JP2014181331A - Adhesive composition - Google Patents
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- JP2014181331A JP2014181331A JP2013058601A JP2013058601A JP2014181331A JP 2014181331 A JP2014181331 A JP 2014181331A JP 2013058601 A JP2013058601 A JP 2013058601A JP 2013058601 A JP2013058601 A JP 2013058601A JP 2014181331 A JP2014181331 A JP 2014181331A
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- 239000000853 adhesive Substances 0.000 title claims abstract description 51
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 51
- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 57
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 238000009820 dry lamination Methods 0.000 claims description 7
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 7
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 6
- 229920006158 high molecular weight polymer Polymers 0.000 claims description 6
- 229920000058 polyacrylate Polymers 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 4
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 claims description 4
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 claims description 4
- 239000000839 emulsion Substances 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- -1 vinyl compound Chemical class 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 125000000962 organic group Chemical group 0.000 description 4
- 239000005056 polyisocyanate Substances 0.000 description 4
- 229920001228 polyisocyanate Polymers 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- NICLKHGIKDZZGV-UHFFFAOYSA-N 2-cyanopentanoic acid Chemical compound CCCC(C#N)C(O)=O NICLKHGIKDZZGV-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000012939 laminating adhesive Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000012941 solvent-based polyurethane adhesive Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
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- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は接着剤組成物に関する。 The present invention relates to an adhesive composition.
従来、レトルトパウチのような、性質の異なるフイルムを貼り合わせる技術として例えば、ドライラミネーションが使用されている。ドライラミネーションは、接着剤を有機溶剤で適当な粘度に希釈してフイルムに塗布し、乾燥後もう一方のフイルムと圧着して貼り合わせる方法である。ドライラミネーションには、接着剤を有機溶剤で希釈する一般的な方法のほか、最近ではエマルジョンタイプ（水の中に接着剤を分散した水性タイプ）がある。またウレタン系接着剤組成物として例えば特許文献１が提案されている。 Conventionally, for example, dry lamination has been used as a technique for bonding films having different properties such as a retort pouch. Dry lamination is a method in which an adhesive is diluted to an appropriate viscosity with an organic solvent, applied to a film, dried, and then bonded to the other film by pressure bonding. In addition to the general method of diluting an adhesive with an organic solvent, dry lamination recently includes an emulsion type (an aqueous type in which an adhesive is dispersed in water). For example, Patent Document 1 has been proposed as a urethane-based adhesive composition.
しかし、本願発明者は従来の接着剤組成物は接着性が低いことを見出した。
そこで、本発明は接着性に優れる接着剤組成物を提供することを目的とする。
However, the present inventor has found that conventional adhesive compositions have low adhesion.
Then, this invention aims at providing the adhesive composition which is excellent in adhesiveness.
本発明者は、上記課題を解決すべく鋭意研究した結果、重量平均分子量が１５，０００〜３５，０００であるポリアクリルアミドと、重量平均分子量が３００，０００〜１，０００，０００である高分子ポリマー（但し前記ポリアクリルアミドを除く。）とを含有し、前記ポリアクリルアミドと前記高分子ポリマーとの質量比が５：１００〜２０：１００である組成物が接着性に優れることを見出し、本発明を完成させた。 As a result of intensive studies to solve the above problems, the present inventor has found that a polyacrylamide having a weight average molecular weight of 15,000 to 35,000 and a polymer having a weight average molecular weight of 300,000 to 1,000,000. It is found that a composition containing a polymer (excluding the polyacrylamide) and having a mass ratio of the polyacrylamide to the high molecular weight polymer of 5: 100 to 20: 100 is excellent in adhesiveness. Was completed.
すなわち、本発明は、下記１〜７を提供する。
１． 重量平均分子量が１５，０００〜３５，０００であるポリアクリルアミドと、
重量平均分子量が３００，０００〜１，０００，０００である高分子ポリマー（但し前記ポリアクリルアミドを除く。）とを含有し、
前記ポリアクリルアミドと前記高分子ポリマーとの質量比が５：１００〜２０：１００である、接着剤組成物。
２． 前記ポリアクリルアミドを構成するモノマーが、アクリルアミド及び／又はＮ，Ｎ−ジメチルアクリルアミドである上記１に記載の接着剤組成物。
３． 前記高分子ポリマーが、アクリル系ポリマー及び／又はエチレン酢酸ビニル共重合体である上記１又は２に記載の接着剤組成物。
４． 更に硬化剤を含有する上記１〜３のいずれかに記載の接着剤組成物。
５． 前記硬化剤の量は、前記ポリアクリルアミド（固形分）と前記高分子ポリマー（固形分）との合計１００質量部に対して、１〜２０質量部である上記４に記載の接着剤組成物。
６． 更に水を含有する上記１〜５のいずれかに記載の接着剤組成物。
７． ドライラミネーションに使用される上記１〜６のいずれかに記載の接着剤組成物。
That is, this invention provides the following 1-7.
1. A polyacrylamide having a weight average molecular weight of 15,000 to 35,000,
A high molecular weight polymer having a weight average molecular weight of 300,000 to 1,000,000 (excluding the polyacrylamide),
The adhesive composition whose mass ratio of the said polyacrylamide and the said high molecular polymer is 5: 100-20: 100.
2. 2. The adhesive composition according to 1 above, wherein the monomer constituting the polyacrylamide is acrylamide and / or N, N-dimethylacrylamide.
3. 3. The adhesive composition according to 1 or 2 above, wherein the polymer is an acrylic polymer and / or an ethylene vinyl acetate copolymer.
4). Furthermore, the adhesive composition in any one of said 1-3 containing a hardening | curing agent.
5. 5. The adhesive composition according to 4, wherein the amount of the curing agent is 1 to 20 parts by mass with respect to a total of 100 parts by mass of the polyacrylamide (solid content) and the polymer polymer (solid content).
6). Furthermore, the adhesive composition in any one of said 1-5 containing water.
7). The adhesive composition according to any one of the above 1 to 6, which is used for dry lamination.
本発明の接着剤組成物は接着性に優れる。 The adhesive composition of this invention is excellent in adhesiveness.
本発明について以下詳細に説明する。
本発明の接着剤組成物は、
重量平均分子量が１５，０００〜３５，０００であるポリアクリルアミドと、
重量平均分子量が３００，０００〜１，０００，０００である高分子ポリマー（但し前記ポリアクリルアミドを除く。）とを含有し、
前記ポリアクリルアミドと前記高分子ポリマーとの質量比が５：１００〜２０：１００である、接着剤組成物である。
The present invention will be described in detail below.
The adhesive composition of the present invention comprises:
A polyacrylamide having a weight average molecular weight of 15,000 to 35,000,
A high molecular weight polymer having a weight average molecular weight of 300,000 to 1,000,000 (excluding the polyacrylamide),
It is an adhesive composition whose mass ratio of the said polyacrylamide and the said high molecular polymer is 5: 100-20: 100.
本発明の接着剤組成物は、特定の範囲の重量平均分子量を有するポリアクリルアミドと、高分子ポリマー（但し前記ポリアクリルアミドを除く。）とを特定の量比で含有することによって、従来のウレタン系ドライラミネート用接着剤より高い接着力を有する。 The adhesive composition of the present invention contains a conventional urethane system by containing polyacrylamide having a weight average molecular weight in a specific range and a high molecular weight polymer (excluding the polyacrylamide) in a specific quantitative ratio. Higher adhesive strength than dry laminating adhesive.
ポリアクリルアミドについて以下に説明する。本発明の接着剤組成物に含有されるポリアクリルアミドは、アミド基又はアミド結合（−ＣＯ−Ｎ−Ｒ2）を有し、主鎖がアクリル樹脂である。−ＣＯ−Ｎ−Ｒ2で表されるアミド結合は、式中（−ＣＯ−Ｎ−Ｒ2）、Ｒは水素原子又は炭化水素基を表し、２つのＲは同じでも異なってもよい。２つのＲが水素原子である場合は除かれる。Ｒとしては、例えば、脂肪族炭化水素基、脂環式炭化水素基、芳香族炭化水素基、これらの組み合わせが挙げられる。
ポリアクリルアミドは単独重合体、共重合体のいずれであってもよい。共重合体である場合、モノマーとして（メタ）アクリルアミド系モノマー以外のビニル性化合物を使用することができる。
The polyacrylamide will be described below. The polyacrylamide contained in the adhesive composition of the present invention has an amide group or an amide bond (—CO—N—R 2 ), and the main chain is an acrylic resin. Amide bond represented by -CO-N-R 2 has the formula (-CO-N-R 2) , R represents a hydrogen atom or a hydrocarbon group, two R's may be the same or different. Excluded when two R are hydrogen atoms. Examples of R include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and combinations thereof.
The polyacrylamide may be either a homopolymer or a copolymer. In the case of a copolymer, a vinyl compound other than a (meth) acrylamide monomer can be used as a monomer.
本発明において、ポリアクリルアミドの重量平均分子量は１５，０００〜３５，０００であり、破壊モードが適正となり接着性により優れ、基材との濡れが高いという観点から、１５０００〜３００００であるのが好ましく、１７０００〜３００００であるのがより好ましい。 In the present invention, the polyacrylamide has a weight average molecular weight of 15,000 to 35,000, preferably 15000 to 30000 from the viewpoint that the fracture mode is appropriate, the adhesion is excellent, and the wettability with the substrate is high. More preferably, it is 17000-30000.
ポリアクリルアミドはその製造について特に制限されない。例えば、水中で重合開始剤の存在下で（メタ）アクリルアミド系モノマーを重合（水溶液重合）させることによって製造することができる。
（メタ）アクリルアミド系モノマーは、アミド基又はアミド結合とビニル重合性基とを有する化合物であれば特に制限されない。
ビニル重合性基としては、例えば、ＣＨ2＝ＣＲ−（Ｒは水素原子又はメチル基）が挙げられる。
アミド基又はアミド結合とビニル重合性基とは単結合で又は有機基を介して結合することができる。有機基としては、例えば、酸素原子、窒素原子、硫黄原子のようなヘテロ原子を有してもよい炭化水素基が挙げられる。炭化水素基としては、例えば、脂肪族炭化水素基、脂環式炭化水素基、芳香族炭化水素基、これらの組み合わせが挙げられる。炭化水素基は、鎖状、分岐状のいずれでもよく、不飽和結合を有してもよい。
ポリアクリルアミドを構成するモノマー［（メタ）アクリルアミド系モノマー］としては、例えば、接着性により優れ、粘度が低いという観点から、アクリルアミド、アミドの窒素原子が上記Ｒで置換されたアクリルアミド（例えば、Ｎ−モノ又はジアルキル置換アクリルアミド）が好ましく、アクリルアミド及び／又はＮ，Ｎ−ジメチルアクリルアミドであるのがより好ましい。
Polyacrylamide is not particularly limited for its production. For example, it can be produced by polymerizing (aqueous) polymerization of a (meth) acrylamide monomer in water in the presence of a polymerization initiator.
The (meth) acrylamide monomer is not particularly limited as long as it is a compound having an amide group or an amide bond and a vinyl polymerizable group.
Examples of the vinyl polymerizable group include CH 2 ═CR— (R is a hydrogen atom or a methyl group).
The amide group or the amide bond and the vinyl polymerizable group can be bonded by a single bond or through an organic group. As an organic group, the hydrocarbon group which may have hetero atoms, such as an oxygen atom, a nitrogen atom, and a sulfur atom, is mentioned, for example. Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a combination thereof. The hydrocarbon group may be chain-like or branched, and may have an unsaturated bond.
As the monomer [(meth) acrylamide monomer] constituting polyacrylamide, for example, from the viewpoint of excellent adhesiveness and low viscosity, acrylamide, acrylamide in which the nitrogen atom of the amide is substituted with R (for example, N- Mono- or dialkyl-substituted acrylamides) are preferred, and acrylamide and / or N, N-dimethylacrylamide are more preferred.
ポリアクリルアミドを製造する際に使用される重合開始剤としては、例えば、親水性重合開始剤が挙げられ、具体的には例えば、過硫酸アンモニウム及び／又はアゾビスシアノ吉草酸が挙げられる。重合開始剤の量は従来公知の量とすることができる。
重合開始剤は、接着性により優れ、ポリマーに親水性を与え被着体への濡れ性に優れるという観点から、過硫酸アンモニウム、過酸化カリウムが好ましい。
ポリアクリルアミドの製造としては例えば、水に（メタ）アクリルアミド系モノマー、重合開始剤を入れ５０〜８０℃の条件において撹拌しながら重合させることによって製造することができる。
得られた水溶液をそのままポリアクリルアミドとして使用することができる。
As a polymerization initiator used when manufacturing polyacrylamide, a hydrophilic polymerization initiator is mentioned, for example, Specifically, an ammonium persulfate and / or azobis cyanovaleric acid are mentioned, for example. The amount of the polymerization initiator can be a conventionally known amount.
The polymerization initiator is preferably ammonium persulfate or potassium peroxide from the viewpoints of better adhesiveness, hydrophilicity of the polymer and excellent wettability to the adherend.
Polyacrylamide can be produced, for example, by adding a (meth) acrylamide monomer and a polymerization initiator in water and polymerizing the mixture under stirring at 50 to 80 ° C.
The obtained aqueous solution can be used as polyacrylamide as it is.
ポリアクリルアミドとして、ポリアクリルアミドの水溶液を使用するのが好ましい態様の１つとして挙げられる。
ポリアクリルアミドが水溶液である場合、ポリアクリルアミドの量（固形分）は、接着性により優れ、被着体への濡れ性に優れるという観点から、当該水溶液の５〜４０質量％であるのが好ましく、１０〜２５質量％であるのがより好ましい。
必要に応じて水分を除去又は添加することができる。
ポリアクリルアミドはそれぞれ単独でまたは２種以上を組み合わせて使用することができる。
One preferred embodiment of the polyacrylamide is to use an aqueous solution of polyacrylamide.
When the polyacrylamide is an aqueous solution, the amount of the polyacrylamide (solid content) is preferably 5 to 40% by mass of the aqueous solution from the viewpoint that the adhesiveness is excellent and the wettability to the adherend is excellent. More preferably, it is 10-25 mass%.
Water can be removed or added as needed.
Polyacrylamide can be used alone or in combination of two or more.
高分子ポリマーについて以下に説明する。本発明の接着剤組成物に含有される高分子ポリマーは、重量平均分子量が１５，０００〜３５，０００であるポリアクリルアミドを除き、特に制限されない。例えば、アクリル系ポリマー、エチレン酢酸ビニル共重合体、ウレタン樹脂、酢酸ビニルポリマーが挙げられる。
高分子ポリマーの構造は、接着性により優れ、被着体への濡れ性に優れるという観点から、アクリル系ポリマー及び／又はエチレン酢酸ビニル共重合体であるのが好ましい。本発明において、アクリル系ポリマーからポリアクリルアミドを除くことができる。
The high molecular polymer will be described below. The high molecular polymer contained in the adhesive composition of the present invention is not particularly limited except for polyacrylamide having a weight average molecular weight of 15,000 to 35,000. Examples include acrylic polymers, ethylene vinyl acetate copolymers, urethane resins, and vinyl acetate polymers.
The structure of the high molecular polymer is preferably an acrylic polymer and / or an ethylene vinyl acetate copolymer from the viewpoint of excellent adhesion and excellent wettability to the adherend. In the present invention, polyacrylamide can be removed from the acrylic polymer.
本発明において、高分子の重量平均分子量は、３００，０００〜１，０００，０００であり、接着性により優れ、接着耐久性に優れるという観点から、４０００００〜１００００００であるのが好ましく、５０００００〜１００００００であるのがより好ましい。 In the present invention, the weight average molecular weight of the polymer is 300,000 to 1,000,000, and is preferably 400,000 to 1,000,000, and more preferably 500,000 to 1,000,000 from the viewpoint that it is superior in adhesion and excellent in durability. It is more preferable that
高分子ポリマーとして、高分子ポリマーと水とを含有し、該高分子ポリマーを分散質（エマルジョン粒子）とし、該水を分散媒（連続相）とする分散系（エマルジョン）を使用することができる。
高分子ポリマーはその製造について特に制限されない。また高分子ポリマーとして市販品を使用することができる。
高分子ポリマーはそれぞれ単独でまたは２種以上を組み合わせて使用することができる。
As the polymer, a dispersion system (emulsion) containing a polymer and water, using the polymer as a dispersoid (emulsion particles), and using the water as a dispersion medium (continuous phase) can be used. .
The polymer is not particularly limited for its production. Moreover, a commercial item can be used as a high molecular polymer.
The high molecular polymers can be used alone or in combination of two or more.
本発明において、ポリアクリルアミド（固形分）と高分子ポリマー（固形分）との質量比は、５：１００〜２０：１００であり、接着性により優れ、接着耐久性に優れるという観点から、５：１００〜１５：１００であるのが好ましく、７：１００〜１５：１００であるのがより好ましい。 In the present invention, the mass ratio of the polyacrylamide (solid content) to the high molecular polymer (solid content) is 5: 100 to 20: 100, and from the viewpoint that the adhesion is excellent and the adhesion durability is excellent. It is preferable that it is 100-15: 100, and it is more preferable that it is 7: 100-15: 100.
本発明の接着剤組成物は、接着性により優れ、接着耐久性に優れるという観点から、更に硬化剤を含有するのが好ましい。硬化剤は、ポリアクリルアミド、高分子ポリマーに対して使用される硬化剤である、又は、基材と反応及び／若しくは相互作用することができる化合物であるのが好ましい態様として挙げられる。硬化剤は、例えば、イソシアネート基、アルコキシシリル基からなる群から選ばれる少なくとも１種の官能基を２個以上有する化合物が挙げられる。官能基は有機基を介して結合することができる。有機基は上記と同義である。 The adhesive composition of the present invention preferably further contains a curing agent from the viewpoint of being excellent in adhesiveness and excellent in durability. It is preferable that the curing agent is a curing agent used for polyacrylamide or a polymer, or a compound capable of reacting and / or interacting with a substrate. Examples of the curing agent include compounds having two or more functional groups selected from the group consisting of isocyanate groups and alkoxysilyl groups. The functional group can be bonded through an organic group. The organic group is as defined above.
硬化剤としては、ポリイソシアネート、が挙げられる。ポリイソシアネートとしては、例えば、ヘキサメチレンジイソシアネート、イソフォロンジイソシアネートのような脂肪族ポリイソシアネート；ジフェニルメタンジイソシアネート（ＭＤＩ）、ポリメリックＭＤＩ、トルエンジイソシアネートのような芳香族ポリイソシアネートが挙げられる。
硬化剤はそれぞれ単独でまたは２種以上を組み合わせて使用することができる。
Examples of the curing agent include polyisocyanate. Examples of the polyisocyanate include aliphatic polyisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate; aromatic polyisocyanates such as diphenylmethane diisocyanate (MDI), polymeric MDI, and toluene diisocyanate.
The curing agents can be used alone or in combination of two or more.
硬化剤の量は、接着性により優れ、接着耐久性に優れるという観点から、ポリアクリルアミド（固形分）と高分子ポリマー（固形分）との合計１００質量部に対して、１〜２０質量部であるのが好ましく、２〜１０質量部であるのがより好ましい。 The amount of the curing agent is 1 to 20 parts by mass with respect to a total of 100 parts by mass of the polyacrylamide (solid content) and the high molecular polymer (solid content) from the viewpoint of superior adhesion and excellent adhesion durability. It is preferable that it is 2 to 10 parts by mass.
本発明の接着剤組成物は更に水を含有することができる。水の量は、組成物全体中の３０〜６０質量％とすることができる。 The adhesive composition of the present invention can further contain water. The amount of water can be 30 to 60% by mass in the entire composition.
本発明の接着剤組成物は、上記成分以外に、本発明の目的、効果を損なわない範囲で、必要に応じてさらに添加剤を含有することができる。添加剤としては、例えば、タッキファイヤー、充填剤、顔料、ブロッキング防止剤、分散安定剤、揺変剤、粘度調節剤、レベリング剤、ゲル化防止剤、光安定剤、老化防止剤、酸化防止剤、紫外線吸収剤、可塑剤、滑剤、帯電防止剤、補強材、難燃剤、触媒、消泡剤、増粘剤、分散剤、界面活性剤、レオロジー調整剤が挙げられる。添加剤の量は、特に制限されない。
本発明の接着剤組成物は完全無溶剤型（完全無有機溶剤型）、環境対応型とすることができる。
In addition to the above components, the adhesive composition of the present invention may further contain an additive as necessary within a range that does not impair the object and effect of the present invention. Examples of additives include tackifiers, fillers, pigments, antiblocking agents, dispersion stabilizers, thixotropic agents, viscosity modifiers, leveling agents, antigelling agents, light stabilizers, antiaging agents, and antioxidants. UV absorbers, plasticizers, lubricants, antistatic agents, reinforcing materials, flame retardants, catalysts, antifoaming agents, thickeners, dispersants, surfactants, rheology modifiers. The amount of the additive is not particularly limited.
The adhesive composition of the present invention can be of a completely solvent-free type (fully organic solvent-free type) or an environment-friendly type.
本発明の接着剤組成物はその製造について特に制限されない。例えば、高分子ポリマーのエマルジョンとポリアクリルアミド（水溶液であってもよい）とを均一に混合して、高分子ポリマーとポリアクリルアミドとを含有する第１液（主剤）を製造し、硬化剤を含有する第２液を製造して、使用時に第１液と第２液とを混合することによって製造することができる。 The adhesive composition of the present invention is not particularly limited for its production. For example, a polymer polymer emulsion and polyacrylamide (which may be an aqueous solution) are uniformly mixed to produce a first liquid (main agent) containing the polymer and polyacrylamide, which contains a curing agent. The second liquid to be manufactured can be manufactured by mixing the first liquid and the second liquid at the time of use.
本発明の接着剤組成物を適用することができる基材としては、例えば、ドライラミネーションに使用される基材が挙げられ、具体的には例えば、ポリエチレンテレフタレート、ポリプロピレン（延伸ポリプロピレン）、ポリエチレン、ポリイミド、ナイロンのようなポリマー；アルミニウムのような金属が挙げられる。
本発明の接着剤組成物を基材に適用する方法は特に制限されない。例えば、従来公知のものが挙げられる。
本発明の接着剤組成物を適用する塗布工程のあと、必要に応じて乾燥工程を設けることができる。乾燥工程における乾燥温度は３０〜１００℃とすることができる。乾燥方法は特に制限されない。
乾燥工程後、必要に応じて基材を養生させ、その後、接着剤組成物を塗布した基材と別の基材を貼りあわせて積層体とし、これを２０〜６０℃又は２０〜８０℃、０．５〜３ＭＰａ又は０．０５〜３ＭＰａの条件下でプレスして、基材を接着させるプレス工程を設けることができる。
Examples of the substrate to which the adhesive composition of the present invention can be applied include substrates used for dry lamination, specifically, for example, polyethylene terephthalate, polypropylene (stretched polypropylene), polyethylene, polyimide , Polymers such as nylon; metals such as aluminum.
The method for applying the adhesive composition of the present invention to a substrate is not particularly limited. For example, a conventionally well-known thing is mentioned.
After the coating step for applying the adhesive composition of the present invention, a drying step can be provided as necessary. The drying temperature in a drying process can be 30-100 degreeC. The drying method is not particularly limited.
After the drying step, the substrate is cured as necessary, and then the substrate coated with the adhesive composition and another substrate are bonded together to form a laminate, which is 20 to 60 ° C or 20 to 80 ° C. It is possible to provide a pressing step for pressing the substrate under conditions of 0.5 to 3 MPa or 0.05 to 3 MPa to adhere the substrate.
本発明の接着剤組成物の用途としては、例えば、ドライラミネーション用接着剤、プロファイルラッピング用が挙げられる。 Applications of the adhesive composition of the present invention include, for example, dry lamination adhesives and profile wrapping.
以下に、実施例を示して本発明を具体的に説明する。ただし、本発明はこれらに限定されない。
＜ポリアクリルアミドの製造＞
・重合例１〜８
下記第１表に示す成分を同表に示す量（モル比）で用い、これらを水１００ｍｌに加え、６０℃の条件下で６時間反応させ、６時間後反応を停止して、ポリアクリルアミドを製造した。得られた反応液は、ポリアクリルアミドが水に溶解している、ポリアクリルアミドの水溶液であった。
（ポリアクリルアミドの重量平均分子量の測定）
得られたポリアクリルアミドの水溶液についてジメチルフォルムアミド（ＤＭＦ）を溶媒とするゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）により測定し、標準ポリスチレン換算によってポリアクリルアミドの重量平均分子量を得た。結果を第１表に示す。
＜ウレタンプレポリマーの製造＞
・重合例９〜１２
下記第１表に示す成分を同表に示す量（モル比）で用い、これらを７０℃の条件下で６時間反応させ、ウレタンプレポリマーを製造した。
（ウレタンプレポリマーの重量平均分子量の測定）
得られたウレタンプレポリマーについて、ＤＭＦを溶媒とするゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）によって測定し、標準ポリスチレン換算によって重量平均分子量を得た。結果を第１表に示す。
Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
<Manufacture of polyacrylamide>
Polymerization examples 1-8
The components shown in Table 1 below were used in the amounts (molar ratio) shown in the same table, these were added to 100 ml of water, reacted at 60 ° C. for 6 hours, the reaction was stopped after 6 hours, and polyacrylamide was removed. Manufactured. The obtained reaction solution was an aqueous solution of polyacrylamide in which polyacrylamide was dissolved in water.
(Measurement of weight average molecular weight of polyacrylamide)
The obtained polyacrylamide aqueous solution was measured by gel permeation chromatography (GPC) using dimethylformamide (DMF) as a solvent, and the weight average molecular weight of polyacrylamide was obtained by standard polystyrene conversion. The results are shown in Table 1.
<Manufacture of urethane prepolymer>
Polymerization examples 9-12
The components shown in Table 1 below were used in the amounts (molar ratio) shown in the same table, and these were reacted at 70 ° C. for 6 hours to produce a urethane prepolymer.
(Measurement of weight average molecular weight of urethane prepolymer)
About the obtained urethane prepolymer, it measured by the gel permeation chromatography (GPC) which uses DMF as a solvent, and obtained the weight average molecular weight by standard polystyrene conversion. The results are shown in Table 1.
第１表に示す各成分の詳細は以下のとおりである。
・アクリルアミド：和光純薬社製
・Ｎ，Ｎ−ジメチルアクリルアミド：和光純薬社製
・アゾビスシアノ吉草酸：和光純薬社製
・過硫酸アンモニウム：和光純薬社製
・水添ＸＤＩ：水添キシリレンジイソシアネート、試薬、和光純薬社製
・ＰＰＧ４００：ポリプロピレングリコール、試薬、和光純薬社製、分子量４００
・ＰＰＧ１０００：ポリプロピレングリコール、試薬、和光純薬社製、分子量１０００
The details of each component shown in Table 1 are as follows.
Acrylamide: Wako Pure Chemicals, N, N-dimethylacrylamide: Wako Pure Chemicals, Azobiscyanovaleric acid: Wako Pure Chemicals, Ammonium Persulfate: Wako Pure Chemicals, Hydrogenated XDI: Hydrogenated Xylylene Diisocyanate , Reagent, Wako Pure Chemical Industries, Ltd. PPG400: polypropylene glycol, reagent, Wako Pure Chemical Industries, molecular weight 400
PPG1000: polypropylene glycol, reagent, manufactured by Wako Pure Chemical Industries, molecular weight 1000
＜接着剤組成物の製造＞
・主剤の製造
下記第２表に示す主剤の成分を同表に示す量（単位は質量部。主剤の量は固形分量である。）で使用し、これらを均一に混合して接着剤組成物の主剤を製造した。
・主剤と硬化剤との混合
上記のとおり製造された主剤１００質量部に対して、下記第２表に示す硬化剤の成分を同表に示す量（単位は質量部。固形分量）で使用し、主剤と硬化剤とを均一に混合して接着剤組成物を製造した。
<Manufacture of adhesive composition>
-Manufacture of main agent Adhesive composition by mixing the components of the main agent shown in the following Table 2 in the amount shown in the same table (unit is parts by mass. The amount of the main agent is the solid content) and mixing them uniformly. The main ingredient was manufactured.
-Mixing of main agent and curing agent For 100 parts by mass of the main agent produced as described above, the components of the curing agent shown in Table 2 below are used in the amounts shown in the same table (unit: parts by mass, solid content). The base composition and the curing agent were uniformly mixed to produce an adhesive composition.
＜評価＞
上記のとおり製造された接着剤組成物について、接着性を下記の方法で評価した。結果を第２表に示す。
・積層体の製造
まず、厚さ４０μｍのポリエチレンテレフタレート（ＰＥＴ）を２枚準備し、そのうちの１枚に、上記のとおり製造された接着剤組成物をＮｏ．３０バーコーターで塗布し、１００℃の条件下で５分間乾燥させ、乾燥後３時間置いた。３時間経過後、接着剤組成物を塗布したＰＥＴにもう１枚のＰＥＴを貼りあわせて積層体とし、これを８０℃、０．０５ＭＰａの条件下で３分間プレスした。
・剥離強度の測定
プレス後積層体を幅２５ｍｍの短冊状に切って、これを用いて常温にて引張試験機を用いて２００ｍｍ／分の剥離速度でＴ型剥離での剥離強度を測定した。
剥離強度が１．１ｋｇ／２５ｍｍ以上である場合、接着性に優れる。
・破壊モードの確認
また剥離強度測定後の積層体の破壊モードを目視で確認した。ＣＦは接着剤層の凝集破壊を示し、ＡＦは接着剤層と基材との界面破壊を示す。
破壊モードがＣＦである場合、接着性に優れる。
<Evaluation>
About the adhesive composition manufactured as mentioned above, adhesiveness was evaluated by the following method. The results are shown in Table 2.
-Manufacture of laminated body First, two sheets of polyethylene terephthalate (PET) having a thickness of 40 µm were prepared, and the adhesive composition manufactured as described above was prepared as No. 1 on one of them. It was applied with a 30 bar coater, dried at 100 ° C. for 5 minutes, and allowed to stand for 3 hours after drying. After 3 hours, another PET was bonded to the PET coated with the adhesive composition to form a laminate, which was pressed under conditions of 80 ° C. and 0.05 MPa for 3 minutes.
-Measurement of peeling strength After pressing, the laminated body was cut into a strip shape having a width of 25 mm, and using this, the peeling strength at T-type peeling was measured at a peeling rate of 200 mm / min at room temperature using a tensile tester.
When the peel strength is 1.1 kg / 25 mm or more, the adhesiveness is excellent.
-Confirmation of failure mode The failure mode of the laminate after the peel strength measurement was visually confirmed. CF indicates cohesive failure of the adhesive layer, and AF indicates interface failure between the adhesive layer and the substrate.
When the fracture mode is CF, the adhesiveness is excellent.
第２表に示されている各成分の詳細は以下のとおりである。
・アクリルエマルジョン ビニブラン５２０２Ｃ：アクリル系エマルジョン、日信化成社製、表中の分子量は当該エマルジョンに含有されるアクリル樹脂の重量平均分子量である。
・ＥＶＡエマルジョン スミカフレックス４００：エチレン酢酸ビニル共重合体エマルジョン、住友化学社製、表中の分子量は当該エマルジョンに含有されるエチレン酢酸ビニル共重合体の重量平均分子量である。
・ウレタンエマルジョン ハイドランＡＰ−４０：ＤＩＣ社製、表中の分子量は当該エマルジョンに含有されるポリウレタンの重量平均分子量である。
・ＡＤ−５０２：東洋モートン社製、ポリウレタン系接着剤の主剤（ケトン系溶剤を含む溶剤型）
・ポリアクリルアミド：上記のとおり製造例１〜８で製造されたポリアクリルアミド
・ウレタンプレポリマー：上記のとおり製造例９〜１２で製造されたウレタンプレポリマー
・スミジュール４４Ｖ１０：ポリメリックＭＤＩ、スミカバイエルウレタン社製、ポリアクリルアミド又はウレタンプレポリマー用硬化剤として使用。
・ＣＡＴ１０Ｌ：東洋モートン社製、ポリウレタン系硬化剤（ケトン系溶剤を含む溶剤型）
The details of each component shown in Table 2 are as follows.
Acrylic emulsion Vinibrand 5202C: acrylic emulsion, manufactured by Nisshin Kasei Co., Ltd., the molecular weight in the table is the weight average molecular weight of the acrylic resin contained in the emulsion.
-EVA emulsion Sumikaflex 400: ethylene vinyl acetate copolymer emulsion, manufactured by Sumitomo Chemical Co., Ltd., the molecular weight in the table is the weight average molecular weight of the ethylene vinyl acetate copolymer contained in the emulsion.
-Urethane emulsion Hydran AP-40: The product made by DIC, the molecular weight in a table | surface is the weight average molecular weight of the polyurethane contained in the said emulsion.
AD-502: Toyo Morton, the main component of polyurethane adhesives (solvent type including ketone solvents)
Polyacrylamide: Polyacrylamide produced in Production Examples 1-8 as described above Urethane prepolymer: Urethane prepolymer produced in Production Examples 9-12 as described above Sumijour 44V10: Polymeric MDI, Sumika Bayer Urethane Co., Ltd. Used as a curing agent for polyacrylamide or urethane prepolymer.
-CAT10L: Toyo Morton, polyurethane curing agent (solvent type including ketone solvent)
第２表に示す結果から明らかなように、溶剤系ポリウレタンの接着剤を使用する比較例１２は接着力が０．６ｋｇ／２５ｍｍと低く接着性が悪かった。重量平均分子量が３００，０００未満の高分子ポリマーを含有する比較例１は接着性が低かった。ポリアクリルアミドを含有しない比較例２、ポリアクリルアミドの量が高分子ポリマー１００質量部に対して、５質量部未満の比較例３、２０質量部を超える比較例４、５は接着性が低かった。重量平均分子量が１５，０００未満又は３５，０００を超えるポリアクリルアミドを含有する比較例６、７は接着性が低かった。ポリアクリルアミドの代わりにウレタンプレポリマーを含有する比較例８〜１１は接着性が低かった。
これに対して、実施例１〜１４は、接着力が高く、破壊モードが適正であり、接着性に優れる。
As is apparent from the results shown in Table 2, Comparative Example 12 using a solvent-based polyurethane adhesive had a low adhesive strength of 0.6 kg / 25 mm and poor adhesiveness. Comparative Example 1 containing a high molecular weight polymer having a weight average molecular weight of less than 300,000 had low adhesion. Comparative Example 2, which does not contain polyacrylamide, Comparative Example 3 in which the amount of polyacrylamide is less than 5 parts by mass, and Comparative Examples 4, 5 in which the amount of polyacrylamide exceeds 20 parts by mass were low in adhesiveness. Comparative Examples 6 and 7 containing polyacrylamide having a weight average molecular weight of less than 15,000 or more than 35,000 had low adhesion. Comparative Examples 8 to 11 containing a urethane prepolymer instead of polyacrylamide had low adhesion.
On the other hand, Examples 1 to 14 have high adhesive strength, proper destruction mode, and excellent adhesiveness.
Claims (7)
重量平均分子量が３００，０００〜１，０００，０００である高分子ポリマー（但し前記ポリアクリルアミドを除く。）とを含有し、
前記ポリアクリルアミドと前記高分子ポリマーとの質量比が５：１００〜２０：１００である、接着剤組成物。 A polyacrylamide having a weight average molecular weight of 15,000 to 35,000,
A high molecular weight polymer having a weight average molecular weight of 300,000 to 1,000,000 (excluding the polyacrylamide),
The adhesive composition whose mass ratio of the said polyacrylamide and the said high molecular polymer is 5: 100-20: 100.
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Citations (8)
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| JPH069847A (en) * | 1992-06-26 | 1994-01-18 | Arakawa Chem Ind Co Ltd | Resin composition curable by actinic energy ray |
| JPH06271780A (en) * | 1993-01-20 | 1994-09-27 | Dai Ichi Kogyo Seiyaku Co Ltd | Thermoplastic resin composition and antistatic resin composite film |
| JPH09143446A (en) * | 1995-11-20 | 1997-06-03 | Toyo Ink Mfg Co Ltd | Adhesive |
| JP2001503465A (en) * | 1996-11-08 | 2001-03-13 | ミネソタ マイニング アンド マニュファクチャリング カンパニー | Moisture curable hot melt composition |
| JP2001089731A (en) * | 1999-09-20 | 2001-04-03 | Lintec Corp | Pressure-sensitive adhesive composition and adhesive optical function member made thereof |
| JP2007326899A (en) * | 2006-06-06 | 2007-12-20 | Nitto Denko Corp | Pressure-sensitive adhesive composition, pressure-sensitive adhesive sheet and pressure-sensitive adhesive-adhered functional film |
| JP2008239848A (en) * | 2007-03-28 | 2008-10-09 | Kuraray Co Ltd | Adhesive agent |
| US20090133846A1 (en) * | 2005-12-29 | 2009-05-28 | Grigoriev Vladimir A | Creping adhesives comprising blends of high and low molecular weight resins |
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| JPH069847A (en) * | 1992-06-26 | 1994-01-18 | Arakawa Chem Ind Co Ltd | Resin composition curable by actinic energy ray |
| JPH06271780A (en) * | 1993-01-20 | 1994-09-27 | Dai Ichi Kogyo Seiyaku Co Ltd | Thermoplastic resin composition and antistatic resin composite film |
| JPH09143446A (en) * | 1995-11-20 | 1997-06-03 | Toyo Ink Mfg Co Ltd | Adhesive |
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| JP2007326899A (en) * | 2006-06-06 | 2007-12-20 | Nitto Denko Corp | Pressure-sensitive adhesive composition, pressure-sensitive adhesive sheet and pressure-sensitive adhesive-adhered functional film |
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