JP5137058B2 - 2-cyanoacrylate adhesive composition for wood repair - Google Patents

Description

The present invention relates to a 2-cyanoacrylate-based adhesive composition for repairing wood, which mainly aims at repairing a defect portion due to scratches, cracks, and nodes of wood, and has good workability when processed after curing.

The 2-cyanoacrylate-based adhesive starts polymerization with weak anions such as slight moisture adhering to the adherend surface due to the unique anionic polymerization property of 2-cyanoacrylate as the main component, Various materials can be firmly bonded in a short time. For this reason, it is widely used as a so-called instantaneous adhesive in fields such as industrial use, medical use, and home use.

The demands for instant adhesives are diversifying every day, and the repair of wood listed in this topic is one of them.

2-Cyanoacrylate adhesive is a good adhesive that hardens quickly due to moisture in the air and moisture on the wood surface, and exhibits excellent adhesion speed and adhesion strength to metals, plastics, wood, rubber, etc. On the other hand, since the cured resin layer is hard, it is difficult to perform surface polishing after curing,
This causes damage to the tool and the process stops, so it cannot be said that it is a good adhesive when repairing wood by mixing an adhesive with wood flour.

Therefore, a method of filling a colored epoxy resin adhesive is usually used for repairing wood. However, since the epoxy resin has a slow curing rate, the productivity is poor, and there is a defect that the repaired part is peeled off due to poor adhesiveness.

As a method for solving the above problem, a method using a 2-cyanoacrylate adhesive has been proposed. For example, (1) a composition in which 2-cyanoacrylate is mixed with fillers as a machinability improver; A method using a two-part filling adhesive composed of inorganic or organic hollow microspheres (Patent Document 1), (2) a method using an adhesive composition having a cured product with a Shore hardness of 40 to 60 (Patent Document 2) (3) A plasticizer selected from a phthalate ester, an acetylcitrate triester, or a monomer or oligomer having a (meth) acryloyl group, and an acid content of 1.0 × 10 ^{−6 to} 10.0 × 10 ^{− A} method using a 2-cyanoacrylate-based adhesive with ⁶ gram equivalent number / g has been proposed (Patent Document 3).

  However, (1) is a two-component adhesive, which requires a step of mixing two agents immediately before use, and the characteristics of the instantaneous adhesive characterized by rapid curing with one liquid are impaired, resulting in a longer process. Yes. Further, in (2) and (3), the surface after curing is too hard, and there is a problem that the polishing treatment cannot be performed substantially. Therefore, the fast curing property and stability of the 2-cyanoacrylate adhesive itself It does not impair performance such as adhesiveness, and also maintains the characteristics of being one-component and easy to operate, and when mixed with wood flour and cured, the surface of the cured product can be polished. Development of a cyanoacrylate adhesive composition has been desired.

JP-A-6-329995

Japanese Patent No. 3389846

JP 2005-89532 A

The purpose of the present invention is not to impair the performance of the 2-cyanoacrylate adhesive itself, such as fast curability, stability and adhesiveness, and also to maintain the characteristics that it is one-component and easy to operate. It is another object of the present invention to provide a 2-cyanoacrylate adhesive composition that can be mixed with wood flour and cured, and then the surface of the cured product can be polished.

（式中、Ｒ_１は水素原子、直鎖または分岐のあるアルキル基またはアルコキシアルキル基をＲ_２は水素原子、直鎖または分岐のあるアルキル基またはアルコキシアルキル基を表し、Ｒ_１およびＲ_２は同一であっても異なっていてもよい。ｒは、１〜３の整数を表す。）により、上記課題が解決されることを見出し、発明を完成させた。 As a result of intensive studies, the inventors of the present invention (A) 2-cyano containing 0.05 to 2 parts by weight of the aromatic carboxylic acid compound represented by the formula (1) with respect to 100 parts by weight of 2-cyanoacrylate. Acrylate adhesive composition

(Wherein R ₁ represents a hydrogen atom, a linear or branched alkyl group or an alkoxyalkyl group, R ₂ represents a hydrogen atom, a linear or branched alkyl group or an alkoxyalkyl group, and R ₁ and R ₂ represent It may be the same or different. R represents an integer of 1 to 3), and the inventors have found that the above problem can be solved and completed the invention.

  The 2-cyanoacrylate-based adhesive composition of the present invention does not impair the performance of the 2-cyanoacrylate-based adhesive itself, such as fast curability, stability, and adhesiveness, and is also one-packed and easy to operate. After maintaining and repairing the wood, it is possible to polish the surface of the cured product after mixing with wood powder and curing.

As the (A) 2-cyanoacrylate in the present invention, 2-cyanoacrylate represented by the formula (2) is preferably used.

（式中Ｒは炭素数１〜１６の置換基を有していてもよい飽和または不飽和の脂肪族もしくは脂環族基又は芳香族基を示す。）

(In the formula, R represents a saturated or unsaturated aliphatic or alicyclic group or aromatic group which may have a substituent having 1 to 16 carbon atoms.)

Specific examples of (A) 2-cyanoacrylate in the present invention include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, octyl, neopentyl, cyclohexyl of 2-cyanoacrylic acid. , Ethylhexyl, dodecyl, allyl, methoxyethyl, ethoxyethyl, methoxypropyl, benzyl, phenyl, chloroethyl, tetrahydrofurfuryl and the like. Moreover, these 2-cyanoacrylates can be used 1 type or in mixture of 2 or more types.

（式中、Ｒ_１は水素原子、直鎖または分岐のあるアルキル基またはアルコキシアルキル基をＲ_２水素原子、直鎖または分岐のあるアルキル基またはアルコキシアルキル基を表し、Ｒ_１およびＲ_２は同一であっても異なっていてもよい。ｒは、１〜３の整数を表す。）で示される芳香族カルボン酸類化合物としては、例えば、サルチル酸、アセチルサリチル酸、バニリン酸、レゾルシン酸、プロトカテキュ酸、ピペロニル酸、没食子酸、没食子酸メトキシエチルエステルなどが挙げられ、これらの中でもサルチル酸およびアセチルサリチル酸が好ましい。 Formula (B) in the present invention (1)

(In the formula, R ₁ represents a hydrogen atom, a linear or branched alkyl group or an alkoxyalkyl group as an R ₂ hydrogen atom, a linear or branched alkyl group or an alkoxyalkyl group, and R ₁ and R ₂ are the same. As the aromatic carboxylic acid compound represented by (2), for example, salicylic acid, acetylsalicylic acid, vanillic acid, resorcinic acid, protocatecic acid, Examples include piperonic acid, gallic acid, methoxyethyl gallate and the like. Among these, salicylic acid and acetylsalicylic acid are preferable.

The aromatic carboxylic acid compound can be used as one or a mixture of two or more if necessary, and the addition amount is 0.05 to 2 parts by weight with respect to 100 parts by weight of 2-cyanoacrylate, It is 0.06-1.4 weight part, More preferably, it is 0.1-1 weight part. When the added amount is less than 0.05 parts by weight, sufficient softness cannot be obtained when mixed and solidified with wood flour, and the desired processability cannot be obtained. When the amount is more than 2 parts by weight, the fast curability inherent to the 2-cyanoacrylate adhesive is lowered.

Examples of the (C) fast-curing additive in the present invention usually include polyhydric alcohols, polyalkylene oxide derivatives, calixarene compounds, etc. Among them, polyalkylene oxide derivatives and calixarene compounds are preferably used.

Among the fast-curing additives, specifically as polyhydric alcohols, for example, ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol, octamethylene glycol, polybutadiene diol, chloropropylene glycol, 3-methylpentanediol, 2,2-diethylpropanediol, 2-ethyl-1,4-butanediol, glycerin, trimethylolmethane, trimethylolethane, trimethylolpropane, 1,2,6-hexanetriol, 2,5-hexanediol, etc. These derivatives include the alkyl, alkenyl, aryl, and aralkyl ethers or esters thereof, such as methyl cellosolve, ethyl cellosolve, ethylene glycol-n-butyl. Ether, ethylene glycol phenyl ether, ethylene glycol benzyl ether, propylene glycol methyl ether, tetramethylene glycol propyl ether, ethylene glycol diethyl ether, ethylene glycol acetate, ethylene glycol monolaurate, ethylene glycol monostearate, ethylene glycol distearate , Ethyl cellosolve stearate, glycerol monolaurate, glycerol monostearate, sorbitan monolaurate, cellosolve acrylate, cellosolve methacrylate, cellosolve crotonate and the like.

（式中、Ｘ_１ およびＸ_２ は、それぞれ独立に水素原子、ハロゲン原子、水酸基、置換若しくは非置換のアルキル、アルケニル、アリール又はアラルキル基を示す。ｐは１以上の整数、ｑは２以上の整数を示し、末端は環形成されていてもよい。）
なる繰り返し単位を有する化合物から選ばれた１種以上が挙げられる。 Among the fast-curing additives, the polyalkylene oxide derivative has the formula (3)

(Wherein, X ₁ and X ₂ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted alkyl, alkenyl, aryl, or aralkyl group. P is an integer of 1 or more, and q is 2 or more. An integer is shown, and the end may be ring-formed.)
1 type or more chosen from the compound which has the repeating unit which becomes.

Specific examples of the polyalkylene oxide derivative include, for example, a trioxane polymer, a polyalkylene glycol (for example, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (# 200, # 400, # 600, # 1000, # 2000). Etc.), dipropylene glycol, polypropylene glycol, polytetramethylene oxide, poly 3,3-bis (chloromethyl) butylene oxide, poly 1,3-dioxolane, ethylene oxide-propylene oxide block polymer, etc.), polyalkylene glycol monoether (For example, methyl carbitol, carbitol, diethylene glycol-n-butyl ether, diethylene glycol phenyl ether, diethylene glycol ben Ether, dipropylene glycol ethyl ether, tripropylene glycol methyl ether, polyethylene glycol methyl ether, polyethylene glycol propyl ether, polyethylene glycol lauryl ether, polyethylene glycol stearyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol allyl ether, etc.), poly Alkylene glycol diethers (eg, diethylene glycol diethyl ether, diethylene glycol di-n-butyl ether, triethylene glycol dimethyl ether, tetraethylene glycol distearyl ether, polyethylene glycol dimethyl ether, etc.), polyalkylene glycol monoesters (eg, diethylene glycol) Nopropionate, tetraethylene glycol monoacetate, tripropylene glycol mono-n-butyrate, polyethylene glycol monoacetate, polyethylene glycol monopropionate, polyethylene glycol laurate, polyethylene glycol sebacate, polyethylene glycol stearate, polyethylene glycol oleate, poly Oxyethylene sorbitan monolaurate, diethylene glycol acrylate, diethylene glycol methacrylate, diethylene glycol crotonate, etc.), polyalkylene glycol diesters (eg, diethylene glycol diacetate, diethylene glycol dipropionate, diethylene glycol diacrylate, diethylene glycol distearate, Diethylene glycol dimethacrylate, tetraethylene glycol dicrotonate, polyethylene glycol diacetate, polyethylene glycol di-n-butyrate, polyethylene glycol diurarate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polyethylene glycol dicrotonate, polyethylene glycol di- 2-cyanoacrylate, polyethylene glycol stearyl-methacrylate, polyethylene glycol lauryl-acrylate and the like. ), Polyalkylene glycol monoether monoester (for example, methyl carbitol, carbitol, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, tetraoxyethylene glycol monomethyl ether, polyoxyethylene glycol) Acrylates, methacrylates, crotonates, or 2-cyanoacrylates of glycol monoether compounds such as monolauryl ether and polyoxyethylene glycol monononyl phenyl ether), other bisphenol A-polyalkylene oxide adducts, trimethylolpropane-polyalkylene Oxide adduct, glycerin-polyalkyleneoxy De adducts, adipic acid - polyalkylene oxide adducts, trimellitic acid - such as polyalkylene oxide adducts. Other cyclic compounds include, for example, 18-crown-6-ether, 15-crown-5-ether, 12-crown-4-ether, dithio-15-crown ether, dibenzo-18-crown-6-ether, dicyclohexyl- 18-crown-6-ether, 1.2-naphth-15-crown-5-ether, 1.2-methylbenzo-18-crown-6-ether, etc. Among these, polyethylene glycol # 200, polyethylene glycol # 400, polyethylene Glycol # 600, polyethylene glycol # 1000, polyethylene glycol # 2000, polyethylene glycol monomethyl ether acrylate, polyethylene glycol monomethyl ether methacrylate, polyethylene glycol monomer Ether ether crotonate, polyethylene glycol monomethyl ether 2-cyanoacrylate, polyethylene glycol monoethyl ether acrylate, polyethylene glycol monoethyl ether methacrylate, polyethylene glycol monoethyl ether crotonate, polyethylene glycol monoethyl ether 2-cyanoacrylate, polyethylene Glycol monophenyl ether acrylate, polyethylene glycol monophenyl ether methacrylate, polyethylene glycol monophenyl ether crotonate, polyethylene glycol monophenyl ether 2-cyanoacrylate, 18-crown-6-ether, 15-crown-5-ether 12-crown-4-ether is preferred Good. These additives may be used alone or in combination of two or more.

（式中、Ｒ_４は水素原子、更に置換されていてもよいアルキル基、置換されていてもよいアルコキシル基および置換されていてもよいアルキルオキシカルボニル基であり、Ｒ_５はＨ又は置換されていてもよいアルキル基である。また、ｙは４，６又は８である。）
で示されるカリックスアレン化合物が挙げられる。このようなカリックスアレン化合物としては、具体的には、５，１１，１７，２３，２９，３５−ヘキサ−ｔｅｒｔ−ブチル−３７，３８，３９，４０，４１，４２−ヘキサヒドロオキシカリックス〔６〕アレン、３７，３８，３９，４０，４１，４２−ヘキサヒドロオキシカリックス〔６〕アレン、或いは例えば特開昭６０−１７９４２８号公報に記載されている３７，３８，３９，４０，４１，４２−ヘキサ−（２−エトキシ−２−オキソエトキシ）−カリックス〔６〕アレン、２５，２６，２７，２８−テトラ−（２−エトキシ−２−オキソエトキシ）−カリックス〔４〕アレン等が挙げられ、これらの中でも５，１１，１７，２３，２９，３５−ヘキサ−ｔｅｒｔ−ブチル−３７，３８，３９，４０，４１，４２−ヘキサヒドロオキシカリックス〔６〕アレンおよび２５，２６，２７，２８−テトラ−（２−エトキシ−２−オキソエトキシ）−カリックス〔４〕アレンが好ましい。 As the calixarene compound, a conventionally known calixarene compound can be used, and specifically, the formula (4)

(Wherein R ₄ is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxyl group and an optionally substituted alkyloxycarbonyl group, and R ₅ is H or substituted. And y is 4, 6 or 8.)
The calixarene compound shown by these is mentioned. As such calixarene compounds, specifically, 5,11,17,23,29,35-hexa-tert-butyl-37,38,39,40,41,42-hexahydroxycalix [6 ] Allene, 37,38,39,40,41,42-hexahydroxycalix [6] allene, or 37,38,39,40,41,42 described in, for example, JP-A-60-179428 -Hexa- (2-ethoxy-2-oxoethoxy) -calix [6] arene, 25,26,27,28-tetra- (2-ethoxy-2-oxoethoxy) -calix [4] allene and the like. Among these, 5,11,17,23,29,35-hexa-tert-butyl-37,38,39,40,41,42-hexahydrooxy Calix [6] arene and 25,26,27,28- tetra - (2-ethoxy-2-oxo-ethoxy) - calix [4] arene is preferred.

The addition amount of the quick curing additive is 0.05 to 2 parts by weight, preferably 0.1 to 1 part by weight, with respect to 100 parts by weight of 2-cyanoacrylate. When the added amount is more than 2 parts by weight, sufficient softness cannot be obtained when mixed and solidified with wood flour, and the processability is lowered. When the added amount is less than 0.05 parts by weight, the 2-cyanoacrylate adhesive is originally The fast curability it has decreases.

Specific examples of the (D) anionic polymerization inhibitor in the present invention include sulfur dioxide, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, boron trifluoride diethyl ether, borohydrofluoric acid, and trialkylborate. Of these, sulfur dioxide, boron trifluoride diethyl ether, and borohydrofluoric acid are preferable. Of these, borofluoric acid is more preferable, and these compounds can be used alone or in combination of two or more according to the purpose.

The addition amount of the anionic polymerization inhibitor is 0.00001 to 0.01 part by weight with respect to 100 parts by weight of 2-cyanoacrylate, and preferably 0.00005 to 0.005 part by weight.
If the added amount is less than 0.00001 part by weight, sufficient softness cannot be obtained when mixed and solidified with wood flour, resulting in a decrease in workability. If the added amount is more than 0.01 part by weight, a 2-cyanoacrylate adhesive is used. Decreases the inherent fast curability.

The 2-cyanoacrylate adhesive of the present invention can be mixed with a thickener such as an elastomer as long as the effects of the present invention are not inhibited.

The elastomer used as necessary in the present invention means an elastomer having a rubber-like elasticity around room temperature where α-cyanoacrylate can be dissolved or dispersed, and specifically, an acrylate copolymer elastomer. , Styrene-butadiene copolymer elastomer, polyurethane elastomer, chloroprene elastomer, carboxylated acrylonitrile-butadiene copolymer elastomer, polyester elastomer, fluorine elastomer, polyisoprene elastomer, epichlorohydrin elastomer, ethylene-propylene copolymer Those selected from elastomers, ethylene-vinyl acetate copolymer elastomers and the like may be mentioned, and these may be used alone or in combination of two or more.

In particular, acrylic ester copolymer elastomers, polyester elastomers, and urethane elastomers are preferably used. The acrylic ester copolymer elastomer is generally called an acrylic rubber. Specifically, for example, methyl acrylate, ethyl acrylate, butyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, acrylic acid 2- Binary, ternary or higher copolymers made of chloroethyl, acrylic acid, acrylonitrile, ethylene, etc., which are Knoxtite A, PA (Nippon Oil Seal), Nipol AR (ZEON), Baymac (Vamac) (DuPont), Leo Coat R (Toray Records), Paracron BX (Shin Nakamura Chemical), Cyanacryl (Cyanacryl R, L, C) (American Cyanamid), Hycar (BF Gudrich), What is marketed under the trade name such as Toacron AR, SA (Toa Paint) It is used as it is in a sulfurized or uncrosslinked state. Examples of commercially available polyester elastomers include Elitel UE3400 (manufactured by Unitika), Byron (Toyobo), Chemit (Toray), etc., and commercially available urethane elastomers include Desmocol (Sumitomo Bayer Urethane). (E.g., urethane-based elastomer).

In addition, the 2-cyanoacrylate adhesive composition of the present invention includes a stabilizer (for example, hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, conventionally used by adding to a 2-cyanoacrylate adhesive). Radical polymerization inhibitors such as catechol and pyrogallol), plasticizers (dimethyl phthalate, diethyl phthalate, diisodecyl phthalate, etc.), colorants, fragrances, solvents, strength improvers, aliphatic polycarboxylic acids, aromatic poly Depending on the purpose, such as a polyvalent carboxylic acid, it can be used by appropriately adding and blending it within a range not inhibiting the stability of the 2-cyanoacrylate monomer.
(Example)

  Hereinafter, the present invention will be described in more detail with reference to examples.

<Test method>
(Wood powder curing rate)
1 g of cedar powder was weighed on a polyethylene plate having a diameter of 31.0 mm, and 0.1 g of 2-cyanoacrylate adhesive was dropped on it, and the time until curing was completed was measured.

(viscosity)
It measured with the B-type rotational viscometer (made by Toki Sangyo) by the method according to JIS K-6833 "General test method of adhesives". In the table, the initial viscosity is a value measured immediately after blending the adhesive composition, and the post-storage viscosity is a value measured after storing the adhesive composition at 70 ° C. for 7 days. Indicates.

(Adhesiveness)
JIS G-3141 compliant steel test piece (engineering test service) and maple test piece (engineering test service) are bonded at a bonding area of 12.5 × 25 mm, stored at room temperature for 24 hours, and then sheared. A tensile test was performed.

(Method for making wood powder mixed cured resin and machinability)
0.5 g of 100 mesh-through walnut powder or cedar powder is measured on a polyethylene plate having a diameter of 31.0 mm, and 0.5 g of 2-cyanoacrylate adhesive is dropped on it, and then stored at room temperature for 24 hours. The wood powder mixed cured resin was taken out from the polyethylene dish and cut with scissors for work (made of 420-J2 stainless steel) one day later and one week later. Hereinafter, evaluation was performed according to the criteria shown in the next section.

(Machinability criteria)
Items that could be cut smoothly without cracking were marked as ◎, those that did not crack but felt hard, △ those that had some cracks during cutting, and those that had large cracks during cutting as ×, It described in Table-1.

(A) 0.1 part by weight of salicylic acid, (C) 0.4 part by weight of Nk ester M90G and (D) 0.001 part by weight of borohydrofluoric acid with respect to 100 parts by weight of ethyl-2-cyanoacrylate Hydrochloric acid was added to prepare an adhesive composition 1. Each test of wood powder curing rate, viscosity, adhesiveness, and machinability was performed on the 2-cyanoacrylate adhesive composition 1 and the results are shown in Table 1.

In Example 1, with respect to 100 parts by weight of (A) ethyl-2-cyanoacrylate, instead of adding 0.1 parts by weight of (B) salicylic acid, (B) 0.3 parts by weight of salicylic acid was added. In the same manner as in Example 1, a 2-cyanoacrylate adhesive composition 2 was prepared. With respect to this 2-cyanoacrylate adhesive composition 2, each test of wood powder curing rate, viscosity, adhesiveness and machinability was carried out, and the results are shown in Table 1.

In Example 1, instead of adding 0.001 part by weight of (D) hydrofluoric acid to 100 parts by weight of (A) ethyl-2-cyanoacrylate, (D) 0.005 part by weight of borohydrofluoric acid A 2-cyanoacrylate-based adhesive composition 3 was prepared in the same manner as in Example 1 except that was added. With respect to this 2-cyanoacrylate adhesive composition 3, each test of wood powder curing rate, viscosity, adhesiveness, and machinability was performed, and the results are shown in Table 1.

  In Example 1, with respect to 100 parts by weight of (A) ethyl-2-cyanoacrylate, instead of adding 0.1 part of (B) salicylic acid, (B) 0.5 part by weight of acetylsalicylic acid was added. In the same manner as in Example 1, a 2-cyanoacrylate adhesive composition 4 was prepared. About this 2-cyanoacrylate adhesive composition 4, each test of wood powder hardening rate, a viscosity, adhesiveness, and machinability was implemented, and the result was described in Table 2.

  In Example 1, instead of adding 0.1 part by weight of (B) salicylic acid and 0.4 part by weight of (C) Nk ester M90G to 100 parts by weight of (A) ethyl-2-cyanoacrylate, (B) salicylic acid A 2-cyanoacrylate adhesive composition 5 was prepared in the same manner as in Example 1 except that 0.3 part by weight and 0.5 part by weight of (C) 12-crown-4-ether were added. About this 2-cyanoacrylate adhesive composition 5, each test of wood powder hardening rate, a viscosity, adhesiveness, and machinability was implemented, and the result was described in Table 2.

  In Example 1, instead of adding 0.1 part by weight of (B) salicylic acid and 0.4 part by weight of (C) Nk ester M90G to 100 parts by weight of (A) ethyl-2-cyanoacrylate, (B) salicylic acid 2-Cyanoacrylate adhesive composition 6 in the same manner as in Example 1 except that 0.3 part by weight, 0.5 part by weight of (C) 12-crown-4-ether and 1 part by weight of Leocoat R1020 were added. Was prepared. With respect to this 2-cyanoacrylate adhesive composition 6, each test of wood powder curing rate, viscosity, adhesiveness, and machinability was performed, and the results are shown in Table 2.

(Comparative Example 1)
In Example 1, 2-cyanoacrylate adhesive composition 7 was prepared in the same manner as in Example 1 except that 0.1 part by weight of salicylic acid was not added to 100 parts by weight of (A) ethyl-2-cyanoacrylate. Prepared. With respect to this 2-cyanoacrylate-based adhesive composition 7, tests of wood powder curing rate, viscosity, adhesiveness, and machinability were performed, and the results are shown in Table 3.

(Comparative Example 2)
In Example 1, instead of adding 0.1 part by weight of (B) salicylic acid and 0.4 part by weight of (C) Nk ester M90G to 100 parts by weight of (A) ethyl-2-cyanoacrylate, (C) 12 A 2-cyanoacrylate adhesive composition 8 was prepared in the same manner as in Example 1 except that 0.5 parts by weight of crown-4-ether and 20 parts by weight of tributyl acetylcitrate (ATBC) were added. . The 2-cyanoacrylate adhesive composition 8 was subjected to each test of wood powder curing rate, viscosity, adhesiveness, and machinability, and the results are shown in Table 3.

ＳＡ：サリチル酸 ＡＳＡ：アセチルサルチル酸
Ｍ９０Ｇ：メトキシポリエチレングリコール＃４００メタクリレート
（新中村化学工業製）

SA: salicylic acid ASA: acetylsalicylic acid M90G: methoxypolyethylene glycol # 400 methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)

１２ＣＲＥ：１２−クラウン−４−エーテル（田岡化学工業製）
Ｒ１０２０：レオコートＲ１０２０（アクリルゴム 東レコーテックス製）

12CRE: 12-crown-4-ether (Taoka Chemical Industries)
R1020: Leocoat R1020 (acrylic rubber, manufactured by Toray Cortex)

Claims (3)

A 2-cyanoacrylate-based adhesive composition for wood repair used by mixing with wood flour, (A) aromatic carboxylic acids represented by formula (1) with respect to 100 parts by weight of 2-cyanoacrylate 0.05 to 2 parts by weight of compound, (C) 0.05 to 2 parts by weight of fast-curing additive, (D) 0.00001 to 0.01 parts by weight of an anionic polymerization inhibitor 2-cyanoacrylate adhesive composition.

(Wherein R ₁ represents a hydrogen atom, a linear or branched alkyl group or an alkoxyalkyl group, R ₂ represents a hydrogen atom, a linear or branched alkyl group or an alkoxyalkyl group, and R ₁ and R ₂ represent (It may be the same or different. R represents an integer of 1 to 3.) (B) The 2-cyanoacrylate adhesive composition for wood repair according to claim 1, wherein the aromatic carboxylic acid compound represented by the formula (1) is salicylic acid and / or acetylsalicylic acid. (D) An anionic polymerization inhibitor is borohydrofluoric acid, The 2-cyanoacrylate adhesive composition for wood repair as described in any one of Claim 1 or 2 characterized by the above-mentioned .