CN108368385B - Adhesive composition - Google Patents
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- CN108368385B CN108368385B CN201680072583.6A CN201680072583A CN108368385B CN 108368385 B CN108368385 B CN 108368385B CN 201680072583 A CN201680072583 A CN 201680072583A CN 108368385 B CN108368385 B CN 108368385B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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Abstract
The invention provides an adhesive composition which is useful for bonding low surface energy substrates such as polypropylene, has excellent safety compared with the acrylic adhesives for low surface energy substrates known at present, and does not need a primer. The adhesive composition of the present invention comprises a compound having a polymerizable unsaturated group such as a (meth) acrylic monomer, a reducing agent which is a carboxylic acid salt of a transition metal, and a polyamine which is a polyamine having at least one tertiary amino group.
Description
Technical Field
The present invention relates to an adhesive composition.
Background
As an adhesive useful for bonding a low surface energy substrate such as polypropylene, an acrylic adhesive using an alkylborane/amine complex initiator and a cyanoacrylate adhesive using a primer are known.
However, alkylboranes, which are raw materials for acrylic adhesives using alkylborane/amine complex initiators, naturally catch fire when they come into contact with air, and therefore, they need to be produced in facilities isolated from air, which is a factor of increasing the cost. Furthermore, the alkylborane/amine complex is relatively stable if formed, but is formed by contact with acidic species, and care is therefore also taken in handling adhesive compositions comprising the alkylborane/amine complex.
Since the cyanoacrylate-based adhesive is cured with water, there is a technical problem that it is affected by the use environment such as humidity. In the bonding of low surface energy substrates such as polypropylene, it is necessary to apply a primer to a predetermined bonding surface of the substrate as a pre-step, and then immediately apply a primary adhesive agent to bond the substrates together, which is problematic in that the number of steps is large and the operation is complicated. Further, there is a problem that the adhesive strength is extremely lowered when the primer is left for a long time after application.
As an adhesive suitable for a plastic which is difficult to adhere, such as polyphenylene ether, polypropylene, and aromatic nylon, a radical curable adhesive composition containing chlorosulfonated polyethylene, a styrene and/or acrylic monomer, a transition metal compound, and a polyamine compound is known (for example, see patent document 1). The radical-curable adhesive composition described in patent document 1 obtains the toughness of the adhesive by chlorosulfonated polyethylene.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2009-51944
Disclosure of Invention
Technical problem to be solved by the invention
The present invention addresses the problem of providing an adhesive composition useful for bonding low-surface-energy substrates such as polypropylene, which is superior in safety compared to conventionally known acrylic adhesives for low-surface-energy substrates and does not require a primer.
Technical scheme for solving technical problem
The present inventors have conducted extensive studies to solve the above-mentioned problems, and as a result, have found that a binder composition comprising a compound having a polymerizable unsaturated group such as a (meth) acrylic monomer, a specific reducing agent, and a specific polyamine can solve the above-mentioned problems, and have completed the present invention.
That is, the adhesive composition of the present invention comprises a compound having a polymerizable unsaturated group, a reducing agent and a polyamine, wherein the reducing agent is a carboxylate of a transition metal, and the polyamine is a polyamine having at least one tertiary amino group.
The compound having 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 number of the transition metal constituting the carboxylate of the transition metal is preferably 2 or less.
The polyamine is preferably a polyamine having at least two tertiary amino groups.
At least a part of the (meth) acrylic monomer is preferably a (meth) acrylic monomer having a polar group.
The above polar group preferably contains at least one atom selected from oxygen and nitrogen.
The molar ratio of the reducing agent to the polyamine (reducing agent: polyamine) is preferably 1:0.05 to 1: 5.
The content of the reducing agent is preferably 0.01 to 1mmol per 1g of the compound having a polymerizable unsaturated group.
The adhesive composition of the present invention may further comprise an oxidizing agent.
The above-mentioned oxidizing agent is preferably at least one selected from the group consisting of superoxide and peroxide.
Effects of the invention
According to the present invention, an adhesive composition useful for bonding low surface energy substrates such as polypropylene can be obtained. The adhesive composition of the present invention is superior in safety compared to conventionally known acrylic adhesives for low surface energy substrates, and does not require a primer.
Detailed Description
Next, the present invention will be specifically described.
In the present invention, the compound having a polymerizable unsaturated group may, for example, be a (meth) acrylic monomer, vinyl chloride or vinyl acetate, and a (meth) acrylic monomer is particularly preferable. Here, "(meth) acrylic acid" is used as a general meaning of acrylic acid and methacrylic acid. That is, "(meth) acrylic monomer" is used as a general meaning of acrylic monomer and methacrylic monomer. Furthermore, the method is simple. "(meth) acrylate" is used as the meaning of the generic term acrylate and methacrylate.
The adhesive composition of the invention is characterized in that: the composition comprises a compound having a polymerizable unsaturated group, a reducing agent and a polyamine, wherein the reducing agent is a carboxylic acid salt of a transition metal, and the polyamine is a polyamine having at least one tertiary amino group.
[ Compound having polymerizable unsaturated group ]
The adhesive composition of the present invention contains a compound having a polymerizable unsaturated group, and preferably contains a (meth) acrylic monomer.
In the pressure-sensitive adhesive composition of the present invention, the compound having a polymerizable unsaturated group is preferably a (meth) acrylic monomer. Hereinafter, the pressure-sensitive adhesive composition will be described mainly when the compound having a polymerizable unsaturated group is a (meth) acrylic monomer, that is, the pressure-sensitive adhesive composition contains a (meth) acrylic monomer, a reducing agent which is a carboxylic acid salt of a transition metal, and a polyamine which is a polyamine having at least one tertiary amino group.
The pressure-sensitive adhesive composition can bond substrates and the like by polymerizing a compound having a polymerizable unsaturated group such as a (meth) acrylic monomer.
((meth) acrylic acid monomer)
The (meth) acrylic monomer is an acrylic monomer or a methacrylic monomer, as described above. The acrylic monomer means having an acryloyl group (H)2C ═ CH-CO-) and the methacrylic monomer is a monomer having a methacryloyl group (H)2C＝CCH3-CO-.
As the (meth) acrylic monomer, at least one monomer selected from acrylic monomers and methacrylic monomers can be used.
Examples of the (meth) acrylic monomer include (meth) acrylic monomers having a polar group in a portion other than an acryloyl group and a methacryloyl group, and (meth) acrylic monomers having no polar group.
As the polar group, at least one atom selected from oxygen, nitrogen and sulfur is preferably contained, and at least one atom selected from oxygen and nitrogen is more preferably contained.
The (meth) acrylic monomer having a polar group may, for example, be an oxygen-containing (meth) acrylic monomer, a nitrogen-containing (meth) acrylic monomer or a sulfur-containing (meth) acrylic monomer, and preferably an oxygen-containing (meth) acrylic monomer or a nitrogen-containing (meth) acrylic monomer.
Examples of the oxygen-containing (meth) acrylic monomer include tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, methoxyethyl (meth) acrylate, and (3-ethyloxetan-3-yl) methyl (meth) acrylate.
Examples of the nitrogen-containing (meth) acrylic monomer include dimethylaminoethyl (meth) acrylate, diethylaminoethyl methacrylate, dimethyl (meth) acrylamide, and acryloylmorpholine.
Examples of the sulfur-containing (meth) acrylic monomer include 2-methylthioethyl (meth) acrylate and the like.
Examples of the (meth) acrylic monomer having no polar group include (meth) acrylate monomers and (meth) acrylic acid. Specific examples of the (meth) acrylic ester monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and isobornyl (meth) acrylate.
As the (meth) acrylic acid monomer, 1 kind may be used alone, or 2 or more kinds may be used.
As the (meth) acrylic monomer, at least a part of the (meth) acrylic monomer is preferably a (meth) acrylic monomer having a polar group. The (meth) acrylic monomer having a polar group is preferably 10 to 100 parts by mass, more preferably 30 to 100 parts by mass, and particularly preferably 50 to 100 parts by mass, based on 100 parts by mass of the (meth) acrylic monomer.
Although a detailed mechanism is not clear, the (meth) acrylic acid monomer is preferably tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, dimethylacrylamide, glycidyl (meth) acrylate, methoxyethyl acrylate, (3-ethyloxetan-3-yl) methyl (meth) acrylate, acryloylmorpholine, and more preferably tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, and dimethylacrylamide, from the viewpoint of improving the adhesive strength with a low surface energy substrate such as polypropylene by using a (meth) acrylate monomer having a polar group.
[ reducing agent ]
The adhesive composition of the present invention comprises a reducing agent which is a carboxylate salt of a transition metal.
The adhesive composition of the present invention can be used for bonding a low surface energy substrate such as polypropylene by containing the reducing agent and polyamine described later.
Examples of the transition metal constituting the carboxylate of the transition metal include iron, copper, zinc, nickel, cobalt, manganese and chromium, and iron or copper is preferable. That is, as the carboxylate of the transition metal, iron carboxylate and copper carboxylate are preferable.
The valence number of the transition metal constituting the carboxylate of the transition metal is usually 2 or less, preferably 1 or 2. The transition metal is preferably in the valence state of 2 when it is iron, and in the valence state of 1 when it is copper.
The carboxylate of the transition metal may, for example, be an acetate of the transition metal, a formate of the transition metal, an oxalate of the transition metal, a stearate of the transition metal, a 2-ethylhexanoate of the transition metal, a naphthenate of the transition metal, or a benzoate of the transition metal, and preferably an acetate of the transition metal or a formate of the transition metal.
The carboxylate of the transition metal may be contained in the binder composition in the form of a hydrate.
Examples of the carboxylate of a transition metal Include Iron (II) acetate, copper (I) acetate, iron (II) formate, copper (I) formate, iron (II) oxalate, copper (I) oxalate, iron (II) stearate, copper (I) stearate, iron (II) bis (2-ethylhexanoate), copper (I) bis (2-ethylhexanoate), iron (II) naphthenate, and copper (I) naphthenate, preferably iron (II) acetate, copper (I) acetate, and iron (II) formate, and more preferably iron (II) acetate and iron (II) formate.
The transition metal carboxylate may be used alone in 1 kind, or may be used in 2 or more kinds.
[ polyamine ]
The binder composition of the present invention contains a polyamine, wherein the polyamine means a molecule having two or more amino groups in the molecule, and the polyamine used in the present invention has at least one tertiary amino group.
The polyamine used in the present invention has two or more amino groups in the molecule, and usually has 2 to 6 amino groups, preferably 2 to 4 amino groups, and more preferably 2 or 3 amino groups in the molecule. Within the above range, the balance between adhesiveness and cost is excellent, and therefore, the preferred range is.
The polyamine used in the present invention has at least one tertiary amino group, preferably at least two tertiary amino groups, more preferably at least two tertiary amino groups, and has no primary amino group and no secondary amino group, and particularly preferably has two or three tertiary amino groups, and has no primary amino group and no secondary amino group.
Examples of the polyamine to be used in the present invention include N, N, N ', N' -tetramethylethylenediamine, N, N, N ', N ", N" -pentamethyldiethylenetriamine, tris [2- (dimethylamino) ethyl ] amine, N, N-dimethyl-1, 2-ethylenediamine, 1,4,7,10, 10-hexamethyltriethylenetetramine, 1,4,8, 11-tetramethyl-1, 4,8, 11-tetraazacyclotetradecane, 2' -bipyridine, 4 '-dimethyl-2, 2' -bipyridine, 4 '-di-tert-butyl-2, 2' -bipyridine, tris (2-pyridylmethyl) amine, N, N, N ', N' -tetrakis (2-pyridylmethyl) ethylenediamine, n, N, N ', N' -tetramethylethylenediamine, N, N, N ', N' -pentamethyldiethylenetriamine, tris [2- (dimethylamino) ethyl ] amine are preferred.
The polyamine may be used alone in 1 kind, or may be used in 2 or more kinds.
[ adhesive composition ]
As described above, the adhesive composition of the present invention is characterized by: the composition comprises a compound having a polymerizable unsaturated group such as a (meth) acrylic monomer, a reducing agent and a polyamine, wherein the reducing agent is a carboxylate of a transition metal, and the polyamine is a polyamine having at least one tertiary amino group. As the compound having a polymerizable unsaturated group such as a (meth) acrylic monomer, the reducing agent, and the polyamine, the above-mentioned compound having a polymerizable unsaturated group, the reducing agent, and the polyamine can be used.
The adhesive composition of the present invention is an adhesive composition useful for bonding a low-surface-energy substrate such as polypropylene, and is superior in safety and does not require a primer compared to conventionally known acrylic adhesives for low-surface-energy substrates.
The pressure-sensitive adhesive composition of the present invention generates radicals by reacting with oxygen present in an atmosphere such as air and/or an oxidizing agent and a reducing agent added as optional components, and exhibits adhesiveness by radical polymerization of a compound having a polymerizable unsaturated group such as a (meth) acrylic monomer.
The reason why the adhesive composition of the present invention is suitable for bonding of low surface energy substrates is not clear, but the present inventors presume that the reason is: the transition metal carboxylate as the reducing agent of the present invention and the polyamine form a transition metal complex having an appropriate catalytic activity, and the metal complex reacts with oxygen in the air or an oxidizing agent blended as an optional component to generate highly active O radicals such as OH radicals, and hydrogen is extracted from the C — H bond on the surface of the low surface energy base material such as polypropylene, and a compound having a polymerizable unsaturated group such as a (meth) acrylic monomer is graft polymerized from the generated C radicals to obtain strong adhesion in which the adhesion interface is bonded by a covalent bond.
In the adhesive composition, the molar ratio of the reducing agent to the polyamine (reducing agent: polyamine) is usually 1:0.05 to 1:5, preferably 1:0.1 to 1:4, and more preferably 1:0.2 to 1: 3.
When the binder composition does not contain an oxidizing agent as an optional component, the molar ratio of the reducing agent to the polyamine (reducing agent: polyamine) is preferably 1:0.7 to 1:4, and more preferably 1:1 to 1: 3. Within the above range, the carboxylate of a transition metal is preferable because it is easily dissolved or dispersed, and polymerization also proceeds appropriately, thereby improving the adhesive strength.
When the binder composition contains an oxidizing agent 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, and more preferably 1:0.2 to 1:1. Within the above range, the carboxylate of a transition metal is preferable because it is easily dissolved or dispersed, and polymerization also proceeds appropriately, thereby improving the adhesive strength.
In the adhesive composition, the content of the reducing agent is preferably 0.01 to 1mmol, more preferably 0.05 to 0.5mmol, based on 1g of the compound having a polymerizable unsaturated group such as the (meth) acrylic monomer. Within the above range, the curing rate and the bonding property of the adhesive are preferably balanced.
The adhesive composition contains a compound having a polymerizable unsaturated group such as a (meth) acrylic monomer, a reducing agent, and a polyamine. An oxidizing agent may also be included as an optional ingredient in the adhesive composition.
The pressure-sensitive adhesive composition may further contain a component (other component) other than the compound having a polymerizable unsaturated group such as a (meth) acrylic monomer, the reducing agent, the polyamine, and the optionally used oxidizing agent.
As other components, a plasticizer, a lubricant, a curing accelerator, a thickener, a film-forming aid, a release agent, a filler, an antifoaming agent, a heat resistance imparting agent, a flame retardancy imparting agent, an antistatic agent, a conductivity imparting agent, an ultraviolet absorber, an antifogging agent, an antibacterial and antifungal agent, a photocatalyst, a dye, a pigment, a coupling agent, a thixotropic agent, a flexibility imparting agent, a reinforcing material (fibers, cloth, nonwoven fabric, etc.), a curable monomer and oligomer other than a (meth) acrylic monomer, a solvent, and the like may be blended.
The oxidizing agent is not particularly limited as long as it can act as a redox initiator in combination with the reducing agent used in the present invention, and examples thereof include peroxides and superoxides.
Examples of the peroxide include organic peroxides and inorganic peroxides. Examples of the organic peroxide include diacyl peroxides, alkyl peroxides, peroxydicarbonates, monoperoxycarbonates, peroxyketals, dialkyl peroxides, hydroperoxides, ketone peroxides, etc., and hydroperoxides such as cumyl hydroperoxide and t-butyl hydroperoxide, and benzoyl peroxide are preferred. The inorganic peroxide may, for example, be hydrogen peroxide or hydrogen peroxide water, and from the viewpoint of safety, hydrogen peroxide water of 35% or less is preferred.
Examples of the superoxide include alkali metal superoxide salts such as potassium superoxide (potassium superoxide) and sodium superoxide (sodium superoxide), and sodium superoxide and potassium superoxide are preferred.
The oxidizing agent may be used alone in 1 kind, or 2 or more kinds.
When the binder composition contains an oxidizing agent, the binder composition can be bonded in an atmosphere when the binder composition is used, even in the absence of oxygen.
When the binder composition contains 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, and more preferably 1:1.5 to 1: 0.05.
When the binder composition contains components other than the compound having a polymerizable unsaturated group such as a (meth) acrylic monomer, the reducing agent, the polyamine, and optionally the oxidizing agent, the amount of the other components is not particularly limited, and is usually 0 to 95 parts by mass, preferably 5 to 90 parts by mass, per 100 parts by mass of the whole binder composition.
The adhesive composition of the present invention has sufficient adhesiveness even if it does not contain a modified polyolefin such as chlorosulfonated polyethylene. Therefore, the adhesive composition of the present invention is excellent in the degree of freedom of blending because it is not necessary to consider the solubility of the modified polyolefin in the blending system, and is excellent in productivity because it does not require a step of dissolving the modified polyolefin and the (meth) acrylic monomer.
The method for producing the adhesive composition is not particularly limited. The adhesive composition of the present invention can be obtained by mixing a compound having a polymerizable unsaturated group such as a (meth) acrylic monomer, a reducing agent, a polyamine, and optionally an oxidizing agent and other components, which are components generally constituting the composition.
The binder composition needs to be stored in an oxygen-insulated state because the reducing agent itself and the mixture of the reducing agent and the polyamine slowly react with oxygen in the air. In the presence of oxygen or in the case where an oxidizing agent is contained, when oxygen or an oxidizing agent is brought into contact with a reducing agent, radicals start to be generated. Therefore, the respective components may be mixed immediately before use, or a two-or multi-component type (some of the components may be solid or powder) binder may be prepared so that oxygen or an oxidizing agent is not in contact with a reducing agent, and both or all of the components may be mixed immediately before use.
The adhesive composition of the present invention can bond various substrates, and particularly, can bond even a low surface energy substrate such as polypropylene. The adhesive composition of the present invention is superior to conventional adhesives in safety and does not require a primer.
The adhesive composition of the present invention has the above-described characteristics, and therefore can bond substrates made of various materials, for example, substrates made of polypropylene, polyethylene, acrylonitrile butadiene styrene copolymer, nylon, polyacetal, Carbon Fiber Reinforced Thermoplastic (CFRTP), and the like, and can also produce a composite of different types of materials. Therefore, the adhesive composition can be used for adhesion, coating, or the like of parts constituting various structures such as electric devices, automobiles, vehicles, ships, and housing equipment.
Examples
The present invention will be described in further detail below with reference to examples, but the present invention is not limited thereto.
[ example 1]
0.1mmol of iron acetate was weighed as a reducing agent, 0.2mmol of N, N, N ', N' -tetramethylethylenediamine was weighed as a polyamine, and 1g of tetrahydrofurfuryl methacrylate was weighed as a monomer, and put into a polyethylene container. Then, the components were mixed for about 1 minute until the components were uniformly dissolved or dispersed, to prepare an adhesive composition.
Using the obtained adhesive composition and polypropylene sheet (25 mm. times.100 mm. times.1.6 mm thick) (two sheets), the adhesive composition was applied to one base material and bonded to the other base material in accordance with JIS K6850 (tensile shear bond strength) under the conditions that the bonding surface was 25 mm. times.12.5 mm and the adhesive thickness was 50 μm, to prepare a sample.
A plurality of samples were prepared, and the tensile shear adhesion strength was measured at a tensile rate of 1 cm/min using a 10kN load cell and an Autograph AG-X manufactured by Shimadzu corporation every 24 hours at 23 ℃ under 50% RH.
The adhesive strength was increased with the lapse of time, and the time (number of days) required for the increase rate of the adhesive strength to be 10% or less with respect to the previous measurement was taken as the adhesive time, and the result was 2 days. The adhesion strength at this time was 2.16MPa as the adhesion strength of the sample.
Examples 2 to 6, 10 to 14, and comparative examples 1 to 4
Adhesive compositions were prepared from the components shown in tables 1,2 and 4 using 0.1mmol of a reducing agent, 0.2mmol of a polyamine and 1g of a monomer in the same manner as in example 1, and evaluated. Further, as the monomers, 1g was used in the case of only 1 species, and 0.5g each and 1g in total were used in the case of 2 species, to prepare a composition. The results are shown in tables 1,2 and 4.
[ examples 7 to 9 ]
The reducing agent and the polyamine were prepared and evaluated by the same method as in example 1 except that 1g of tetrahydrofurfuryl methacrylate was used as the monomer in the amount shown in table 3 based on the components shown in table 3 and the monomer was tetrahydrofurfuryl methacrylate. The results are shown in Table 3.
[ example 15 ]
Adhesive compositions were prepared and evaluated in the same manner as in example 1, except that 0.4mmol of a reducing agent, 0.1mmol of a polyamine, 1g of a monomer and 0.05mmol of an oxidizing agent were used in the compositions shown in Table 5. The results are shown in Table 5.
[ example 16 ]
0.4mmol of iron acetate was weighed as reducing agent, put into a glass bottle and capped tightly. 0.1mmol of N, N, N ', N' -tetramethylethylenediamine was weighed as the polyamine, and 0.5g of tetrahydrofurfuryl methacrylate was weighed as the monomer, and put into another glass bottle and capped tightly. In addition, 0.05mmol of cumyl hydroperoxide as an oxidizing agent and 0.5g of tetrahydrofurfuryl methacrylate were weighed, put into another glass bottle and capped tightly.
The three tightly-covered glass bottles and polypropylene sheets (25 mm. times.100 mm. times.1.6 mm in thickness) (two sheets) were placed inside a polyethylene glove bag.
The caps of the glass bottles were opened, respectively, and the access port of the glove bag was closed. Then, the glove bag was left to stand for 18 hours in a nitrogen atmosphere by repeating the introduction and discharge of nitrogen gas three times and introducing nitrogen gas again.
Then, the contents of the three glass bottles were mixed in a glove bag to prepare an adhesive composition.
The adhesion time and the adhesion strength were measured by the same methods as in example 1. The results are shown in Table 5.
[ examples 17 to 19 ]
Adhesive compositions were prepared from the components shown in Table 5 by the same method as in example 16 using 0.4mmol of a reducing agent, 0.1mmol of a polyamine, 1g of tetrahydrofurfuryl methacrylate as a monomer, and 0.05mmol of an oxidizing agent, and evaluated. The results are shown in Table 5.
[ examples 20 to 24 ]
Adhesive compositions were prepared and evaluated using 0.1mmol of a reducing agent, 0.2mmol of polyamine, and 1g of a monomer, based on the components shown in table 6, in the same manner as in example 1. In examples 22 to 24, the prepared specimens were placed in an oven at 80 ℃ and the adhesive strength was evaluated every 1 hour. The results are shown in Table 6.
[ example 25, comparative examples 5 and 6]
The same adhesive composition as in example 1 (example 25) was prepared, and the adhesive composition prepared in example 57 of japanese patent No. 3535167 (comparative example 5) and a cyanoacrylate-based adhesive (Aron Alpha, general-purpose, tokyo chemical co., ltd.) (comparative example 6) were referred to as an alkylborane/amine complex system adhesive, and the following safety test and the comparison of the adhesiveness without using a primer were carried out.
(safety test)
The adhesive composition (adhesive) was dropped into an aqueous acetic acid solution, and its characteristics were visually observed.
(adhesion without primer)
An adhesive composition (adhesive) was applied to the bonding surface of a PP plate (Kobe polysheet PP-N-BN, Xinsheng Motor company, Xinsheng ) to a thickness of 50 μm, the plate was bonded, and after aging at 23 ℃ and 50% RH for 7 days, Autograph AG-X manufactured by Shimadzu corporation was used and the tensile bonding strength was measured at a tensile rate of 1 cm/min using a 10kN force sensor. The results are shown in Table 7.
The reducing agents, polyamines, monomers, and oxidizing agents used in the examples and comparative examples are as follows.
(reducing agent)
Iron (II) acetate: (C) manufactured by Tokyo chemical industry Co., Ltd (Chinese imperial ceramics chemical Co., Ltd.)2H3O2)2Fe, molecular weight 173.93, 0.1mmol ═ 0.0174 g;
iron (II) formate: (HCO) manufactured by Sanjin and Chemicals corporation2)2Fe·2H2O, molecular weight 181.9, 0.1mmol ═ 0.0182 g;
copper (I) acetate: (C) manufactured by Tokyo chemical industry Co., Ltd2H3O2) Cu, molecular weight 122.59, 0.1mmol ═ 0.0122 g;
iron (II) perchlorate: made by pure photo-chemical Co., Ltd (and pure photo-medicine), Fe (ClO)4)2·6H2O, molecular weight 362.84, 0.1mmol ═ 0.0363 g;
iron (II) chloride: FeCl, product of Aldrich Co (Ardrich)2Molecular weight 126.75, 0.1mmol ═ 0.0127 g;
copper (I) chloride: product of aldrich, CuCl, molecular weight 99.00, 0.1mmol 0.0099 g.
(polyamine)
TMEDA：N,NN ', N' -Tetramethylethylenediamine, product of Kyoho chemical Co., Ltd., C6H16N2Molecular weight 116.21, 0.2mmol ═ 0.0232 g;
PMDETA: n, N, N' -pentamethyldiethylenetriamine, manufactured by Tokyo chemical industry Co., Ltd., C9H23N3173.3, 0.2mmol ═ 0.0347 g;
Me6TREN: tris [2- (dimethylamino) ethyl group]Amine, Tokyo chemical industry Co., Ltd., product C12H30N4Molecular weight 230.4, 0.2 mmol-0.0460 g;
DMAEA: n, N-dimethyl-1, 2-ethanediamine, manufactured by Tokyo Kasei Kogyo K.K., C4H12N2＝88.15(0.2mmol＝0.0176g)；
EDA (electronic design automation): 1, 2-Ethylenediamine, manufactured by Tokyo chemical industries, Ltd., C2H8N2Molecular weight 60.10, 0.2mmol ═ 0.0120 g.
(monomer)
THFMA: tetrahydrofurfuryl methacrylate;
2 HEMA: 2-hydroxyethyl methacrylate;
DM: dimethylaminoethyl methacrylate;
DMAA: dimethylacrylamide;
THFA: tetrahydrofurfuryl acrylate.
(oxidizing agent)
Cumyl hydroperoxide: PERCUMYL H (R.RTM.) manufactured by Nichioil Co., Ltd., purity 82%, C9H12O2Molecular weight 152.19, 0.05mmol ═ 0.0093 g;
potassium superoxide: KO manufactured by Strem Chemicals, Inc2Molecular weight 71.10, 0.05mmol ═ 0.0036 g;
hydrogen peroxide water: tokyo chemical industry Co., Ltd., purity 35%, H2O2Molecular weight 34.01, 0.05mmol ═ 0.0049 g;
benzoyl peroxide: NYPER BW manufactured by Nichiyan oil Co., Ltd., purity 75%, C14H10O4Molecular weight 242.22, 0.05mmol ═ 0.0161 g.
The substrates used in examples and comparative examples are shown below.
PP: polypropylene (Kobe polyshell PP-N-BN, New Konju electric company)
PE: polyethylene (Kobe polysheet EL-N-AN, New Konjac electric company)
ABS: acrylonitrile butadiene styrene copolymer (Kobe polyshell ABS-N-WN, New Kobe Motor Co., Ltd.)
NY 6: nylon 6(N6(NC) Standard grade, Dongli plastics Seiko (imperial to imperial sciences レプラスチック))
NY 66: nylon 66(N66(NC) Standard grade, Tooli plastics Seiko Co., Ltd.)
POM: polyacetal (M25, Toray plastics Seiki Co., Ltd.).
Tables 1 to 6 show the results of evaluation of the reducing agent, the polyamine, the monomer, the molar ratio of the reducing agent to the polyamine (examples 7 to 9), the type of the oxidizing agent, the type of the base material, and the adhesive composition used in each of the examples and comparative examples. Table 7 shows the results of the safety test and the evaluation of the adhesion without using a primer.
In table 4, the portion described as THFA + THFMA as the monomer means that 0.5g (1 g in total) of each of THFA and THFMA is used as the monomer. In table 4, the portion described as THFMA +2HEMA as a monomer means that 0.5g (1 g in total) of each of THFMA and 2HEMA was used as a monomer.
[ Table 1]
[ Table 2]
[ Table 3]
[ Table 4]
[ Table 5]
[ Table 6]
[ Table 7]
Claims (6)
1. An adhesive composition comprising a compound having a polymerizable unsaturated group, a reducing agent, a polyamine, and an oxidizing agent,
the reducing agent is a carboxylate of iron (2) or copper (1),
the polyamine is a polyamine having at least one tertiary amino group,
the oxidant is at least one selected from superoxide and peroxide,
the compound having a polymerizable unsaturated group is a (meth) acrylic monomer.
2. The adhesive composition of claim 1, wherein the polyamine is a polyamine having at least two tertiary amino groups.
3. The adhesive composition of claim 1, wherein at least a portion of the (meth) acrylic monomer is a (meth) acrylic monomer having a polar group.
4. The adhesive composition of claim 3, wherein the polar group comprises at least one atom selected from the group consisting of oxygen and nitrogen.
5. The binder composition according to any one of claims 1 to 4, wherein the molar ratio of the reducing agent to the polyamine (reducing agent: polyamine) is 1:0.05 to 1: 5.
6. The adhesive composition according to any one of claims 1 to 4, wherein the reducing agent is contained in an amount of 0.01 to 1mmol based on 1g of the compound having a polymerizable unsaturated group.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2015256459 | 2015-12-28 | ||
| JP2015-256459 | 2015-12-28 | ||
| PCT/JP2016/088030 WO2017115697A1 (en) | 2015-12-28 | 2016-12-21 | Adhesive composition |
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| CN108368385A CN108368385A (en) | 2018-08-03 |
| CN108368385B true CN108368385B (en) | 2021-10-01 |
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| JP (1) | JP6886408B2 (en) |
| CN (1) | CN108368385B (en) |
| TW (1) | TW201736539A (en) |
| WO (1) | WO2017115697A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| FR3098818B1 (en) | 2019-07-18 | 2021-06-25 | Bostik Sa | Two-component adhesive composition comprising an organoborane-amine complex |
| SE546259C2 (en) * | 2022-12-19 | 2024-09-17 | Stora Enso Oyj | Bonding resin, method to prepare the bonding resin and fibrous insulation product comprising said bonding resin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103237821A (en) * | 2010-12-03 | 2013-08-07 | 三键株式会社 | Curable composition |
| CN103987734A (en) * | 2011-12-05 | 2014-08-13 | 三键精密化学有限公司 | Two component hardening resin composition |
| EP2824155A1 (en) * | 2013-07-09 | 2015-01-14 | HILTI Aktiengesellschaft | Reaction resin composition and its use |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5311932A (en) * | 1976-07-19 | 1978-02-02 | Kyoritsu Kagaku Sangyo | Adhesive composition |
| JPS54158444A (en) * | 1978-06-03 | 1979-12-14 | Kyoritsu Kagaku Sangyo | Adhesive composition |
| TW353666B (en) * | 1996-04-18 | 1999-03-01 | Denki Kagaku Kogyo Kk | Curable resin composition |
| JPH1149983A (en) * | 1997-08-07 | 1999-02-23 | Denki Kagaku Kogyo Kk | Curable emulsion |
| MXPA01011393A (en) * | 2000-11-30 | 2004-05-21 | Rohm & Haas | Redox system and process. |
| AU2006214086B2 (en) * | 2005-02-17 | 2012-01-19 | Monsanto Technology Llc | Transition metal-containing catalysts and catalyst combinations including transition metal-containing catalysts and processes for their preparation and use as oxidation catalysts |
| US8067500B2 (en) * | 2007-03-02 | 2011-11-29 | Denki Kagaku Kogyo Kabushiki Kaisha | Curable composition, bonding method and assembly |
| JP2009051944A (en) * | 2007-08-27 | 2009-03-12 | Toray Fine Chemicals Co Ltd | Radical-curable adhesive composition |
| FR2928931B1 (en) * | 2008-03-21 | 2011-03-25 | Jacret | COMPOSITION FOR STRUCTURAL ADHESIVE |
| CN101781536B (en) * | 2010-03-04 | 2012-06-06 | 北京天山新材料技术股份有限公司 | Thermosetting acrylic structural adhesive and preparation method |
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- 2016-12-21 JP JP2017559152A patent/JP6886408B2/en active Active
- 2016-12-21 CN CN201680072583.6A patent/CN108368385B/en active Active
- 2016-12-21 WO PCT/JP2016/088030 patent/WO2017115697A1/en active Application Filing
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103237821A (en) * | 2010-12-03 | 2013-08-07 | 三键株式会社 | Curable composition |
| CN103987734A (en) * | 2011-12-05 | 2014-08-13 | 三键精密化学有限公司 | Two component hardening resin composition |
| EP2824155A1 (en) * | 2013-07-09 | 2015-01-14 | HILTI Aktiengesellschaft | Reaction resin composition and its use |
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| Publication number | Publication date |
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| TW201736539A (en) | 2017-10-16 |
| CN108368385A (en) | 2018-08-03 |
| JP6886408B2 (en) | 2021-06-16 |
| WO2017115697A1 (en) | 2017-07-06 |
| JPWO2017115697A1 (en) | 2018-10-18 |
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