JP2005281630A - Adhesive composition - Google Patents
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- JP2005281630A JP2005281630A JP2004101686A JP2004101686A JP2005281630A JP 2005281630 A JP2005281630 A JP 2005281630A JP 2004101686 A JP2004101686 A JP 2004101686A JP 2004101686 A JP2004101686 A JP 2004101686A JP 2005281630 A JP2005281630 A JP 2005281630A
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- emulsion
- vinyl acetate
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- polyvinyl alcohol
- monomer
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- 239000000853 adhesive Substances 0.000 title claims abstract description 30
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 30
- 239000000203 mixture Substances 0.000 title claims abstract description 21
- 239000000839 emulsion Substances 0.000 claims abstract description 48
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 23
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 23
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 19
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 19
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 8
- 239000000084 colloidal system Substances 0.000 claims abstract description 8
- 230000001681 protective effect Effects 0.000 claims abstract description 8
- 125000002339 acetoacetyl group Chemical group O=C([*])C([H])([H])C(=O)C([H])([H])[H] 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 24
- 239000011347 resin Substances 0.000 abstract description 22
- 229920005989 resin Polymers 0.000 abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 19
- 239000004014 plasticizer Substances 0.000 abstract description 10
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 5
- 229920000877 Melamine resin Polymers 0.000 abstract description 2
- 239000004640 Melamine resin Substances 0.000 abstract description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 abstract description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 abstract description 2
- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- 229920001577 copolymer Polymers 0.000 abstract 1
- 239000011342 resin composition Substances 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011120 plywood Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- YHSYGCXKWUUKIK-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C=C YHSYGCXKWUUKIK-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 235000018185 Betula X alpestris Nutrition 0.000 description 1
- 235000018212 Betula X uliginosa Nutrition 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は可塑剤、ホルムアルデヒド或いはホルムアルデヒドを遊離する原料を使用することなく、優れた耐水性、低温接着性などを実現した酢酸ビニル樹脂系エマルジョンからなる接着剤組成物に関するものである。 The present invention relates to an adhesive composition comprising a vinyl acetate resin emulsion that achieves excellent water resistance, low-temperature adhesion, and the like without using a plasticizer, formaldehyde or a raw material that liberates formaldehyde.
従来、例えば、合板の表面に化粧紙を接着し更に塗装仕上する化粧合板、突き板を接着する天然木化粧合板、あるいは集成材の表面に化粧単板を接着する化粧単板貼りなどには、接着力、耐水性などが強く求められるため、メラミン樹脂、尿素樹脂、フェノール樹脂、或いはこれらに酢酸ビニルエマルジョンを混合したもの、或いはＮ−メチロールアクリルアミドなどの架橋性モノマーを共重合させた酢酸ビニル樹脂エマルジョンなどが使用されてきた。しかし、これらはホルムアルデヒドを放出するために、好ましくないとして採用されなくなってきている。 Conventionally, for example, a decorative plywood that adheres decorative paper to the surface of the plywood and further finishes the painting, a natural wood decorative plywood that adheres the veneer, or a decorative veneer that adheres the decorative veneer to the surface of the laminated material, etc. Adhesive strength, water resistance, etc. are strongly required, so melamine resin, urea resin, phenol resin, or those mixed with vinyl acetate emulsion, or vinyl acetate resin copolymerized with crosslinkable monomers such as N-methylolacrylamide Emulsions have been used. However, they are no longer adopted as undesirable because they release formaldehyde.
これに対応する手段としてアセトアセチル化ポリビニルアルコール（以下ＡＡｃＰＶＡと略称）を保護コロイドとして使用するとともに、ＡＡｃ基含有モノマーと酢酸ビニルモノマー（以下ＶＡｃと略称）とを乳化共重合させ、架橋により耐水性、接着力などを実現する方法が検討されてきた。
この方法ではホルムアルデヒドを使用することなく耐水性を獲得しており、この点においては環境対応型とみなすこともできる。しかし、得られた樹脂エマルジョンは従来の酢酸ビニル樹脂エマルジョンと同様に低温造膜性が悪く、気温が低下する冬場に使用するためには可塑剤を配合する必要があった。しかし代表的な可塑剤であるフタル酸ジブチル（ＤＢＰ）は環境ホルモンの懸念が指摘されており、その他の可塑剤もＶＯＣ成分となるため、完全な環境対応型とはいえなかった。
As a means to cope with this, acetoacetylated polyvinyl alcohol (hereinafter abbreviated as AAcPVA) is used as a protective colloid, and an AAc group-containing monomer and a vinyl acetate monomer (hereinafter abbreviated as VAc) are emulsion-copolymerized and water-resistant by crosslinking. A method for realizing adhesive strength has been studied.
In this method, water resistance is obtained without using formaldehyde, and in this respect, it can be regarded as an environment-friendly type. However, the resulting resin emulsion has poor low-temperature film-forming properties as in the case of conventional vinyl acetate resin emulsions, and it is necessary to add a plasticizer for use in winter when the temperature decreases. However, dibutyl phthalate (DBP), which is a typical plasticizer, has been pointed out as a concern for environmental hormones, and other plasticizers are also VOC components, so they were not completely environmentally friendly.
また、アセトアセチル化エチレン・酢酸ビニル共重合樹脂エマルジョンの存在下で、ＡＡｃＰＶＡとエチレン変性ポリビニルアルコールを用いて、ＶＡｃとアセトアセチル（以下ＡＡｃと略称する）化（メタ）アクリル酸エステルを乳化共重合することにより耐水性、接着力のある接着剤を実現しようとする試みが為されている。
しかし、この方法により得られる樹脂エマルジョンでは低温造膜性の改良や低温作業性の改良には一定の効果が得られるものの、なお低温造膜性が不足し可塑剤の配合なくしては冬季の使用が難しい。
In the presence of an acetoacetylated ethylene / vinyl acetate copolymer resin emulsion, VAc and acetoacetyl (hereinafter abbreviated as AAc) (meth) acrylic acid ester are emulsion copolymerized using AAcPVA and ethylene-modified polyvinyl alcohol. Thus, attempts have been made to realize an adhesive having water resistance and adhesive strength.
However, although the resin emulsion obtained by this method has a certain effect in improving the low-temperature film-forming property and improving the low-temperature workability, it is still insufficient in low-temperature film-forming property and used in winter without the addition of a plasticizer. Is difficult.
本発明の目的は、前記のような状況に鑑みて可塑剤、ホルムアルデヒド、ホルムアルデヒドを遊離する原料を使用することなく低温造膜性、低温作業性、耐水接着性能など備えた接着剤組成物を提供することにある。 An object of the present invention is to provide an adhesive composition having low-temperature film-forming properties, low-temperature workability, water-resistant adhesive performance and the like without using a plasticizer, formaldehyde, and a raw material that liberates formaldehyde in view of the above situation. There is to do.
前記のような、可塑剤、ホルムアルデヒド、ホルムアルデヒドを遊離する原料を使用することなく低温造膜性、低温作業性、耐水接着性能などを備える接着剤組成物を得るために、本発明においては、最低造膜温度（以下ＭＦＴと略称する）が０℃以下であつて、カルボキシル基を含有するアクリル樹脂エマルジョンの存在下、或いは該アクリル樹脂エマルジョンとその他の樹脂エマルジョンとが混合された樹脂エマルジョンの存在下において、保護コロイドとしてポリビニルアルコール（以下ＰＶＡと略称する）とＡＡｃＰＶＡとを併用するか、もしくはＡＡｃＰＶＡを使用して、ＶＡｃを乳化重合、或いはＶＡｃとＡＡｃ基含有モノマーとを乳化共重合することより調製しようとするものである。 In order to obtain an adhesive composition having low-temperature film-forming properties, low-temperature workability, water-resistant adhesion performance and the like without using a plasticizer, formaldehyde, and a raw material that liberates formaldehyde as described above, The film forming temperature (hereinafter abbreviated as MFT) is 0 ° C. or lower and in the presence of an acrylic resin emulsion containing a carboxyl group or in the presence of a resin emulsion in which the acrylic resin emulsion and other resin emulsions are mixed. Prepared by using polyvinyl alcohol (hereinafter abbreviated as PVA) and AAcPVA together as a protective colloid, or by using AAcPVA to emulsion-polymerize VAc, or emulsion-copolymerize VAc and AAc group-containing monomer. It is something to try.
本発明になる接着剤組成物は、ＭＦＴが０℃以下であつて、カルボキシル基を含有するアクリル樹脂エマルジョンの存在下、或いは該アクリル樹脂エマルジョンとその他の樹脂エマルジョンとが混合された樹脂エマルジョンの存在下において、保護コロイドとしてＰＶＡとＡＡｃＰＶＡとを併用するか、もしくはＡＡｃＰＶＡを使用して、ＶＡｃを乳化重合、或いはＶＡｃとＡＡｃ基含有モノマーとを乳化共重合することより調製されているため、高い耐水接着性能を持ち、低温造膜性に優れ冬季でも安定した接着性能が得られる。更に一液タイプであるため可使時間の制約を受けず、木工用、紙加工用、繊維加工用などの用途に安心して利用できる。
しかもホルムアルデヒド、可塑剤を含有しないため、接着剤組成物自体が環境に優しいばかりか、これを使用して生産或いは加工した各種製品を環境に優しい商品に仕上ることができる。
The adhesive composition according to the present invention has an MFT of 0 ° C. or less and the presence of an acrylic resin emulsion containing a carboxyl group or the presence of a resin emulsion in which the acrylic resin emulsion is mixed with other resin emulsions. Below, PVA and AAcPVA are used in combination as protective colloids, or AAcPVA is used to emulsion-polymerize VAc, or emulsion-copolymerize VAc and AAc group-containing monomer. Adhesive performance, excellent low-temperature film-forming properties, and stable adhesive performance can be obtained even in winter. Furthermore, because it is a one-component type, it can be used with confidence in applications such as woodworking, paper processing, and fiber processing without being restricted by the usable time.
Moreover, since it does not contain formaldehyde or a plasticizer, not only the adhesive composition itself is environmentally friendly, but also various products produced or processed using it can be made into environmentally friendly products.
以下、本発明について詳細に説明する。
本発明になる接着剤組成物は、ＭＦＴが０℃以下であつて、カルボキシル基を含有するアクリル樹脂エマルジョンの存在下、或いは該アクリル樹脂エマルジョンとその他の樹脂エマルジョンとが混合された樹脂エマルジョンの存在下において、保護コロイドとしてＰＶＡとＡＡｃＰＶＡとを併用するか、もしくはＡＡｃＰＶＡを使用して、ＶＡｃを乳化重合、或いはＶＡｃとＡＡｃ基含有モノマーとを乳化共重合することより調製したものであつて、詳しくは、該アクリル樹脂系エマルジョンには、固形分中にカルボキシル基含有モノマーを固形分中に０．１〜１０重量％を含有するものであつて、かつ調製された酢酸ビニル樹脂系エマルジョンの固形分中に２〜３０％配合される。また、酢酸ビニル１００重量部に対してＡＡｃ基含有モノマー２〜２５重量部が乳化共重合されること、保護コロイドとしてＡＡｃＰＶＡのＰＶＡとの併用、もしくはＡＡｃＰＶＡ単独使用などにより、一層の性能向上が図られる。
とりわけＡＡｃＰＶＡを２０〜１００％含むことが耐水性を確保する点から望ましい。ＡＡ化ＰＶＡを２０％以下含むものでは十分な耐水性が得られないため好ましくない。
Hereinafter, the present invention will be described in detail.
The adhesive composition according to the present invention has an MFT of 0 ° C. or less and the presence of an acrylic resin emulsion containing a carboxyl group, or the presence of a resin emulsion in which the acrylic resin emulsion is mixed with another resin emulsion. Below, PVA and AAcPVA are used in combination as protective colloids or AAcPVA is used to prepare VAc by emulsion polymerization, or VAc and AAc group-containing monomer by emulsion copolymerization. The acrylic resin emulsion contains a carboxyl group-containing monomer in the solid content of 0.1 to 10% by weight in the solid content, and the solid content of the prepared vinyl acetate resin emulsion. 2-30% is blended in. In addition, 2-25 parts by weight of an AAc group-containing monomer is copolymerized with 100 parts by weight of vinyl acetate, and a combination of AAcPVA with PVA as a protective colloid or AAcPVA alone is used to further improve performance. It is done.
In particular, 20 to 100% of AAcPVA is desirable from the viewpoint of ensuring water resistance. A material containing 20% or less of AA-PVA is not preferable because sufficient water resistance cannot be obtained.
シード用に使用されるアクリル樹脂エマルジョンは、メチル（メタ）アクリート、エチル（メタ）アクリレート、２―エチルヘキシルアクリレート、ブチルアクリレート、エチレングリコールジ（メタ）アクリレート、グリシジル（メタ）アクリレート、プロピレングリコール（メタ）アクリレート、スチレン、２−ヒドロキシエチル（メタ）アクリレート、アクリルアミドなどのモノマーをベースに、好ましくはアクリル樹脂エマルジョンの固形分に対して０．１〜１０重量％のアクリル酸、メタクリル酸、イタコン酸、無水マレイン酸などカルボキシル基含有モノマーが乳化共重合されたものからなり、０℃以下のＭＦＴを備えるように調製されたものが使用される。 Acrylic resin emulsions used for seeds are methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl acrylate, butyl acrylate, ethylene glycol di (meth) acrylate, glycidyl (meth) acrylate, propylene glycol (meth) Based on monomers such as acrylate, styrene, 2-hydroxyethyl (meth) acrylate, acrylamide, preferably 0.1 to 10% by weight of acrylic acid, methacrylic acid, itaconic acid, anhydrous, based on the solid content of the acrylic resin emulsion A monomer prepared by emulsion-copolymerizing a carboxyl group-containing monomer such as maleic acid and having an MFT of 0 ° C. or lower is used.
該アクリル樹脂エマルジョンは、調製される酢酸ビニル樹脂エマルジョンの固形分の２〜３０重量％、より好ましくは３〜２０重量％の範囲で使用されることが好ましい。２重量％以下では、調製される酢酸ビニル樹脂エマルジョンの２℃以下の最低造膜温度が確保できないため適さない。また、耐水性を確保することも出来ない。
３０重量％以上になると酢酸ビニル樹脂エマルジョンが余りに柔らかくなりすぎ接着剤組成物の凝集力の低下が著しく好ましくない。
The acrylic resin emulsion is preferably used in the range of 2 to 30% by weight, more preferably 3 to 20% by weight of the solid content of the vinyl acetate resin emulsion to be prepared. If it is 2% by weight or less, the minimum film-forming temperature of 2 ° C. or less of the prepared vinyl acetate resin emulsion cannot be secured, which is not suitable. Moreover, water resistance cannot be ensured.
If it is 30% by weight or more, the vinyl acetate resin emulsion becomes too soft, and the cohesive strength of the adhesive composition is remarkably lowered.
上記のようなアクリル樹脂エマルジョンの存在下おいて、ＶＡｃが乳化重合、或いはＶＡｃとＡＡｃ基含有モノマーが乳化共重合されて本発明の接着剤組成物に調製される。
ＡＡｃ基含有モノマーとしてはアセトアセトキシエチルアクリレート、アセトアセトキシエチルメタクリレートなどが挙げられ、ＶＡｃ１００重量部に対して２〜２５重量部、より好ましくは３〜１０重量部が採用される。
２重量部以下では十分な耐水性が得られないため好ましくない。一方、２５重量部以上では酢酸ビニルの重合性が著しく低下するため採用できない。
In the presence of the acrylic resin emulsion as described above, VAc is emulsion-polymerized, or VAc and an AAc group-containing monomer are emulsion-copolymerized to prepare the adhesive composition of the present invention.
Examples of the AAc group-containing monomer include acetoacetoxyethyl acrylate and acetoacetoxyethyl methacrylate, and 2 to 25 parts by weight, more preferably 3 to 10 parts by weight, are employed with respect to 100 parts by weight of VAc.
Less than 2 parts by weight is not preferable because sufficient water resistance cannot be obtained. On the other hand, when the amount is 25 parts by weight or more, the polymerizability of vinyl acetate is remarkably lowered, so that it cannot be employed.
ＡＡｃ基含有モノマーの添加方法については、予め酢酸ビニルモノマーと混合して同時に添加しても良いし、酢酸ビニルモノマーとは別の系から添加しても良い。また、ＡＡｃ基含有モノマーの添加開始を、酢酸ビニルモノマーの添加開始から一定時間遅らせても良い。 About the addition method of an AAc group containing monomer, it may mix with a vinyl acetate monomer previously and may add simultaneously, and may add from a system different from a vinyl acetate monomer. Further, the start of addition of the AAc group-containing monomer may be delayed for a certain time from the start of addition of the vinyl acetate monomer.
また、シード重合する際にアクリル樹脂系エマルジョンに加えて、他のエマルジョンを併用することができる。特にＰＶＡを保護コロイドとするエマルジョンを併用した場合、酢酸ビニルの乳化重合時の重合性を高めたり、得られる樹脂エマルジョンの粘性を調整することができる。このような樹脂エマルジョンの例としては、酢酸ビニル樹脂エマジョン、エチレン・酢酸ビニル共重合樹脂エマルジョン、酢酸ビニル・アクリル樹脂共重合エマルジョン等が挙げられる。他の樹脂エマルジョンを、得られる酢酸ビニル樹脂系エマルジョンの固形分１００重量部に対して、３〜２０重量部を配合して乳化重合することもできる。 In addition to the acrylic resin emulsion, other emulsions can be used in combination for seed polymerization. In particular, when an emulsion using PVA as a protective colloid is used in combination, it is possible to increase the polymerizability during the emulsion polymerization of vinyl acetate or to adjust the viscosity of the resulting resin emulsion. Examples of such resin emulsions include vinyl acetate resin emulsion, ethylene / vinyl acetate copolymer resin emulsion, vinyl acetate / acrylic resin copolymer emulsion, and the like. Other resin emulsions can be emulsion polymerized by blending 3 to 20 parts by weight with respect to 100 parts by weight of the solid content of the resulting vinyl acetate resin emulsion.
実施例、比較例
攪拌機、温度計、還流冷却管を備えたフラスコ中に水、ＰＶＡ（電気化学工業株式会社 Ｂ−０５ 平均重合度５００、ケン化度８８％）、ＡＡｃＰＶＡ（日本合成化学株式会社 ゴーセファイマー Ｚ−２００ 、ケン化度９９％）を仕込んで８０℃に加熱して溶解させ、シード用のアクリル樹脂エマルジョン（以下ＡＣと略称する）を配合したのち、過硫酸アンモニウムを投入し、８０℃に保つた状態でＶＡｃ及びＡＡｃ基含有モノマーとしてのアセトアセトキシエチルアクリレート（以下ＡＡｃＥＭと略称する）を３時間かけて滴下しながら乳化重合を進めて表２、表３に記載する配合（配合数値は重量部を表す）の実施例、比較例の接着剤組成物を調製した。
なお、実施例、比較例のＡＣには、ＡＣ１、ＡＣ２、ＡＣ３、ＡＣ４、ＡＣ５、ＡＣ６として、下記の表１のモノマー組成（配合数値は重量部を表す）を採用し、攪拌機、加熱手段、還流冷却管を備えた反応容器中で、モノマーの合計１００重量部と水１２０重量部並びに乳化剤としてドデシルベンゼンスルホン酸ナトリウム２重量部を配合し、重合触媒として過硫酸アンモニウムを０．７重量部添加し、８５℃においてモノマー反応率が９５％以上になるまで乳化重合して調製したものを使用した。
Examples, Comparative Examples In a flask equipped with a stirrer, thermometer, reflux condenser, water, PVA (Denki Kagaku Kogyo Co., Ltd., B-05, average polymerization degree 500, saponification degree 88%), AAcPVA (Nippon Synthetic Chemical Co., Ltd. Goosephimer Z-200, saponification degree 99%) was charged and dissolved by heating to 80 ° C., and after blending an acrylic resin emulsion for seed (hereinafter abbreviated as AC), ammonium persulfate was added, and 80 The emulsion polymerization proceeded while dripping VAc and acetoacetoxyethyl acrylate (hereinafter abbreviated as AAcEM) as an AAc group-containing monomer over a period of 3 hours while maintaining the temperature at ℃. Represents parts by weight) and adhesive compositions of Examples and Comparative Examples were prepared.
In addition, as AC1, AC2, AC3, AC4, AC5, and AC6, the monomer composition shown in the following Table 1 (the compounding numerical value represents parts by weight) is adopted for AC of Examples and Comparative Examples, and a stirrer, heating means, In a reaction vessel equipped with a reflux condenser, a total of 100 parts by weight of monomer and 120 parts by weight of water and 2 parts by weight of sodium dodecylbenzenesulfonate as an emulsifier were blended, and 0.7 parts by weight of ammonium persulfate was added as a polymerization catalyst. The one prepared by emulsion polymerization until a monomer reaction rate of 95% or higher at 85 ° C. was used.
注）２−ＥＨＡ：アクリル酸２−エチルヘキシル、ＢＡ：アクリル酸ブチル
ＥＡ ：アクリル酸エチル、ＭＭＡ：アクリル酸メチル
Ｓｔ：スチレン、ＡＡ：アクリル酸、ＭＡＡ：メタアクリル酸
Ｃ基含有率：カルボキシル基重量％、ＭＦＴ：最低造膜温度（℃）
各接着剤組成物の性状値、接着性能、造膜温度、低温作業性などは表２、３に示す。
Note) 2-EHA: 2-ethylhexyl acrylate, BA: butyl acrylate EA: ethyl acrylate, MMA: methyl acrylate St: styrene, AA: acrylic acid, MAA: methacrylic acid C group content: carboxyl group weight %, MFT: Minimum film-forming temperature (° C)
Tables 2 and 3 show property values, adhesive performance, film-forming temperature, low-temperature workability and the like of each adhesive composition.
注）ＶＡｃ／酢酸ビニル、ＡＡｃＥＭ／アセトアセトキシエチルメタクリレート、ＡＣ１、ＡＣ２、ＡＣ３／アクリル樹脂エマルジョン、ＡＡｃＰＶＡ／アセトアセチル化ポリビニルアルコール、ＰＶＡ／ポリビニルアルコール、ＭＦＴ／最低造膜温度℃、ＡＰＳ／過硫酸アンモニウム
Note) VAc / vinyl acetate, AAcEM / acetoacetoxyethyl methacrylate, AC1, AC2, AC3 / acrylic resin emulsion, AAcPVA / acetoacetylated polyvinyl alcohol, PVA / polyvinyl alcohol, MFT / minimum film forming temperature, APS / ammonium persulfate
注）
ＶＡｃ／酢酸ビニル、ＡＡｃＥＭ／アセトアセトキシエチルメタクリレート、ＡＣ／アクリル樹脂エマルジョン、ＡＡｃＰＶＡ／アセトアセチル化ポリビニルアルコール、ＰＶＡ／一般ホリビニルアルコール、ＭＦＴ／最低造膜温度℃、ＡＰＳ／過硫酸アンモニウム、＊＊重合が進行しないため中断。
note)
VAc / vinyl acetate, AAcEM / acetoacetoxyethyl methacrylate, AC / acrylic resin emulsion, AAcPVA / acetoacetylated polyvinyl alcohol, PVA / general polyvinyl alcohol, MFT / minimum film-forming temperature C, APS / ammonium persulfate, ** polymerization Suspended because it does not progress.
測定方法
１．最低造膜温度
ＪＩＳＫ６８０４（１９９４年版）に記載の測定方法により測定した。
２．耐水接着力
ＪＩＳＫ６８０４（１９９４年版）に記載の測定方法により、カバ材同士を接着したものについて常態接着強さ（単位：Ｎ／ｍｍ２）及び耐水接着強さ（単位：Ｎ／ｍｍ２、３０℃の水中に３時間浸せきした後、２３℃の水中に１０分間浸し、ぬれたままの状態で試験）を測定した。
Measuring method 1. Minimum film-forming temperature It measured by the measuring method as described in JISK6804 (1994 edition).
2. Water-resistant adhesive strength Normal adhesive strength (unit: N / mm 2 ) and water-resistant adhesive strength (unit: N / mm 2 , 30 ° C.) of those obtained by adhering birch materials according to the measurement method described in JISK6804 (1994 edition) Was immersed in water for 3 hours, then immersed in water at 23 ° C. for 10 minutes, and the wet condition was measured).
本発明になる接着剤組成物は、可塑剤、ホルムアルデヒド或いはホルムアルデヒドを遊離する原料に使用することなく、優れた接着性能、耐水性能並びに低温造膜性を実現したもので、低温作業性に優れるため木工用、紙加工用、繊維加工用、建築用などの分野において安心して使用できる。
The adhesive composition according to the present invention achieves excellent adhesion performance, water resistance performance and low-temperature film-forming property without using it as a plasticizer, formaldehyde or a raw material that liberates formaldehyde, and is excellent in low-temperature workability. It can be used with peace of mind in fields such as woodwork, paper processing, textile processing, and construction.
Claims (5)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010229307A (en) * | 2009-03-27 | 2010-10-14 | Aica Kogyo Co Ltd | Method for producing adhesive composition and veneer decorative material |
| WO2013077293A1 (en) * | 2011-11-22 | 2013-05-30 | 三菱レイヨン株式会社 | Method for producing acrylic polymer, acrylic polymer, and plastisol composition |
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2004
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010229307A (en) * | 2009-03-27 | 2010-10-14 | Aica Kogyo Co Ltd | Method for producing adhesive composition and veneer decorative material |
| WO2013077293A1 (en) * | 2011-11-22 | 2013-05-30 | 三菱レイヨン株式会社 | Method for producing acrylic polymer, acrylic polymer, and plastisol composition |
| CN103946253A (en) * | 2011-11-22 | 2014-07-23 | 三菱丽阳株式会社 | Method for producing acrylic polymer, acrylic polymer, and plastisol composition |
| JPWO2013077293A1 (en) * | 2011-11-22 | 2015-04-27 | 三菱レイヨン株式会社 | Acrylic polymer production method, acrylic polymer, and plastisol composition |
| CN103946253B (en) * | 2011-11-22 | 2016-06-22 | 三菱丽阳株式会社 | The manufacture method of acrylic acid series polymeric compounds, acrylic acid series polymeric compounds and acrylic sol composition |
| US9453096B2 (en) | 2011-11-22 | 2016-09-27 | Mitsubishi Rayon Co., Ltd. | Method for producing acrylic polymer, acrylic polymer, and plastisol composition |
| JP2017002317A (en) * | 2011-11-22 | 2017-01-05 | 三菱レイヨン株式会社 | Acrylic polymer and method for producing plastisol composition |
| US9738743B2 (en) | 2011-11-22 | 2017-08-22 | Mitsubishi Chemical Corporation | Method for producing acrylic polymer, acrylic polymer, and plastisol composition |
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