TW201736539A - Adhesive composition - Google Patents

Abstract

The present invention relates to an adhesive composition useful for adhering low surface energy substrate such as polypropylene and the like, which is superior in safety as compared with conventionally known acrylic adhesives for low surface energy substrate and does not require primers. The adhesive composition of the present invention contains a compound having a polymerizable unsaturated group such as (meth) acrylic monomer, a reducing agent, and a polyamine, wherein the reducing agent is a carboxylate of transition metal, the polyamine is a polyamine having at least one tertiary amino group.

Description

Adhesive composition

The present invention relates to an adhesive composition.

In the case of an adhesive which can be used for a low surface energy substrate such as polypropylene, it is known as an acrylic adhesive using an alkylborane/amine complex initiator, and a cyanoacrylate using a primer. An ester-based adhesive.

However, in the case of an acrylic adhesive using an alkylborane/amine complex initiator, the alkylborane of the raw material spontaneously ignites when exposed to air, and therefore must be produced in an apparatus for insulating air, which is costly. main reason. Further, although the alkylborane/amine complex is formed to be stable, an alkylborane is formed upon contact with an acidic substance, and thus the alkyl borane/amine complex-containing adhesive composition is operationally operated. Need to pay attention.

Since the cyanoacrylate-based adhesive is hardened by moisture, there is a problem that it is affected by the environment when it is used such as humidity. Further, in the case of a low surface energy substrate such as polypropylene, after the primer is applied as a pre-step to the subsequent predetermined surface of the substrate, the adhesive main agent must be applied immediately and adhered, thereby increasing the number of steps and Make the job a cumbersome problem. However, after the primer is applied, there is a problem that the strength is extremely lowered if it is left for a long period of time.

Further, in the case of an adhesive suitable for a difficult-to-adhesive plastic such as polyphenylene ether, polypropylene, or aromatic nylon, there are known chlorosulfonated polyethylene, styrene and/or acrylic monomers, transition metal compounds, and A radically curable adhesive composition of a polyamine compound (refer to Patent Document 1). The radical-curable adhesive composition described in Patent Document 1 can be obtained by using chlorosulfonated polyethylene to obtain the toughness of the adhesive.

[Previous Technical Literature] Patent literature

Patent Document 1: Patent Laid-Open Publication No. 2009-51944

An object of the present invention is to provide a binder composition which can be used for a low surface energy substrate such as polypropylene, and which is superior in safety to an acrylic binder of a low surface energy substrate which is conventionally known, and which does not require a primer. The adhesive composition of the agent.

As a result of deliberate review of the above problems, the present inventors have found that a compound containing a polymerizable unsaturated group such as a (meth)acrylic monomer, and a specific reducing agent and a specific polyamine adhesive composition are found. The above problem can be solved and the present invention is completed.

That is, the adhesive composition of the present invention contains a compound containing a polymerizable unsaturated group, a reducing agent, and a polyamine, and the reducing agent is a carboxylate of a transition metal, and the polyamine is Contain at least one A grade 3 amine based polyamine.

The compound containing a polymerizable unsaturated group is preferably a (meth)acrylic monomer.

The carboxylate of the transition metal is preferably at least one selected from the group consisting of iron carboxylate and copper carboxylate.

The valence of the transition metal constituting the carboxylate of the transition metal is preferably 2 or less.

The above polyamine is preferably a polyamine having at least two tertiary amine groups.

At least a part of the aforementioned (meth)acrylic monomer is preferably a polar group-containing (meth)acrylic monomer.

The aforementioned polar group preferably contains at least one atom selected from the group consisting of oxygen and nitrogen.

The molar ratio of the aforementioned reducing agent to the aforementioned polyamine (reducing agent: polyamine) is preferably from 1:0.05 to 1:5.

It is preferable to contain 0.01 to 1 mmol of the above-mentioned reducing agent with respect to 1 g of the compound containing a polymerizable unsaturated group.

The adhesive composition of the present invention may also contain an oxidizing agent.

The oxidizing agent is preferably at least one selected from the group consisting of superoxide and peroxide.

According to the present invention, a subsequent adhesive composition for a low surface energy substrate such as polypropylene can be obtained. The adhesive composition of the present invention is superior in safety to the acrylic adhesive for low surface energy base materials which are generally known, and does not require a primer.

Next, the present invention will be specifically described.

In the present invention, the compound containing a polymerizable unsaturated group means a (meth)acrylic monomer, a vinyl chloride, a vinyl acetate or the like, and particularly preferably a (meth)acrylic monomer. Among them, "(meth)acrylic acid" is used to collectively refer to acrylic acid and methacrylic acid. That is, "(meth)acrylic monomer" is intended to be used collectively as an acrylic monomer and a methacrylic monomer. Further, "(meth) acrylate" is intended to be used collectively as acrylate and methacrylate.

The adhesive composition of the present invention is characterized by comprising: a compound containing a polymerizable unsaturated group, a reducing agent, and a polyamine, wherein the reducing agent is a carboxylate of a transition metal, and the polyamine has at least one Grade 3 amine based polyamine.

[Compound containing polymerizable unsaturated group]

The adhesive composition of the present invention contains a compound containing a polymerizable unsaturated group, and a (meth)acrylic acid-containing monomer is preferred.

In the adhesive composition of the present invention, the compound containing a polymerizable unsaturated group is preferably a (meth)acrylic monomer. Hereinafter, an adhesive composition in which a compound containing a polymerizable unsaturated group is a (meth)acrylic monomer, that is, a (meth)acrylic monomer, a reducing agent, and a polyamine, and the above reduction The agent is a carboxylate of a transition metal, and the above polyamine is described as an adhesive composition of a polyamine having at least one tertiary amino group.

The composition of the subsequent agent is not polymerizable by (meth)acrylic monomer or the like. The compound of the saturated group is polymerized, followed by a substrate or the like.

((meth)acrylic monomer)

The (meth)acrylic monomer is an acrylic monomer or a methacrylic monomer as described above. Further, an acrylic monomer, which is a monomer containing propylene fluorenyl (H ₂ C=CH-CO-), a monomer of methacrylic acid, which is a methacryl oxime group (H ₂ C=CCH ₃ -CO-) body.

As the (meth)acrylic monomer, at least one monomer selected from the group consisting of an acrylic monomer and a methacrylic monomer can be used.

Examples of the (meth)acrylic monomer include a (meth)acrylic monomer having a polar group in a portion other than an acrylonitrile group or a methacrylonitrile group, and a (meth)acrylic acid group having no polar group. body.

The polar group is preferably at least one atom selected from the group consisting of oxygen, nitrogen, and sulfur, and more preferably at least one atom selected from the group consisting of oxygen and nitrogen.

Examples of the (meth)acrylic monomer having a polar group include an oxygen-containing (meth)acrylic monomer, a nitrogen-containing (meth)acrylic monomer, and a sulfur-containing (meth)acrylic acid. Preferably, the (meth)acrylic acid monomer containing oxygen and the (meth)acrylic acid monomer containing nitrogen are preferred.

Examples of the oxygen-containing (meth)acrylic monomer include tetrahydrofurfuryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and glycidyl (meth)acrylate. Methyl (meth)acrylate, (meth)acrylic acid-(3-ethyloxetane-3-yl)methyl ester, and the like.

Examples of the nitrogen-containing (meth)acrylic monomer include dimethylaminoethyl (meth)acrylate and diethylamine methacrylate. Ethyl ethyl ester, dimethyl (meth) acrylamide, acryl hydrazino or the like.

Examples of the sulfur-containing (meth)acrylic monomer include (meth)acrylic acid-2-methylthioethyl ester.

Examples of the (meth)acrylic monomer which does not contain a polar group include a (meth)acrylate type monomer and (meth)acrylic acid. Specific examples of the (meth)acrylate-based monomer include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and isopropyl (meth)acrylate. Ester, butyl (meth)acrylate, isobutyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, ( Stearyl methacrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isodecyl (meth) acrylate, and the like.

In the case of the (meth)acrylic monomer, one type may be used alone or two or more types may be used.

In the case of the (meth)acrylic monomer, it is preferred that at least a part of the (meth)acrylic monomer is a (meth)acrylic monomer having a polar group. The (meth)acrylic monomer is preferably 10 to 100 parts by mass, more preferably 30 to 100 parts by mass, based on 100 parts by mass of the (meth)acrylic monomer, of the (meth)acrylic monomer having a polar group. Especially preferably from 50 to 100 parts by mass.

In the case of a (meth)acrylic monomer, although the detailed mechanism is unknown, the use of a (meth)acrylic monomer containing a polar group can improve the adhesion strength to a low surface energy substrate such as polypropylene. Tetrahydrofurfuryl methacrylate, 2-hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, dimethyl methacrylate, glycidyl (meth) acrylate, Methoxyethyl acrylate, (3-ethyloxaindole-3-yl)methyl (meth)acrylate, and propylene fluorenyl porphyrin are preferred, tetrahydrofurfuryl (meth) acrylate, methacrylic acid More preferably, 2-hydroxyethyl ester, dimethylaminoethyl methacrylate, and dimethyl acrylamide.

[reducing agent]

The adhesive composition of the present invention contains a reducing agent, and the reducing agent is a carboxylate of a transition metal.

The adhesive composition of the present invention can be used for the subsequent deposition of a low surface energy substrate such as polypropylene by containing the reducing agent and a polyamine described later.

The transition metal constituting the carboxylate of the transition metal may, for example, be iron, copper, zinc, nickel, cobalt, manganese or chromium, and preferably iron or copper. That is, in terms of the carboxylate of the transition metal, iron carboxylate or copper carboxylate is preferred.

The valence of the transition metal constituting the carboxylate of the transition metal is usually 2 or less, and more preferably 1 or 2. When the transition metal is iron, it is 2 valence, and when it is copper, it is preferably valence.

Further, examples of the carboxylate of the transition metal include a transition metal acetate, a transition metal formate, a transition metal oxalate, a transition metal stearate, and a transition metal 2-B. The hexanoic acid salt, the naphthenate of the transition metal, the benzoate of the transition metal, and the like, and the acetate of the transition metal and the formate of the transition metal are preferred.

Further, the carboxylate of the transition metal may be contained in the adhesive composition in the form of a hydrate.

Examples of the carboxylate of the transition metal are as follows: Ferrous acid, cuprous acetate, ferrous acetate, cuprous formate, ferrous oxalate, cuprous oxalate, ferrous stearate, cuprous stearate, ferrous (bis-ethylhexanoate), bis ( 2-ethylhexanoic acid) cuprous, ferrous hexacarboxylate or cuprous hexacarboxylate, and ferrous acetate, cuprous acetate, ferrous formate, preferably ferrous acetate or ferrous acetate.

The carboxylate of the transition metal may be used singly or in combination of two or more.

[polyamine]

The adhesive composition of the present invention contains a polyamine, wherein the polyamine refers to a molecule containing two or more amines in the molecule, and the polyamine used in the present invention contains at least one tertiary amine group.

The polyamine-based molecule used in the present invention contains two or more amines, and usually contains 2 to 6 amines in the molecule, and more preferably 2 to 4 amines, and 2 or 3 amines. good. Within the foregoing range, it is preferable in terms of balance between adhesion and cost.

The polyamine used in the present invention contains at least one tertiary amine group, and more preferably contains at least two tertiary amine groups, and contains at least two tertiary amine groups, and does not contain primary and secondary amines. The base is more preferably, particularly preferably having two or three tertiary amine groups and not containing the primary and secondary amine groups.

Examples of the polyamine used in the present invention include N, N, N', N'-tetramethylethylenediamine, N, N, N', N", N"-pentamethyldi Ethylenetriamine, tris[2-(dimethylamino)ethyl]amine, N,N-dimethyl-1,2-ethanediamine, 1,1,4,7,10,10-hexa Triethylenetetramine, 1,4,8,11-tetramethyl-1,4,8,11- Tetraazacyclotetradecane, 2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine, 4,4'-di-3 butyl-2,2' -bipyridine, tris(2-pyridylmethyl)amine, N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine, and N,N,N',N'- Tetramethylethylenediamine, N,N,N',N",N"-pentamethyldiethylenetriamine, and tris[2-(dimethylamino)ethyl]amine are preferred.

In the case of the polyamine, one type may be used alone or two or more types may be used.

[Binder composition]

The adhesive composition of the present invention is characterized in that it contains a compound containing a polymerizable unsaturated group such as a (meth)acrylic monomer, a reducing agent, and a polyamine, and the reducing agent is a carboxylate of a transition metal. And the aforementioned polyamine is a polyamine having at least one tertiary amino group. As the compound containing a polymerizable unsaturated group such as a (meth)acrylic monomer, a reducing agent, and a polyamine, the above may be used.

The adhesive composition of the present invention can be used as a subsequent adhesive composition for a low surface energy substrate such as polypropylene, and is superior in safety to an acrylic adhesive for a low surface energy substrate which is conventionally known, and is not required to be used. Primer.

The adhesive composition of the present invention reacts with a reducing agent via an oxygen present in an environment such as air and/or an oxidizing agent added as an optional component to generate a radical, and is unsaturated by a (meth)acrylic monomer or the like. The radical polymerization of the compound of the base serves as a binder.

The reason why the adhesive composition of the present invention is suitable for the subsequent surface of the low surface energy substrate is not clear, but the inventors of the present invention have speculated that it should be Since the transition metal carboxylate of the reducing agent of the present invention and the polyamine can form a transition metal complex having an appropriate catalyst activity, the metal complex is reacted with oxygen in the air or an oxidizing agent as an optional component. a highly active O radical such as an OH radical is generated, and hydrogen is extracted from a CH bond on the surface of a low surface energy substrate such as polypropylene, and is formed by a C radical grafted (meth)acrylic acid monomer or the like which is formed. The compound of the polymerizable unsaturated group is obtained by the strong bond of the conjugated bond at the subsequent interface.

In the foregoing adhesive composition, the molar ratio of the reducing agent to the polyamine (reducing agent: polyamine) is usually 1:0.05 to 1:5, and more preferably 1:0.1 to 1:4, 1: 0.2 to 1:3 is even better.

In the above adhesive composition, when the oxidizing agent as an optional component is not contained, the molar ratio of the reducing agent to the polyamine (reducing agent: polyamine) is preferably 1:0.7 to 1:4, and 1:1 to 1:3 is better. When it is in the above range, since the carboxylate of the transition metal is easily dissolved or dispersed, it is also possible to carry out polymerization as appropriate to make the adhesion force stronger and therefore more preferable.

Further, in the adhesive composition, when the oxidizing agent is contained as an optional component, the molar ratio of the reducing agent to the polyamine (reducing agent: polyamine) is preferably 1:0.05 to 1:4, 1:0.2. Better to 1:1. When it is in the above range, since the carboxylate of the transition metal is easily dissolved or dispersed, it is also possible to carry out polymerization as appropriate to make the adhesion force stronger and therefore more preferable.

In the above-mentioned adhesive composition, the reducing agent is preferably contained in an amount of 0.01 to 1 mmol, more preferably 0.05 to 0.5 mmol, based on 1 g of the compound containing a polymerizable unsaturated group such as the (meth)acrylic acid monomer. In the foregoing range, the hardening speed of the adhesive and the subsequent properties are balanced and thus more good.

The adhesive composition contains a compound containing a polymerizable unsaturated group such as a (meth)acrylic monomer, a reducing agent, and a polyamine. The oxidizing agent of any component may also be contained in the subsequent composition.

Further, the adhesive composition may further contain a compound containing a polymerizable unsaturated group such as a (meth)acrylic monomer, a reducing agent, and a polyamine, and a component other than the oxidizing agent which can be used arbitrarily (other components). .

Other ingredients, adjustable: plasticizer, slip agent, hardening accelerator, viscosity agent, film forming aid, mold release agent, filler, antifoaming agent, heat-resistant agent, anti-flammability agent, anti-charged Agent, conductive agent, ultraviolet absorber, antifogging agent, antibacterial/mold inhibitor, photocatalyst, dye, pigment, coupling agent, tactile denaturing agent, flexible agent, reinforcing material (fiber, cloth, non-woven fabric, etc.) ), a curable monomer/oligomer other than a (meth)acrylic monomer, a solvent, and the like.

The oxidizing agent is not particularly limited as long as it can be combined with the reducing agent used in the present invention and has a role as a redox initiator, and examples thereof include a peroxide and a superoxide.

Examples of the peroxides include organic peroxides and inorganic peroxides. Examples of the organic peroxide include diterpene peroxide, alkyl peroxylate, peroxydicarbonate, monoperoxycarboester, peroxyketal, and peroxidation. A dialkyl type, a hydroperoxide type, a ketone peroxide type, etc., and a hydroperoxide type such as a cumene hydroperoxide type or a butyl type hydroperoxide type, or a benzamidine peroxide is preferable. Examples of inorganic peroxides include hydrogen peroxide, hydrogen peroxide water, etc., and are safe. It is preferable to use hydrogen peroxide water of 35% or less.

Examples of the superoxide include superoxide alkali metal salts such as potassium superoxide and sodium superoxide, and sodium superoxide and potassium superoxide are preferred.

The oxidizing agent may be used alone or in combination of two or more.

When the above-mentioned adhesive composition contains an oxidizing agent, when an adhesive composition is used, it can be carried out even if oxygen is not present in the surroundings.

In the above-mentioned adhesive composition, in the case of containing an oxidizing agent, the molar ratio of the reducing agent to the oxidizing agent (reducing agent: oxidizing agent) is preferably 1:2 to 1:0.01, more preferably 1:1.5 to 1:0.05.

When the above-mentioned adhesive composition contains a compound containing a polymerizable unsaturated group such as a (meth)acrylic acid monomer, a reducing agent, and a polyamine, and a component other than the oxidizing agent used arbitrarily, the amount of the other components is not In particular, it is usually from 0 to 95 parts by mass, and preferably from 5 to 90 parts by mass, per 100 parts by mass of the total of the adhesive composition.

The adhesive composition of the present invention has sufficient adhesion even if it is not modified with a chlorosulfonated polyethylene or the like. Therefore, the adhesive composition of the present invention does not need to consider the solubility of the modified polyolefin to the blended system, and the degree of freedom of blending is excellent, and the dissolution step of the polyolefin and the (meth)acrylic monomer is not required. Therefore, the productivity is excellent.

The method for producing the subsequent composition is not particularly limited. The adhesive composition of the present invention usually contains a polymerizable unsaturated group by a component constituting the composition, that is, a (meth)acrylic monomer or the like. The compound, the reducing agent, and the polyamine, and the oxidizing agent and other components which can be used arbitrarily are obtained by mixing.

In the subsequent composition, since the reducing agent itself and the mixture of the reducing agent and the polyamine react slowly with oxygen in the air, there is a need to protect the oxygen from being stored. Further, in the presence of oxygen or in the presence of an oxidizing agent, the generation of free radicals upon the contact of the oxygen or oxidizing agent with the reducing agent begins. Therefore, it is possible to mix the components before use, or to prepare an adhesive which is a two-liquid type or a multi-component type (which may also be a solid component, a powder component) which is not in contact with oxygen or an oxidizing agent and a reducing agent, and is used before use. Mix both or all of the ingredients.

The adhesive composition of the present invention can be followed by various substrates, particularly low surface energy substrates such as polypropylene. Further, the adhesive composition of the present invention is excellent in safety as compared with the conventionally known adhesive, and does not require a primer.

Since the adhesive composition of the present invention has the aforementioned characteristics, it can be followed by a substrate formed of various materials, for example, polypropylene, polyethylene, acrylonitrile butadiene styrene copolymer, nylon, polyacetal, carbon fiber. A substrate formed of a thermoplastic plastic (CFRTP) or the like can be produced, and a composite of dissimilar materials can also be produced. Therefore, it is possible to use an electric device, an automobile, a vehicle, a ship, a house equipment, or the like to form a component such as a component of various structures, a coating film, or the like.

(Example)

Next, the present invention will be further described in detail with reference to the illustrated embodiments, but the invention is not limited thereto.

[Example 1]

First weighed: 0.1 mmol of iron acetate as a reducing agent, 0.2 mmol of N,N,N',N'-tetramethylethylenediamine as a polyamine, and 1 g of tetrahydrofurfuryl methacrylate as a monomer. Into a polyethylene container. Then, it is mixed for about 1 minute until the components are uniformly dissolved or dispersed to prepare an adhesive composition.

The obtained adhesive composition and polypropylene flakes (25 mm × 100 mm × 1.6 mm thick) (two sheets) were used to form a bonding surface of 25 mm × 12.5 mm in accordance with JIS K 6850 (tensile shear strength). The adhesive composition was applied to one of the substrates in a thickness of 50 μm, and then bonded to the other substrate to prepare a sample.

Then, a plurality of samples were prepared, and the prepared sample was placed at 23 ° C, 50% RH, and the tensile force was measured at a stretching speed of 1 cm/min using a 10 kN dynamometer using a 10 kN dynamometer every 24 hours at Shimadzu Corporation. Shear strength.

Then, the strength is increased as time passes, and the time (days) required for the subsequent strength increase rate at the time of the previous measurement is 10% or less is 2 days. When the subsequent strength of the subsequent time was the adhesive strength of the sample, it was 2.16 MPa.

[Examples 2 to 6, 10 to 14, and Comparative Examples 1 to 4]

The components described in Tables 1, 2, and 4 were treated in the same manner as in Example 1 to prepare an adhesive composition of 0.1 mmol of a reducing agent, 0.2 mmol of a polyamine, and 1 g of a monomer. Further, when only one type of the monomer is shown, it is 1 g, and when it is two types, it is a total of 0.5 g, and the total amount is 1 g of the composition. The result is as Tables 1, 2, and 4.

[Examples 7 to 9]

According to the components described in Table 3, the amount of the reducing agent and the polyamine was 1 g of tetrahydrofurfuryl methacrylate in the amounts shown in Table 3, and the other components were prepared and evaluated in the same manner as in Example 1. The results are shown in Table 3.

[Example 15]

The composition of the adhesive was prepared and evaluated in the same manner as in Example 1 except that the reducing agent 0.4 mmol, the polyamine 0.1 mmol, the monomer 1 g, and the oxidizing agent 0.05 mmol were used. The results are shown in Table 5.

[Example 16]

The reducing agent was weighed 0.4 mmol of iron acetate, and it was placed in a glass bottle and capped. Polyamine is weighed 0.1mmol of N,N,N',N'-tetramethylethylenediamine, and 0.5g of tetrahydrofurfuryl methacrylate is weighed in a single system. It is packed in other glass bottles and capped. . Further, the oxidizing agent is referred to as 0.05 mmol of cumene hydroperoxide and 0.5 g of tetrahydrofurfuryl methacrylate, and is placed in another glass bottle and capped.

Then, three glass bottles and polypropylene sheets (25 mm × 100 mm × 1.6 mm thick) (two pieces) were placed and placed inside a polyethylene glove bag.

Open the lid of the glass bottle and close the entrance and exit of the glove bag. Subsequently, in the glove bag, nitrogen gas was repeatedly introduced and discharged three times, and nitrogen gas was again introduced, and the inside of the glove bag was placed in a nitrogen atmosphere, and left for 18 hours.

The contents of the three glass vials are then mixed in a glove bag to form an adhesive composition.

The measurement of the time and the subsequent strength was measured in the same manner as in Example 1. The results are shown in Table 5.

[Examples 17 to 19]

According to the components described in Table 5, in the same manner as in Example 16, a reducing agent: 0.4 mmol, a polyamine 0.1 mmol, a monomeric tetrahydrofurfuryl methacrylate 1 g, and an oxidizing agent 0.05 mmol were used to prepare an adhesive composition. Evaluate. The results are shown in Table 5.

[Examples 20 to 24]

The composition and the substrate were measured in accordance with the components shown in Table 6, and the composition of the adhesive was adjusted in the same manner as in Example 1 except that 0.1 mmol of a reducing agent, 0.2 mmol of a polyamine, and 1 g of a monomer were prepared. Further, the samples prepared in Examples 22 to 24 were placed in an oven at 80 ° C, and the strength evaluation was performed every one hour. The results are shown in Table 6.

[Example 25, Comparative Examples 5, 6]

First, the same adhesive composition as in Example 1 (Example 25) was prepared, and the composition of the adhesive was prepared in accordance with Example 57 of Japanese Patent No. 3535167, which is an alkylborane/amine complex-based adhesive. The adhesive composition (Comparative Example 5) and the cyanoacrylate-based adhesive (Aron-α, generally used, East Asian Synthetic Company) (Comparative Example 6), the following safety test and unused bottom The adhesion of the paint was compared.

(safety test)

The adhesive composition (adhesive) was dropped into an aqueous acetic acid solution, and the change was visually observed.

(adhesiveness when no primer is used)

A 50 μm thick adhesive composition (adhesive) was applied to the back surface of a PP plate (KOBE POLYSHEET PP-N-BN, Shin-Kobe), and then bonded, and cured at 23 ° C, 50% RH for 7 days, and Shimadzu The Autograph AG-X of the manufacturing institute measured the tensile shear strength at a tensile speed of 1 cm/min using a 10 kN dynamometer. The results are shown in Table 7.

The reducing agent, polyamine, monomer, and oxidizing agent used in the examples and comparative examples are as follows.

(reducing agent)

Ferrous acetate: manufactured by Tokyo Chemical Industry, (C ₂ H ₃ O ₂ ) ₂ Fe, molecular weight 173.93, 0.1 mmol = 0.0174 g, ferrous formate: Sanjin and chemical manufacturing, (HCO ₂ ) ₂ Fe. 2H ₂ O, molecular weight 181.9, 0.1 mmol=0.0182 g, cuprous acetate: manufactured by Tokyo Chemical Industry, (C ₂ H ₃ O ₂ )Cu, molecular weight 122.59, 0.1 mmol=0.0122 g, ferrous perchlorate: manufactured by Wako Pure Chemical Industries, Ltd. , Fe(ClO ₄ ) ₂ . 6H ₂ O, molecular weight 362.84, 0.1 mmol=0.0363 g, ferrous chloride: manufactured by Aldrich, FeCl ₂ , molecular weight 126.75, 0.1 mmol=0.0127 g, cuprous chloride: manufactured by Aldrich, CuCl, molecular weight 99.00, 0.1 mmol=0.0099 g,

(polyamine)

TMEDA: N, N, N', N'-tetramethylethanediamine, manufactured by Kwong Wing Chemical Co., Ltd., C ₆ H ₁₆ N ₂ , molecular weight 116.21, 0.2 mmol = 0.0232 g, PMDETA: N, N, N' , N", N"-pentamethyldiethylenetriamine, manufactured by Tokyo Chemical Industry, C ₉ H ₂₃ N ₃ , molecular weight 173.3, 0.2 mmol = 0.0347 g, Me ₆ TREN: tris[2-(dimethylamino) Ethyl]amine, manufactured by Tokyo Chemical Industry Co., Ltd., C ₁₂ H ₃₀ N ₄ , molecular weight 230.4, 0.2 mmol=0.0460 g, DMAEA: N,N-dimethyl-1,2-ethanediamine, manufactured by Tokyo Chemical Industry Co., Ltd., C ₄ H ₁₂ N ₂ = 88.15 (0.2 mmol = 0.0176 g), EDA: 1,2-ethylenediamine, manufactured by Tokyo Chemical Industry Co., Ltd., C ₂ H ₈ N ₂ , molecular weight 60.10, 0.2 mmol = 0.0120 g,

(monomer)

THFMA: tetrahydrofurfuryl methacrylate, 2HEMA: 2-hydroxyethyl methacrylate, DM: dimethylaminoethyl methacrylate, DMAA: dimethyl methacrylate, THFA: tetrahydroanthracene ester,

(oxidant)

Cumene hydroperoxide: PERCUMYL H manufactured by Nippon Oil, purity 82%, C ₉ H ₁₂ O ₂ , molecular weight 152.19, 0.05 mmol = 0.0093 g, potassium superoxide: manufactured by Strem Chemicals, KO ₂ , molecular weight 71.10, 0.05 mmol = 0.0036g, hydrogen peroxide water: manufactured by Tokyo Chemical Industry, purity 35%, H ₂ O ₂ , molecular weight 34.01, 0.05mmol = 0.0049g, benzoyl peroxide: NYPER BW manufactured by Nippon Oil, purity 75%, C ₁₄ H ₁₀ O ₄ , a molecular weight of 242.22, 0.05 mmol = 0.0161 g, and the substrates used in the examples and the comparative examples are as follows.

PP: Polypropylene (KOBE POLYSHEET PP-N-BN, New Kobe Motor)

PE: Polyethylene (KOBE POLYSHEET EL-N-AN, New Kobe Motor)

ABS: Acrylonitrile Butadiene Styrene Copolymer (KOBE POLYSHEET ABS-N-WN, New Kobe Motor)

NY6: Nylon 6 (N6 (NC) standard grade, Dongpu Plastic Seiko)

NY66: Nylon 66 (N66 (NC) standard grade, Dongpu Plastic Seiko)

POM: Polyacetal (M25, Dongpu Plastic Seiko).

In each of the examples and comparative examples, the molar ratio of the reducing agent, the polyamine, the monomer, the reducing agent and the polyamine (Examples 7 to 9), the type of the oxidizing agent, the kind of the substrate, and the composition of the adhesive. The results of the evaluation were shown in Tables 1 to 6. The results of the safety test and the adhesion when the primer was not used are shown in Table 7.

In addition, in Table 4, in the case where the monomer is represented by THFA+THFMA, the monomer is TFA and THFMA, and 0.5 g (total 1 g) is used. In Table 4, where the monomer is represented by THFMA + 2HEMA, the monomers are THFMA and 2HEMA, and 0.5 g each (total 1 g) is used.

Claims (11)

An adhesive composition comprising: a compound containing a polymerizable unsaturated group, a reducing agent, and a polyamine, wherein the reducing agent is a carboxylate of a transition metal, and the polyamine has at least one amine group of 3 Polyamine. The adhesive composition according to claim 1, wherein the polymerizable unsaturated group-containing compound is a (meth)acrylic monomer. The adhesive composition according to claim 1 or 2, wherein the carboxylate of the transition metal is at least one selected from the group consisting of iron carboxylate and copper carboxylate. The adhesive composition according to any one of claims 1 to 3, wherein the valence of the transition metal constituting the carboxylate of the transition metal is 2,000 or less. The adhesive composition according to any one of claims 1 to 4, wherein the polyamine is a polyamine having at least two tertiary amine groups. The adhesive composition according to any one of claims 2 to 5, wherein at least a part of the (meth)acrylic monomer is a (meth)acrylic monomer having a polar group. The adhesive composition according to claim 6, wherein the polar group contains at least one atom selected from the group consisting of oxygen and nitrogen. The adhesive composition according to any one of claims 1 to 7, wherein the molar ratio of the reducing agent to the polyamine (reducing agent: polyamine) is 1:0.05 to 1: 5. The adhesive composition according to any one of claims 1 to 8, wherein the compound containing the polymerizable unsaturated group is 1 g contains 0.01 to 1 mmol of the aforementioned reducing agent. The adhesive composition according to any one of claims 1 to 9, which contains an oxidizing agent. The adhesive composition according to claim 10, wherein the oxidizing agent is at least one selected from the group consisting of superoxide and peroxide.