JP5553982B2 - Chloroprene rubber latex adhesive composition - Google Patents
Chloroprene rubber latex adhesive composition Download PDFInfo
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- JP5553982B2 JP5553982B2 JP2008254866A JP2008254866A JP5553982B2 JP 5553982 B2 JP5553982 B2 JP 5553982B2 JP 2008254866 A JP2008254866 A JP 2008254866A JP 2008254866 A JP2008254866 A JP 2008254866A JP 5553982 B2 JP5553982 B2 JP 5553982B2
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- rubber latex
- chloroprene rubber
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- 229920000126 latex Polymers 0.000 title claims description 38
- 239000004816 latex Substances 0.000 title claims description 37
- 229920001084 poly(chloroprene) Polymers 0.000 title claims description 37
- 239000000853 adhesive Substances 0.000 title claims description 28
- 230000001070 adhesive effect Effects 0.000 title claims description 28
- 239000000203 mixture Substances 0.000 title claims description 17
- 239000011347 resin Substances 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 21
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 10
- 229920000098 polyolefin Polymers 0.000 claims description 9
- 239000004014 plasticizer Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000012190 activator Substances 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229920005672 polyolefin resin Polymers 0.000 claims description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000003208 petroleum Substances 0.000 description 7
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 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 description 6
- 150000003505 terpenes Chemical class 0.000 description 6
- 235000007586 terpenes Nutrition 0.000 description 6
- 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 description 6
- -1 glycerin ester Chemical class 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- KESQFSZFUCZCEI-UHFFFAOYSA-N 2-(5-nitropyridin-2-yl)oxyethanol Chemical compound OCCOC1=CC=C([N+]([O-])=O)C=N1 KESQFSZFUCZCEI-UHFFFAOYSA-N 0.000 description 1
- IHLDEDLAZNFOJB-UHFFFAOYSA-N 6-octoxy-6-oxohexanoic acid Chemical compound CCCCCCCCOC(=O)CCCCC(O)=O IHLDEDLAZNFOJB-UHFFFAOYSA-N 0.000 description 1
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- 240000000972 Agathis dammara Species 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 239000004859 Copal Substances 0.000 description 1
- 229920002871 Dammar gum Polymers 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- XTJFFFGAUHQWII-UHFFFAOYSA-N Dibutyl adipate Chemical compound CCCCOC(=O)CCCCC(=O)OCCCC XTJFFFGAUHQWII-UHFFFAOYSA-N 0.000 description 1
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 1
- VIZORQUEIQEFRT-UHFFFAOYSA-N Diethyl adipate Chemical compound CCOC(=O)CCCCC(=O)OCC VIZORQUEIQEFRT-UHFFFAOYSA-N 0.000 description 1
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 241000782205 Guibourtia conjugata Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920001800 Shellac Polymers 0.000 description 1
- 229920004411 Skyprene® Polymers 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- XTTFBGOZENFIAM-UHFFFAOYSA-N bis(2-ethylhexyl) (Z)-but-2-enedioate dibutyl (Z)-but-2-enedioate Chemical compound C(C=C/C(=O)OCCCC)(=O)OCCCC.C(C=C/C(=O)OCC(CCCC)CC)(=O)OCC(CCCC)CC XTTFBGOZENFIAM-UHFFFAOYSA-N 0.000 description 1
- MTPSFISGWJGUGN-UHFFFAOYSA-N bis(2-ethylhexyl) dodecanedioate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCCCC(=O)OCC(CC)CCCC MTPSFISGWJGUGN-UHFFFAOYSA-N 0.000 description 1
- ZDWGXBPVPXVXMQ-UHFFFAOYSA-N bis(2-ethylhexyl) nonanedioate Chemical compound CCCCC(CC)COC(=O)CCCCCCCC(=O)OCC(CC)CCCC ZDWGXBPVPXVXMQ-UHFFFAOYSA-N 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- RSRICHZMFPHXLE-AATRIKPKSA-N bis(2-methylpropyl) (e)-but-2-enedioate Chemical compound CC(C)COC(=O)\C=C\C(=O)OCC(C)C RSRICHZMFPHXLE-AATRIKPKSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- JBSLOWBPDRZSMB-BQYQJAHWSA-N dibutyl (e)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C\C(=O)OCCCC JBSLOWBPDRZSMB-BQYQJAHWSA-N 0.000 description 1
- 229940100539 dibutyl adipate Drugs 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- FLESAADTDNKLFJ-UHFFFAOYSA-N nickel;pentane-2,4-dione Chemical compound [Ni].CC(=O)CC(C)=O FLESAADTDNKLFJ-UHFFFAOYSA-N 0.000 description 1
- WATYAKBWIQTPDE-UHFFFAOYSA-N pentane-2,4-dione;zinc Chemical compound [Zn].CC(=O)CC(C)=O WATYAKBWIQTPDE-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229940113147 shellac Drugs 0.000 description 1
- 239000004208 shellac Substances 0.000 description 1
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 description 1
- 235000013874 shellac Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は初期強度、常態剥離強度、耐熱性に優れ、特にポリオレフィン基材の接着性に優れるクロロプレンゴムラテックス接着剤組成物に関するものである。 The present invention relates to a chloroprene rubber latex adhesive composition which is excellent in initial strength, normal peel strength and heat resistance, and particularly excellent in adhesion to polyolefin substrates.
クロロプレンゴムラテックスは水系であるため安全性が高く、コンタクト性を有し初期接着力に優れるという特徴がある。そこで、例えば従来溶剤ゴム系接着剤が使用されていた分野などにおいて、溶剤を使用しない環境対応型の接着剤としてクロロプレンゴムラテックスをベースとした接着剤への置換えが行われている。 Since chloroprene rubber latex is water-based, it is highly safe, has contact properties and excellent initial adhesive strength. Therefore, for example, in the field where solvent rubber adhesives are conventionally used, replacement with an adhesive based on chloroprene rubber latex as an environmentally friendly adhesive without using a solvent is performed.
また、素材分野においても環境への負荷が少ない材料への置換えが進んでおり、例えば塩化ビニル樹脂は汎用樹脂として様々な分野で用いられてきたが、焼却時に有害な塩素化合物を発生するおそれがあることから、ポリオレフィン樹脂などへ置換えられている。一方、ポリオレフィン樹脂は極性が低く難接着性材料として知られているが、前述のように接着剤が溶剤系から水系に置き換えられている状況において、水系接着剤での接着はさらに難易度が高かった。 In the field of raw materials, replacement with a material having a low environmental impact is progressing. For example, vinyl chloride resin has been used as a general-purpose resin in various fields, but it may generate harmful chlorine compounds during incineration. For this reason, it has been replaced with polyolefin resin. On the other hand, polyolefin resin is known as a low-polarity and low-adhesion material, but in the situation where the adhesive is replaced from solvent-based to water-based as described above, adhesion with water-based adhesive is even more difficult. It was.
特許文献１には、特定のゲル含有率であるクロロプレンゴムラテックスを用いることによって耐熱クリープ性能を向上させた接着剤組成物が開示されているが、初期強度や常態剥離強度において改善の余地があった。
本発明の課題は初期強度、常態剥離強度、耐熱性に優れ、特にポリオレフィン基材の接着性に優れるクロロプレンゴムラテックス接着剤組成物を提供することである。 An object of the present invention is to provide a chloroprene rubber latex adhesive composition that is excellent in initial strength, normal peel strength, and heat resistance, and particularly excellent in adhesion to a polyolefin substrate.
本発明は、ロジン酸塩系活性剤を使用して合成され、ゲル含有率が０〜２０重量％であるクロロプレンゴムラテックス（ａ）と、分子内にカルボキシル基または水酸基を有し、ゲル含有率が５０〜８０重量％であるクロロプレンゴムラテックス（ｂ）を含有し、前記クロロプレンゴムラテックス（ａ）とクロロプレンゴムラテックス（ｂ）の含有量が重量比で３０：７０〜７０：３０であることを特徴とするクロロプレンゴムラテックス接着剤組成物である。
The present invention comprises a chloroprene rubber latex (a) synthesized using a rosinate-based activator and having a gel content of 0 to 20% by weight, a carboxyl group or a hydroxyl group in the molecule, and a gel content The chloroprene rubber latex (b) is 50 to 80% by weight, and the content of the chloroprene rubber latex (a) and the chloroprene rubber latex (b) is 30:70 to 70:30 by weight. It is a characteristic chloroprene rubber latex adhesive composition.
本発明のクロロプレンゴムラテックス接着剤組成物は初期強度、常態剥離強度、耐熱性に優れ、ポリオレフィン基材への密着性に優れている。したがって、少なくとも一方の被着体がポリオレフィンである接着、例えば自動車内装材として使用されるポリオレフィン基材とファブリックなどのクロスなどの接着用として有用である。 The chloroprene rubber latex adhesive composition of the present invention is excellent in initial strength, normal peel strength, heat resistance, and excellent adhesion to a polyolefin substrate. Therefore, it is useful for adhesion in which at least one adherend is a polyolefin, for example, adhesion of a polyolefin substrate used as an automobile interior material and a cloth cloth or the like.
本発明の接着剤組成物は、異なる特徴を有する２種のクロロプレンゴムラテックスを含有することを特徴とする。クロロプレンゴムラテックス（ａ）は、ロジン酸塩系活性剤を使用して合成されたことを特徴とし、ゲル含有率は０〜２０重量％が好ましく、０〜５重量％がより好ましい。また、クロロプレンゴムラテックス（ｂ）は、分子内にカルボキシル基または水酸基を有することを特徴とし、ゲル含有率は３０〜１００重量％が好ましく、５０〜８０重量％がより好ましい。初期強度、常態剥離強度、耐熱性の各性能をバランス良く成立させるため、クロロプレンゴムラテックス（ａ）とクロロプレンゴムラテックス（ｂ）の含有量が重量比で３０：７０〜７０：３０であることが好ましい。
The adhesive composition of the present invention is characterized by containing two types of chloroprene rubber latex having different characteristics. The chloroprene rubber latex (a) is characterized by being synthesized using a rosinate-based activator, and the gel content is preferably 0 to 20% by weight, and more preferably 0 to 5% by weight. The chloroprene rubber latex (b) has a carboxyl group or a hydroxyl group in the molecule, and the gel content is preferably 30 to 100% by weight, and more preferably 50 to 80% by weight. In order to establish the balance between the initial strength, the normal peel strength, and the heat resistance, the contents of the chloroprene rubber latex (a) and the chloroprene rubber latex (b) are 30:70 to 70:30 in weight ratio. preferable.
クロロプレンゴムラテックスのゲル含有率は以下の方法により測定する。クロロプレンゴムラテックスにメタノールを添加して凝集させ、さらに真空乾燥することによりメタノールを除去し、凝集物を得る。凝集物を２日間トルエンに浸漬し、２００メッシュ（目開き０．０７５ｍｍ）に通し、メッシュ上に残ったもの真空乾燥することによりトルエンを除去し、ゲルを得る。ゲルの重量と凝集物の重量の比からゲル含有率を求める。なお、架橋進行防止のため、トルエン浸漬は冷暗所にて行う。 The gel content of chloroprene rubber latex is measured by the following method. Methanol is added to the chloroprene rubber latex for agglomeration and further vacuum dried to remove the methanol and obtain an agglomerate. The agglomerate is immersed in toluene for 2 days, passed through 200 mesh (aperture 0.075 mm), and what remains on the mesh is vacuum dried to remove toluene and obtain a gel. The gel content is determined from the ratio between the weight of the gel and the weight of the aggregate. In addition, in order to prevent crosslinking, toluene immersion is performed in a cool and dark place.
本発明の接着剤組成物は、前記クロロプレンゴムラテックス２種に加えて各種添加剤を用いることができる。特に初期強度、常態剥離強度、耐熱性をさらに向上させたり、ポリオレフィン基材に対する密着性を向上させるため、クロロプレンゴムラテックス（ａ）とクロロプレンゴムラテックス（ｂ）の合計１００重量部に対して、粘着付与樹脂１〜１００重量部、塩素化ポリオレフィン樹脂１〜５０重量部、可塑剤１〜５０重量部、 アセチルアセトン金属塩０．１〜１０重量部を用いることが好ましい。 In the adhesive composition of the present invention, various additives can be used in addition to the two types of chloroprene rubber latex. In particular, in order to further improve the initial strength, normal peel strength, and heat resistance, or to improve the adhesion to the polyolefin substrate, the adhesive to 100 parts by weight of the total of chloroprene rubber latex (a) and chloroprene rubber latex (b). It is preferable to use 1 to 100 parts by weight of an imparting resin, 1 to 50 parts by weight of a chlorinated polyolefin resin, 1 to 50 parts by weight of a plasticizer, and 0.1 to 10 parts by weight of an acetylacetone metal salt.
粘着付与樹脂の具体例として、ガムロジン、トールロジン、ウッドロジン、不均斉化ロジン、重合ロジン、これらロジンのグリセリンエステルやペンタエリスリトールエステル、これらの水素添加物などのロジン系樹脂、テルペン樹脂、炭化水素変性テルペン樹脂、これらの水素添加物などのテルペン系樹脂、テルペンフェノール樹脂、テルペンフェノール樹脂の水素添加物などのテルペンフェノール系樹脂、脂肪族系石油樹脂、脂環族系石油樹脂、芳香族系石油樹脂、共重合系石油樹脂、ジシクロペンタジエン系石油樹脂、ピュアーモノマー系石油樹脂、これらの水素添加物などの石油系樹脂、スチレン系樹脂、クマロンインデン系樹脂、アルキルフェノール系樹脂、キシレン系樹脂、ダンマル、コーパル、シェラックなどが挙げられる。 Specific examples of tackifying resins include gum rosin, tall rosin, wood rosin, disproportionated rosin, polymerized rosin, rosin resins such as glycerin ester and pentaerythritol ester of these rosins, hydrogenated products thereof, terpene resins, hydrocarbon-modified terpenes Resins, terpene resins such as these hydrogenated products, terpene phenol resins, terpene phenol resins such as hydrogenated terpene phenol resins, aliphatic petroleum resins, alicyclic petroleum resins, aromatic petroleum resins, Copolymer petroleum resin, dicyclopentadiene petroleum resin, pure monomer petroleum resin, petroleum resins such as these hydrogenated products, styrene resin, coumarone indene resin, alkylphenol resin, xylene resin, dammar, Examples include copal and shellac.
塩素化ポリオレフィンとして、塩素化ポリエチレン、塩素化ポリプロピレンなどが挙げられ、カルボキシル基などの極性基を有するものでもよい。 Examples of the chlorinated polyolefin include chlorinated polyethylene and chlorinated polypropylene, which may have a polar group such as a carboxyl group.
可塑剤の具体例として、フタル酸ジメチル、フタル酸ジエチル、フタル酸ジブチル、フタル酸ジオクチル、フマル酸ジブチル、フマル酸ジイソブチル、アジピン酸ジメチル、アジピン酸ジエチル、アジピン酸ジブチル、アジピン酸オクチル、マレイン酸ジブチル、マレイン酸ビス（２−エチルヘキシル）、アゼライン酸ビス（２−エチルヘキシル）、セバシン酸ジブチル、セバシン酸ビス（２−エチルヘキシル）、ドデカン二酸ビス（２−エチルヘキシル）、アセチルクエン酸トリブチル、２，２，４−トリメチル−１，３−ペンタンジオールジイソブチレート、アロマオイルのような石油系炭化水素可塑剤などが挙げられる。 Specific examples of plasticizers include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, dibutyl fumarate, diisobutyl fumarate, dimethyl adipate, diethyl adipate, dibutyl adipate, octyl adipate, dibutyl maleate Bis (2-ethylhexyl) maleate, bis (2-ethylhexyl) azelate, dibutyl sebacate, bis (2-ethylhexyl) sebacate, bis (2-ethylhexyl) dodecanedioate, tributyl acetylcitrate, 2,2 , 4-trimethyl-1,3-pentanediol diisobutyrate, petroleum hydrocarbon plasticizers such as aroma oil.
アセチルアセトン金属塩の具体例として、アセチルアセトン亜鉛塩、アセチルアセトンアルミニウム塩、アセチルアセトンニッケル塩、アセチルアセトン第二鉄塩などが挙げられる。 Specific examples of the acetylacetone metal salt include acetylacetone zinc salt, acetylacetone aluminum salt, acetylacetone nickel salt, and acetylacetone ferric salt.
本発明の接着剤組成物には前記各添加剤の他、炭酸カルシウムやシリカなどの無機充填材、老化防止剤、加硫促進剤、界面活性剤、防腐剤、消泡剤、分散剤、レベリング剤、凍結安定剤、硬化剤などを適宜配合できる。 In addition to the above additives, the adhesive composition of the present invention includes inorganic fillers such as calcium carbonate and silica, anti-aging agents, vulcanization accelerators, surfactants, preservatives, antifoaming agents, dispersants, and leveling. An agent, a freezing stabilizer, a curing agent and the like can be appropriately blended.
以下、実施例、比較例により本発明を更に説明する。また、当然のことながら本発明は実施例に制約されるものではない。 The present invention will be further described below with reference to examples and comparative examples. Of course, the present invention is not limited to the embodiments.
実施例１
クロロプレンゴムラテックス（ａ）としてスカイプレンＧＦＬ８９０（東ソー社製、商品名、ロジン酸塩系活性剤使用、ゲル含有率１重量％）５０重量部、クロロプレンゴムラテックス（ｂ）としてディスパコールＬＳ２３７２Ｈ（住化バイエルウレタン社製、商品名、分子内に水酸基を含有、ゲル含有率７５重量％）５０重量部、塩素化ポリオレフィンとしてＥＷ５３０３（東洋化成工業社製、商品名）３０重量部、粘着付与樹脂としてＥ２００ＮＴ（荒川化学工業社製、商品名）６０重量部、可塑剤としてＣＳ−１６（チッソ社製、商品名）１５重量部、アセチルアセトン金属塩としてナーセムＡｌ（日本化学産業社製、商品名）２重量部を添加し、実施例１の接着剤組成物を得た。
Example 1
Skyprene GFL890 (trade name, using rosinate-based activator, gel content 1% by weight) 50 parts by weight as chloroprene rubber latex (a), Dispacol LS2372H (Sumika) as chloroprene rubber latex (b) Made by Bayer Urethane Co., Ltd., trade name, 50 parts by weight containing a hydroxyl group in the molecule, gel content 75% by weight), 30 parts by weight EW5303 (trade name, manufactured by Toyo Kasei Kogyo Co., Ltd.) as chlorinated polyolefin, E200NT as tackifying resin (Arakawa Chemical Industry Co., Ltd., trade name) 60 parts by weight, plasticizer as CS-16 (Chisso Corporation, trade name) 15 parts by weight, acetylacetone metal salt as Nersem Al (Nippon Chemical Industry Co., Ltd., trade name) 2 weights The adhesive composition of Example 1 was obtained.
実施例２、３、比較例１、２
実施例１において、表１のように各配合材料の添加量を変えた他は実施例１と同様に実施し、各接着剤組成物を得た。各接着剤組成物をポリプロピレン板に塗布量２００ｇ／ｍ2でスプレー塗布し、８０℃で１５０秒間乾燥した。乾燥後にファブリック（約４５０ｇ／ｍ2、厚み約１.５ｍｍ）をすぐに貼り合わせ、０．３ＭＰａで６０秒間圧締して接着体を得た。各試験体について、以下の方法で評価を行った。
Examples 2 and 3, Comparative Examples 1 and 2
In Example 1, it carried out similarly to Example 1 except having changed the addition amount of each compounding material like Table 1, and obtained each adhesive composition. Each adhesive composition was spray-coated on a polypropylene plate at a coating amount of 200 g / m 2 and dried at 80 ° C. for 150 seconds. After drying, a fabric (about 450 g / m 2 , thickness about 1.5 mm) was immediately bonded together and pressed at 0.3 MPa for 60 seconds to obtain an adhesive. Each specimen was evaluated by the following method.
試験評価方法
初期強度
接着体を作成後、すぐに２５ｍｍ幅に切断し、デジタルフォースゲージを用いて剥離強度を測定する。
常態強度
接着体を２３℃雰囲気下で１４日間養生後、２５ｍｍ幅に切断してデジタルフォースゲージを用いて剥離強度を測定する。
耐熱クリープ
接着体を２３℃雰囲気下で１４日間養生後、８０℃雰囲気下で９０°方向に１００g／２５ｍｍの荷重をかけ、２４時間後の剥離長さを測定する。
Test evaluation method Initial strength Immediately after producing an adhesive, it is cut into a width of 25 mm, and the peel strength is measured using a digital force gauge.
Normal strength After the adhesive body was cured for 14 days in an atmosphere at 23 ° C., it was cut to a width of 25 mm and the peel strength was measured using a digital force gauge.
Heat-resistant creep After the adhesive body was cured in a 23 ° C. atmosphere for 14 days, a load of 100 g / 25 mm was applied in the 90 ° direction in an 80 ° C. atmosphere, and the peel length after 24 hours was measured.
クロロプレンゴムラテックス（ａ）およびクロロプレンゴムラテックス（ｂ）を含有し、前記クロロプレンゴムラテックス（ａ）とクロロプレンゴムラテックス（ｂ）の含有量が重量比で３０：７０〜７０：３０である各実施例の接着剤組成物は初期強度、常態剥離強度、耐熱性のいずれも良好であった。一方、クロロプレンゴムラテックスを１種類しか含有しない比較例の各接着剤組成物は他に添加剤を用いているものの、初期強度、常態剥離強度、耐熱性の全てを満たすことはできなかった。 Each example containing chloroprene rubber latex (a) and chloroprene rubber latex (b), and the content of the chloroprene rubber latex (a) and chloroprene rubber latex (b) is 30:70 to 70:30 by weight. The adhesive composition had good initial strength, normal peel strength, and heat resistance. On the other hand, each adhesive composition of the comparative example containing only one kind of chloroprene rubber latex could not satisfy all of initial strength, normal peel strength, and heat resistance, although other additives were used.
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