3'-
t, ert-butyl-5'-methyl-2'-hydroxybendi/l/)-4-methylphenylacrylate, etc., and as a π-organic sulfur-based secondary antioxidant, pentaerythritryl-tetrakis-(β -lauryl-thiopropionate), distearyl, -3,3'-thiodipropionate, etc., and adhesive compositions using these anti-grading agents can be used in a molten state even when heated for a long time. It has excellent stability in viscosity and performance, has almost no odor, and shows no discoloration. Adhesive compositions using antioxidants other than those of the present invention, such as 2,6-tert-butyl-4-meterphenol, change color in a short period of time and have a pungent odor. This is not desirable.
本発明において、取分ｔＣ）の酸化防止剤は、成分子ａ
ｌのブロック共１合体１ｏｏ！［４に対して、０．３〜
３．５重量部、好ましくは０．５〜２．５ｆＬｋ齢の範
囲で使用される。酸化防止剤の配合量が０．３重量部未
満だと熱安定性の効果が見られず、６．５重量部ン超え
ると祷られる粘着剤組成物乞用い几衛生材料の粘着特性
が劣り、ま九、長時間加熱時の臭気が多くなるため好ま
しくない。In the present invention, the antioxidant of fraction tC) is the component a
The blocks of l are combined into 1oo! [0.3 to 4
It is used in an amount of 3.5 parts by weight, preferably in the range of 0.5 to 2.5 fLk age. If the amount of antioxidant is less than 0.3 parts by weight, no thermal stability effect will be observed, and if it exceeds 6.5 parts by weight, the adhesive properties of the adhesive composition used for sanitary materials will be poor. Ninth, it is not preferable because it produces a lot of odor when heated for a long time.
本発明においては必要に応じて軟化剤（成分（ｄ））Ｙ
使用できる。成分ｔ（１１の軟化剤は、石油系軟化剤、
パラフィン等である。In the present invention, softening agent (component (d)) Y
Can be used. Component t (the softener in 11 is a petroleum-based softener,
Paraffin, etc.
成分（ｄｉの軟化剤は、一般に成分（ａ）のブロック共
Ｎ曾体１００重′１に郁に対して１５０１量部以下、好
ましくは５〜１００重Ｊｉ部の範囲で使用される。The softener component (di) is generally used in an amount of 1,501 parts by weight or less, preferably from 5 to 100 parts by weight, based on 100 parts by weight of the block compound (a).
１５■１％ン超えると得られる粘着剤組成物を用いた衛
生材料の粘着物性及び保油性、臭気の点で著しく劣るた
め好ましくない。If it exceeds 15.1%, sanitary materials using the resulting adhesive composition will be significantly inferior in terms of adhesive properties, oil retention, and odor, which is not preferred.
本発明の粘着剤組成物は初期粘着性、剥離強さ、保油性
に優゛れ、高崗で長時間放置しても熱劣化が起りにくり
、変色、刺激臭の発生かないことから物に衛生材料用ホ
ットメルト粘着剤として有効である。The adhesive composition of the present invention has excellent initial tackiness, peel strength, and oil retention, and is resistant to thermal deterioration even when left on high surfaces for a long time, and does not cause discoloration or irritating odor, making it useful for objects. Effective as a hot melt adhesive for sanitary materials.
以１に実施例ン示すか、これ等は本発明を代表するもの
であり、本発明の範囲ン制限するものではない。The following examples are representative of the present invention and are not intended to limit the scope of the present invention.
実施例１〜４及び比較例１
第１表に示したＡ−Ｂ−Ａ構造ｙａ′有するスチレン／
ブタジェンブロック共Ｎ合体（分子量は、メルトフロー
が約５ｇ／ｌ［］ｍｉｎになる様に調整し友ン各１’Ｏ
Ｏｍ＆ｉＬ部に対して粘着付与剤樹脂（フィントンＵ−
１８５、日本ゼオン社ａ）１０［Ｊ重ＪＬｆｔＬナフテ
ン系フロセス油（ソニックプロセスオイルＲ−２００ｓ
協同石油製）３０重量部、安定剤（スミライず−ＧＭ、
住友化学社１）ＩＪｆｉ部ン配合してホットメルト粘着
剤組成物７作製したＯ
この様にして製遺した粘着剤組成物乞ポリエステルフィ
ルムにそれぞれ塗布して紙おＣつを想定したベルト部゛
粘着テープン作取し、次の様な性能評価ン行った。初期
粘着性は、７． ＤＯＷ法（Ｐｒｏｃ。Examples 1 to 4 and Comparative Example 1 Styrene having the A-B-A structure ya' shown in Table 1/
Butadiene block co-N coalescence (molecular weight was adjusted so that the melt flow was approximately 5 g/l[]min, and each 1'O
Tackifier resin (Finton U-
185, Nippon Zeon Co., Ltd. a) 10 [J Heavy JLftL Naphthenic Floss Oil (Sonic Process Oil R-200s
Kyodo Oil) 30 parts by weight, stabilizer (Sumiraizu-GM,
Sumitomo Chemical Co., Ltd. 1) A hot melt adhesive composition 7 was prepared by blending the IJfi part. The adhesive composition thus prepared was applied to a polyester film respectively to form a belt part, which was assumed to be a paper tray. Adhesive tape was prepared and the following performance evaluation was performed. Initial tackiness is 7. DOW method (Proc.
工ｎｓｔ、 Ｒｕｂ、工ｎｄ、、 １．１ （Ｊ５ （
ｌ ９５４ ） 〕に準じ、傾斜６０度のステンレス板
上の斜面に長さＩＤｃｍの粘着テープを貼りつけ、テー
プ上端から上方１ｏｃｍの斜面位置より直径１／３イン
チから１インチまでの６２種類の太ぎさのステンレス製
ボ−ルン初速度りでころがして粘泄テープ上で停止する
最大径の球の太きさで表示し几。剥離強さはＪ工Ｓ Ｚ
−１５２２ｉＣ準じ、ステンレス板ニ巾２５１×長さ
１００門として積層テープン貼り付け、２６６Ｃにおい
て３ Ｑ Ｑ ａｍ ／ ｍｉｎ、の速度で１８０度の
方向に剥離して測定した。耐クリープ特性はＪ工ｓ
ｚ−１５２４に準じ、ステンレス板に２５■×２５酊の
面積が接するように粘着テープン貼ジ付け、６０°Ｃに
おいて１的の荷重ビ加えて粘溜テープがすれ落ちるまで
の時間ン測定した。保油性はＪ工５Ａ−５７５７に準じ
、ガラス板上にｙ工５Ｐ−３８０１に規定するろ紙ン５
枚蔦ね１さらに高さ１２朋、内径６５龍、厚さ２１ｕＩ
のリングに粘看剤ｋｒｆ、、物乞光てんしたものン、ろ
紙の上に瓢ぎ、１０００Ｃ，３３６時間後の軟化剤等の
しみこんだろ紙の枚数ン数え次。臭気は、粘着剤組成＠
’１２００℃のイヤーオーブンの中に入れ、２時間後取
出し、２０人の感応テストにより臭気判定ン行い、刺激
臭か強くなるほど数値χ大とし１〜５の５段階表示とじ
几。これらの２０人の平均で表わした。粘着剤配合物の
色調変化については、臭気テストと同条件でイヤーオー
ブンの中に粘着剤Ｍｉｄ＠χ入れ、取出し後の色χ観察
し几。Engineering nst, Rub, Engineering nd,, 1.1 (J5 (
954)], adhesive tape with a length ID cm is pasted on the slope of a stainless steel plate with an inclination of 60 degrees, and 62 different thicknesses from 1/3 inch to 1 inch in diameter are attached from the slope position 1 oc above the top of the tape. It is indicated by the thickness of the largest diameter ball that is rolled at the initial speed of Gisa's stainless steel ball and stopped on the tape. Peel strength is J Engineering S Z
-1522iC, a stainless steel plate with a width of 251 x a length of 100 pieces was attached with laminated tape, and measured by peeling in a direction of 180 degrees at a speed of 3 Q Q am / min at 266C. Creep resistance characteristics are J.
According to Z-1524, an adhesive tape was pasted on a stainless steel plate so that an area of 25 cm x 25 cm was in contact with the adhesive tape, and a load of 1 cm was applied at 60°C, and the time required for the adhesive tape to slip off was measured. Oil retention is in accordance with J-5A-5757, and a filter paper specified in Y-5P-3801 is placed on a glass plate.
Hiratune 1, height 12 mm, inner diameter 65 mm, thickness 21 uI
Put the sticky agent KRF in the ring, put it on the filter paper, count the number of sheets of filter paper soaked with softener etc. after 1000C and 336 hours. The odor depends on the adhesive composition @
Put it in an ear oven at 1200℃, take it out after 2 hours, and conduct a sensitivity test on 20 people to determine the odor. It is expressed as the average of these 20 people. Regarding the color change of the adhesive formulation, we put the adhesive Mid@χ into the ear oven under the same conditions as the odor test and observed the color χ after taking it out.
これら−結果１４４１弄に示しｆｃか本発明で規定する
ブロック弁型せ体、ｖｌＩＳ着付与剤樹脂、酸化防止剤
χ使用し九粘漕剤組成物は良好な初期粘漕性、剥離強さ
、保油性、臭気、耐熱変色物性ン示すことがわかる。The results shown in Table 1441 show that the 9 viscosity agent composition using the block valve type body specified in the present invention, the vlIS adhesion agent resin, and the antioxidant χ has good initial viscosity, peel strength, It can be seen that oil retention, odor, and heat discoloration resistance are exhibited.
（以下余白）
実施例５〜８及び比較例２〜５
粘着付与剤樹脂のａｉａ、粘着付与剤樹脂及び軟化剤の
配合量Ｘ第２表に示され友様に変更する以外は、実施例
１と同様の方法で粘着剤組成物７作製し、七の性能Ｘ評
価し友。(Leaving space below) Examples 5 to 8 and Comparative Examples 2 to 5 Example 1 except for changing the aia of the tackifier resin, the blending amount of the tackifier resin and the softener X as shown in Table 2. Adhesive composition 7 was prepared in the same manner as above, and the performance of 7 was evaluated.
結果ン第２表に示したが本発明で規定する粘着付与剤樹
脂Ｘ使用し７ｔｔ’＋Ｓ着剤組成物は良好な各特性ン示
し、物に初期粘着物性に優れることがわかる。The results are shown in Table 2, and it can be seen that the 7tt'+S adhesive composition using the tackifier resin X defined in the present invention exhibited good properties and was excellent in initial adhesive properties.
（以下余白）
（注−１） Ｆｏｒａｌ ３５ （Ｈｅｒｃｕｌｅｓ
社製）ン使用
（注−２） ＹＩ９レジンＴ○−１０５〔安原油脂社
製〕ン使用
（注−６） フィントンＤ−１００（日本ゼオン社製）
χ使用
（注−４） ハイレジン＃９ｏ（東邦石油化学社裂）ン
使用
（注−５） フィントンＵ−１８５（日本ゼオン社製）
ン使用
実施例９〜１１及び比較例６〜８
酸化防止剤のａＩ類及び配付ｉｋン第６表に示され文様
に変更する以外は、実施例１と同様の方法で粘瀦剤組取
＠ン作製し、七の性能ン評価し次。第６衣の結果かられ
かる様に、本発明で規定する酸化防止剤ン使用し友粘看
剤組成物は、特に耐臭気、色物性に優れる。(Left below) (Note-1) Foral 35 (Hercules
(Note 2) Uses YI9 resin T○-105 (manufactured by Yasuyuki Co., Ltd.) (Note 6) Finton D-100 (manufactured by Nippon Zeon Co., Ltd.)
Using χ (Note-4) Using Hi-Resin #9o (Toho Petrochemical Co., Ltd.) (Note-5) Finton U-185 (manufactured by Nippon Zeon Co., Ltd.)
Examples 9 to 11 and Comparative Examples 6 to 8 Antioxidant aI and distribution The thickening agent was assembled in the same manner as in Example 1, except for changing the pattern shown in Table 6. The performance of seven samples was then fabricated and evaluated. As can be seen from the results of No. 6, the adhesive composition using the antioxidant specified in the present invention is particularly excellent in odor resistance and color properties.
（注−６） 住友化学社製ン使用 （注−７） 同 上(Note-6) Used by Sumitomo Chemical Co., Ltd. (Note-7) Same as above
Claims (1)
る重合体ブロックと少なくとも１つのブタジエンを主と
する重合体ブロックから成り、 （イ）ビニル芳香族炭化水素の含有量〔Ｓ〕が１０〜３
０重量％ （ロ）ブタジエン部のビニル結合含有量〔Ｖ〕が２０〜
５０％ （ハ）上記のビニル芳香族炭化水素の含有量〔Ｓ〕とブ
タジエン部のビニル結合含有量〔Ｖ〕との関係が下式を
満足する ４０≦〔Ｓ〕＋〔Ｖ〕≦７０ ブロック共重合体１００重量部 （ｂ）水添ロジン系樹脂、テルペン系樹脂、Ｃ＿５・Ｃ
＿９系脂肪族芳香族系共重合石油樹脂、脂環族系石油樹
脂の一種又は二種以上を含む粘着付与剤樹脂４０〜２０
０重量部 （ｃ）少なくとも２個以上の芳香族環を有するフェノー
ル系一次酸化防止剤０．３〜３．５重量部からなる衛生
材料用ホットメルト粘着剤組成物[Scope of Claims] (a) Consisting of at least one polymer block mainly composed of vinyl aromatic hydrocarbons and at least one polymer block mainly composed of butadiene, (b) Content of vinyl aromatic hydrocarbons [S] is 10-3
0% by weight (b) The vinyl bond content [V] of the butadiene part is 20~
50% (c) 40≦[S]+[V]≦70 blocks in which the relationship between the vinyl aromatic hydrocarbon content [S] and the vinyl bond content [V] of the butadiene moiety satisfies the following formula: 100 parts by weight of copolymer (b) Hydrogenated rosin resin, terpene resin, C_5・C
Tackifier resin 40 to 20 containing one or more types of _9 aliphatic aromatic copolymerized petroleum resin and alicyclic petroleum resin
0 parts by weight (c) A hot melt adhesive composition for sanitary materials comprising 0.3 to 3.5 parts by weight of a phenolic primary antioxidant having at least two or more aromatic rings.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4019087A JPS63207875A (en) | 1987-02-25 | 1987-02-25 | Hot-melt tacky adhesive composition for sanitary material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4019087A JPS63207875A (en) | 1987-02-25 | 1987-02-25 | Hot-melt tacky adhesive composition for sanitary material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63207875A true JPS63207875A (en) | 1988-08-29 |
Family
ID=12573855
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4019087A Pending JPS63207875A (en) | 1987-02-25 | 1987-02-25 | Hot-melt tacky adhesive composition for sanitary material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63207875A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02240185A (en) * | 1989-03-14 | 1990-09-25 | Nitto Denko Corp | Self-adhesive pressure-sensitive adhesive and adhesive member thereof |
| JPH04153288A (en) * | 1990-10-16 | 1992-05-26 | Nitta Gelatin Inc | Self-adhesive composition for sanitary goods, and sanitary napkin |
| US5250389A (en) * | 1991-02-15 | 1993-10-05 | Asahi Kasei Kogyo Kabushiki Kaisha | Photosensitive elastomer composition |
| JP2007517099A (en) * | 2003-12-31 | 2007-06-28 | クレイトン・ポリマーズ・リサーチ・ベー・ベー | Low viscosity, hot-melt stable adhesive composition |
| JP2007523244A (en) * | 2004-02-19 | 2007-08-16 | クレイトン・ポリマーズ・リサーチ・ベー・ベー | Low viscosity hot melt adhesive composition for nonwoven articles |
| JP2007530714A (en) * | 2004-02-19 | 2007-11-01 | クレイトン・ポリマーズ・リサーチ・ベー・ベー | Hot melt adhesive composition for nonwoven fabric |
| JP2009280824A (en) * | 2001-01-18 | 2009-12-03 | Kraton Polymers Research Bv | Adhesive composition |
| JP2023000196A (en) * | 2021-06-17 | 2023-01-04 | 積水フーラー株式会社 | Hot-melt adhesive |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6327573A (en) * | 1986-07-21 | 1988-02-05 | Asahi Chem Ind Co Ltd | Adhesive composition |
-
1987
- 1987-02-25 JP JP4019087A patent/JPS63207875A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6327573A (en) * | 1986-07-21 | 1988-02-05 | Asahi Chem Ind Co Ltd | Adhesive composition |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02240185A (en) * | 1989-03-14 | 1990-09-25 | Nitto Denko Corp | Self-adhesive pressure-sensitive adhesive and adhesive member thereof |
| JPH04153288A (en) * | 1990-10-16 | 1992-05-26 | Nitta Gelatin Inc | Self-adhesive composition for sanitary goods, and sanitary napkin |
| JPH0681830B2 (en) * | 1990-10-16 | 1994-10-19 | 新田ゼラチン株式会社 | Adhesive composition for sanitary products and sanitary napkin |
| US5250389A (en) * | 1991-02-15 | 1993-10-05 | Asahi Kasei Kogyo Kabushiki Kaisha | Photosensitive elastomer composition |
| JP2009280824A (en) * | 2001-01-18 | 2009-12-03 | Kraton Polymers Research Bv | Adhesive composition |
| JP2007517099A (en) * | 2003-12-31 | 2007-06-28 | クレイトン・ポリマーズ・リサーチ・ベー・ベー | Low viscosity, hot-melt stable adhesive composition |
| JP2007523244A (en) * | 2004-02-19 | 2007-08-16 | クレイトン・ポリマーズ・リサーチ・ベー・ベー | Low viscosity hot melt adhesive composition for nonwoven articles |
| JP2007530714A (en) * | 2004-02-19 | 2007-11-01 | クレイトン・ポリマーズ・リサーチ・ベー・ベー | Hot melt adhesive composition for nonwoven fabric |
| JP2023000196A (en) * | 2021-06-17 | 2023-01-04 | 積水フーラー株式会社 | Hot-melt adhesive |
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