JP2021024910A - Adhesive set and method for producing structure - Google Patents

Abstract

To provide an adhesive set that has excellent quick curability at room temperature.SOLUTION: An adhesive set contains a first liquid containing a polymerization initiator, and a second liquid containing a reductant, and at least one of the first liquid and the second liquid contains (meth) acryloyl morpholine as a monomer.SELECTED DRAWING: None

Description

The present invention relates to an adhesive set and a method for manufacturing a structure using the adhesive set.

Conventionally, (meth) acrylic adhesives have been used in various fields including the automobile field. Among them, a first liquid and a second liquid are provided, and by mixing these, the temperature is about room temperature (for example, 30 ° C.). ) And adhesives that cure in a short time (so-called room temperature fast-curing two-component adhesives) have been studied in various ways. As such a two-component (meth) acrylic adhesive, for example, Patent Document 1 discloses a two-component curable composition containing a cyanoacrylate component.

Special Table 2015-509126

Two-component adhesives tend to have better storage stability than one-component adhesives. However, in the two-component (meth) acrylic adhesive containing cyanoacrylate, the cyanoacrylate polymerizes due to the moisture in the air, so that the storage stability tends to decrease. Therefore, there is a demand for a two-component adhesive that can be rapidly cured at room temperature without containing cyanoacrylate.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an adhesive set having excellent quick-curing property at room temperature, and a method for producing a structure using the adhesive set.

One aspect of the present invention comprises a first solution containing a polymerization initiator and a second solution containing a reducing agent, and at least one of the first solution and the second solution contains (meth) acryloyl morpholine as a monomer. Further relating to the adhesive set contained.

Since the adhesive set contains (meth) acryloyl morpholine as a monomer, it is excellent in quick curing at room temperature. Therefore, by arranging the two liquids provided in the adhesive set between the adherends, rapid curing at room temperature, that is, adhesion between the adherends at room temperature is possible in a short time.

The content of (meth) acryloyl morpholine may be 20 parts by mass or more with respect to 100 parts by mass of the total amount of the monomers contained in the first liquid and the second liquid. The reducing agent may include a transition metal salt.

Another aspect of the present invention includes a step of adhering adherends to each other using the adhesive set, and in the step, the first liquid and the second liquid are arranged between the adherends. Regarding the manufacturing method.

According to the above manufacturing method, the adherends can be adhered to each other in a short time at room temperature, and a structure in which the adherends are suitably adhered to each other can be obtained.

According to the present invention, there is provided an adhesive set having excellent quick-curing properties at room temperature, and a method for producing a structure using the adhesive set.

Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments. In the present specification, (meth) acrylic means acrylic and corresponding methacrylic, and (meth) acryloyl means acryloyl and corresponding methacryloyl.

[Adhesive set]
The adhesive set according to the present embodiment is an adhesive set (also referred to as a two-component adhesive) including a first liquid containing a polymerization initiator and a second liquid containing a reducing agent. At least one of the first solution and the second solution contains (meth) acryloyl morpholine as a monomer.

The adhesive set according to the present embodiment is an adhesive set that can exhibit adhesiveness in a short time after mixing the first liquid and the second liquid and has excellent quick-curing property at room temperature. The reason why such an effect is exerted is not always clear, but by using (meth) acryloyl morpholine as a monomer, radicals generated by the redox reaction between the polymerization initiator and the reducing agent are converted into (meth) acryloyl morpholine. It is considered that this is because the radical reaction is promoted and the polymerization of the monomer proceeds in a chain reaction by the radical generated from (meth) acryloyl morpholine.

In one embodiment, the first solution is composed of (meth) acryloyl morpholine and polymerization initiator from the viewpoint of excellent affinity when mixing the first solution and the second solution, increasing the mixing degree, and suppressing variation in characteristics. It contains an agent, and the second solution contains (meth) acryloyl morpholine and a reducing agent.

In another embodiment, the first solution contains (meth) acryloyl morpholine and a polymerization initiator, and the second solution contains a reducing agent (does not contain (meth) acryloyl morpholine). In another embodiment, the first solution contains a polymerization initiator (does not contain (meth) acryloyl morpholine) and the second solution contains (meth) acryloyl morpholine and a reducing agent.

((Meta) Acryloyl Morpholine)
As the (meth) acryloyl morpholine, 4-acryloyl morpholine or 4-methacryloyl morpholine can be used. When (meth) acryloyl morpholine is contained in both the first solution and the second solution, the (meth) acryloyl morpholine contained in the first solution and the (meth) acryloyl morpholine contained in the second solution are the same as each other. They may be present or different, and are preferably the same as each other.

The total amount of (meth) acryloyl morpholine contained in the first and second liquids (hereinafter, simply referred to as the content of (meth) acryloyl morpholine) is 100 mass by mass of the total amount of monomers contained in the first and second liquids. For example, it may be 10 parts by mass or more and 100 parts by mass or less. From the viewpoint of being more excellent in quick curing at room temperature, the content of (meth) acryloyl morpholine may be 15 parts by mass or more, 20 parts by mass or more, 25 parts by mass or more, or 30 parts by mass or more. From the viewpoint of adjusting the pot life of the mixture of the first solution and the second solution, the content of (meth) acryloyl morpholine is based on 100 parts by mass of the total amount of the monomers contained in the first solution and the second solution. It may be 95 parts by mass or less, 90 parts by mass or less, 85 parts by mass or less, 80 parts by mass or less, or 75 parts by mass or less.

The adhesive set may contain a monomer other than (meth) acryloyl morpholine (hereinafter, simply referred to as another monomer). The other monomer may be contained in one or both of the first liquid and the second liquid, and may be contained in a third liquid different from the first liquid and the second liquid.

The other monomer may be, for example, a (meth) acrylic monomer having at least one (meth) acryloyl group. The (meth) acrylic monomer may be an aliphatic (meth) acrylate, an alicyclic (meth) acrylate, an aromatic (meth) acrylate, a heterocyclic (meth) acrylate or the like. The (meth) acrylic monomer is, for example, a (meth) acrylic monomer having an amino group such as N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, and N-methyl (meth) acrylamide. There may be.

Examples of the aliphatic (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, butoxyethyl (meth) acrylate, and the like. Isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, octyl heptyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate , Lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, methoxyethyl acrylate, methoxypolyethylene glycol Examples thereof include (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, and mono (2- (meth) acryloyloxyethyl) succinate.

Examples of the alicyclic (meth) acrylate include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and isobornyl (meth). ) Acrylate, mono (2- (meth) acryloyloxyethyl) tetrahydrophthalate, and mono (2- (meth) acryloyloxyethyl) hexahydrophthalate.

Examples of the aromatic (meth) acrylate include benzyl (meth) acrylate, phenyl (meth) acrylate, o-biphenyl (meth) acrylate, 1-naphthyl (meth) acrylate, 2-naphthyl (meth) acrylate, and phenoxyethyl ( Meta) acrylate, p-cumylphenoxyethyl (meth) acrylate, o-phenylphenoxyethyl (meth) acrylate, 1-naphthoxyethyl (meth) acrylate, 2-naphthoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonyl Phenoxypolyethylene glycol (meth) acrylate, phenoxypolypropylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3- (o-phenylphenoxy) propyl (meth) acrylate, 2-hydroxy Examples thereof include -3- (1-naphthoxy) propyl (meth) acrylate and 2-hydroxy-3- (2-naphthoxy) propyl (meth) acrylate.

Examples of the heterocyclic (meth) acrylate include 2-tetrahydrofurfuryl (meth) acrylate, N- (meth) acryloyloxyethyl hexahydrophthalimide, and 2- (meth) acryloyloxyethyl-N-carbazole. Can be mentioned.

From the viewpoint of excellent compatibility with (meth) acryloyl morpholine, it is preferable to use a highly polar monomer as another monomer. As a highly polar monomer, at least one selected from methoxyethyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, dimethyl (meth) acrylamide, and 2-tetrahydrofurfuryl (meth) acrylate is used. You may.

Other monomers may be used alone or in combination of two or more. When other monomers are contained in both the first liquid and the second liquid, the other monomers contained in the first liquid and the other monomers contained in the second liquid are different even if they are the same as each other. Also, preferably they are the same as each other.

(Polymerization initiator)
The polymerization initiator may be, for example, a radical polymerization initiator. The radical polymerization initiator may be, for example, an organic peroxide or an azo compound. The organic peroxide may be, for example, hydroperoxide, peroxydicarbonate, peroxyester, peroxyketal, dialkyl peroxide, diacyl peroxide or the like. The azo compound may be AIBN (2,2'-azobisisobutyronitrile), V-65 (azobisdimethylvaleronitrile) or the like. The polymerization initiator may be used alone or in combination of two or more.

Examples of the hydroperoxide include diisopropylbenzene hydroperoxide and cumene hydroperoxide.

Examples of the peroxydicarbonate include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, and di-2-ethoxymethoxyperoxydicarbonate. , Di (2-ethylhexylperoxy) dicarbonate, dimethoxybutylperoxydicarbonate, and di (3-methyl-3methoxybutylperoxy) dicarbonate.

Examples of the peroxy ester include cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, and 1-cyclohexyl-1-methylethylperoxyneodecanoate. , T-Hexylperoxyneodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5- Di (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanonate, t-hexylperoxy-2-ethylhexanonate, t-butylperoxy -2-Ethylhexanonate, t-butylperoxyisobutyrate, 1,1-bis (t-butylperoxy) cyclohexane, t-butylperoxy-3,5,5-trimethylhexanonete, t- Butyl peroxylaurate, 2,5-dimethyl-2,5-di (m-toluole peroxy) hexane, t-hexyl peroxybenzoate, and t-butyl peroxyacetate can be mentioned.

Examples of the peroxyketal include 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, and 1, 1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, and 2,2-bis (t-butylperoxy) Butyl can be mentioned.

Examples of the dialkyl peroxide include α, α'-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and the like. And t-butylcumyl peroxide.

Examples of the diacyl peroxide include isobutyl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, and dichloromethane. Peroxide, benzoyl peroxytoluene, and benzoyl peroxide can be mentioned.

From the viewpoint of storage stability, the radical polymerization initiator is preferably an organic peroxide, more preferably a hydroperoxide, and further preferably a cumene hydroperoxide.

The content of the polymerization initiator in the first liquid is, for example, 0.1 part by mass or more, 0.5 part by mass or more, or 1 with respect to 100 parts by mass of the total amount of the monomers contained in the first liquid and the second liquid. It may be 20 parts by mass or less, 15 parts by mass or less, or 10 parts by mass or less.

(Reducing agent)
The reducing agent may be, for example, a tertiary amine, a thiourea derivative, a transition metal salt or the like. Examples of the tertiary amine include triethylamine, tripropylamine, tributylamine, and N, N-dimethylparatoluidine. Examples of the thiourea derivative include 2-mercaptobenzimidazole, methylthiourea, dibutylthiourea, tetramethylthiourea, and ethylenethiourea. Examples of the transition metal salt include cobalt naphthenate, copper naphthenate, and vanadyl acetylacetonate. The reducing agent may be used alone or in combination of two or more.

From the viewpoint of curing rate, the reducing agent preferably contains a thiourea derivative or a transition metal salt, more preferably contains a transition metal salt, and further preferably contains vanadyl acetylacetonate. The thiourea derivative may be, for example, ethylene thiourea.

The content of the reducing agent in the second liquid is, for example, 0.005 parts by mass or more and 10 parts by mass or less or 0.01 parts by mass or more 5 with respect to 100 parts by mass of the total amount of the monomers contained in the first liquid and the second liquid. It may be less than or equal to a mass part. When the reducing agent contains a transition metal salt, the content of the transition metal salt in the second liquid is more excellent in quick curing at room temperature with respect to 100 parts by mass of the total amount of the monomers contained in the first liquid and the second liquid. From the viewpoint, it may be 0.01 parts by mass or more, 0.015 parts by mass or more, or 0.02 parts by mass or more, and from the viewpoint of adjusting the pot life of the mixture, 2 parts by mass or less and 1 part by mass or less, It may be 0.5 parts by mass or less, or 0.3 parts by mass or less.

The adhesive set may contain other components other than the monomer, polymerization initiator and reducing agent. Other components may be contained in one or both of the first liquid and the second liquid, and may be contained in a third liquid different from the first liquid and the second liquid.

The other components may be polymerization inhibitors for the purpose of improving storage stability. Examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, and phenothiazine.

The other components may be paraffins for the purpose of preventing polymerization inhibition by oxygen. Examples of paraffins include paraffin wax, microcrystalline wax, carnauba wax, beeswax, lanolin, whale wax, ceresin, and candelilla wax.

The other component may be a filler for the purpose of preventing dripping, imparting tincture property, improving adhesive strength, and the like. The shape of the filler may be, for example, fibrous or spherical.

As the components of the filler, for example, metal fillers such as silver powder, gold powder, copper powder, nickel powder; alumina, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, oxidation. Examples thereof include inorganic fillers such as magnesium, aluminum oxide, aluminum hydroxide, crystalline silica, amorphous silica, boron nitride, titania, glass, iron oxide and ceramics; and organic fillers such as carbon and rubber fillers.

The adhesive set according to the present embodiment is a two-component (meth) acrylic adhesive composed of a first solution and a second solution, has excellent storage stability, and can be stored for a long time at room temperature. At the same time, the mixture of the first liquid and the second liquid is excellent in quick curing at room temperature.

[Manufacturing method of structure]
Various adherends can be adhered using the adhesive set according to the present embodiment. The method for manufacturing a structure according to the present embodiment includes a step (adhesion step) of adhering adherends to each other using the above-mentioned adhesive set.

In the bonding step, the first liquid and the second liquid are arranged between the adherends. The adherend is made of, for example, a metal such as steel, iron, copper, tin, aluminum, or stainless steel, a resin, a carbon fiber reinforced plastic, or the like. The two adherends to be bonded may be made of the same kind of material as each other, or may be made of different materials from each other.

In the bonding step, specifically, for example, one adherend and another adherend are arranged with a predetermined gap, and a device such as a mixing nozzle is used to fill the gap with the first liquid and the first liquid. Inject two liquids. In the bonding step, the first liquid and the second liquid may be mixed substantially at the same time as the injection between the adherends, or the first liquid and the second liquid may be mixed immediately before the injection between the adherends. Good. When the first liquid and the second liquid are mixed with each other, the mixture is rapidly cured and the adherends are adhered to each other.

The adhesive set according to this embodiment can be cured in a short time at room temperature. That is, in the adhesive set used in this production method, the mixture of the first liquid and the second liquid has an appropriate pot life at room temperature, and is cured at room temperature when adhering the adherends to each other. The time can be shortened.

The pot life is the time from mixing the first solution and the second solution to the start of thickening. The pot life at room temperature may be, for example, 30 minutes or less or 20 minutes or less, preferably 10 minutes or less or 5 minutes or less. The pot life at room temperature may be, for example, 5 seconds or longer or 10 seconds or longer, and preferably 30 seconds or longer or 1 minute or longer from the viewpoint of workability. The pot life at room temperature can be appropriately adjusted by changing the content of (meth) acryloyl morpholine, the type of reducing agent, and the like.

The curing time refers to the time until the mixture of the first liquid and the second liquid exhibits practical strength. The curing time may be 45 minutes or less, 30 minutes or less, or 20 minutes or less, and is preferably 10 minutes or less or 5 minutes or less from the viewpoint of quick curing at room temperature. The curing time may be, for example, 30 seconds or more. The curing time can be appropriately adjusted by changing the content of (meth) acryloyl morpholine, the type of reducing agent, and the like.

Since the adhesive set according to the present embodiment can be cured at room temperature, the temperature at which the bonding step is carried out may be, for example, 5 ° C or higher, 10 ° C or higher, or 20 ° C or higher, 60 ° C or lower, 50 ° C. Below, or may be 40 ° C. or lower. The bonding step may be carried out while changing the temperature stepwise. For example, after bonding at a temperature of 40 ° C. or lower, aftercure may be performed at a temperature of 100 ° C. or lower.

The structure obtained by the above manufacturing method includes one adherend, another adherend, and an adhesive portion for adhering one adherend and another adherend. The adhesive portion is a cured product of a mixture of liquids (for example, a mixture of first liquid and second liquid) constituting the above-mentioned adhesive set.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the Examples.

Acrylic loylmorpholine (ACMO), phenoxyethyl acrylate (PEA) and dimethylacrylamide (DMAA) were prepared as monomers, and cumene hydroperoxide was prepared as a polymerization initiator. Vanadyl acetylacetonate (reducing agent 1) and ethylenethiourea (reducing agent 2) were prepared as reducing agents.

(Examples 1 to 8 and Comparative Examples 1 to 3)
The monomer and the polymerization initiator were mixed in the blending amounts shown in Table 1 to obtain a first liquid. Further, the monomer and the reducing agent were mixed in the blending amounts shown in Tables 1 and 2 to obtain a second liquid.

<Evaluation of adhesive>
The curability of the mixture of the first solution and the second solution mixed at a mass ratio of 1: 1 at room temperature was evaluated. The results are shown in Tables 1 and 2.

(Available time)
The time until the mixture began to thicken at 25 ° C. was defined as the pot life. The pot life of less than 5 minutes was designated as "A", the pot life of 5 minutes or more and less than 30 minutes was designated as "B", and the pot life of 30 minutes or more was designated as "C".

(Curing time)
The FT-IR spectrum measurement of the mixture was measured at 25 ° C., and the time until the peak derived from the carbon-carbon double bond of the monomer near ^{1620 cm-1 disappeared was defined as the curing time.} The curing time was less than 10 minutes as "A", 10 minutes or more and less than 45 minutes as "B", and 45 minutes or more as "C".

Claims (4)

A first liquid containing a polymerization initiator and a second liquid containing a reducing agent are provided.
An adhesive set in which at least one of the first liquid and the second liquid further contains (meth) acryloyl morpholine as a monomer. The adhesive set according to claim 1, wherein the content of the (meth) acryloyl morpholine is 20 parts by mass or more with respect to 100 parts by mass of the total amount of the monomers contained in the first liquid and the second liquid. The adhesive set according to claim 1 or 2, wherein the reducing agent contains a transition metal salt. A step of adhering adherends to each other using the adhesive set according to any one of claims 1 to 3 is provided.
A method for producing a structure, in which the first liquid and the second liquid are arranged between the adherends in the step.