JP2021014571A - Adhesive set, structure, and method of manufacturing structure - Google Patents

Abstract

To provide an adhesive set which can secure a sufficient pot life and has a high curing rate.SOLUTION: The adhesive set is provided which comprises: a first liquid containing an oxidizing agent containing an organic peroxide; and a second liquid containing a reducing agent. At least one of the first liquid and the second liquid further contains a compound represented by the following general formula (I). At least one of the first liquid and the second liquid further contains a compound having a (meth)acryloyl group. At least one of the first liquid and the second liquid further contains an elastomer soluble in the compound having a (meth)acryloyl group. [In the formula (I), R represents a C1-5 alkyl group; and n represents an integer of 0-4.]SELECTED DRAWING: None

Description

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

Conventionally, (meth) acrylic adhesives have been used in various fields. Among them, for example, a first liquid and a second liquid are provided, and by mixing these, they are cured at about room temperature (for example, 30 ° C.). Adhesive sets such as adhesives (so-called room temperature curable two-component adhesives) and three-agent type curable resin compositions as disclosed in Patent Document 1 below are known.

Japanese Unexamined Patent Publication No. 2001-139369

In conventional adhesive sets, the curing rate tends to decrease as the time (potential time) from mixing each component to the start of curing of the mixture increases, and there is still room for improvement in the curing rate. .. Therefore, it is a main object of the present invention to provide an adhesive set having a sufficient pot life and a high curing rate.

One aspect of the present invention includes a first liquid containing an oxidizing agent containing an organic peroxide and a second liquid containing a reducing agent, and at least one of the first liquid and the second liquid is described below in general. Further containing the compound represented by the formula (I), at least one of the first liquid and the second liquid further contains a compound having a (meth) acryloyl group, and at least one of the first liquid and the second liquid , An adhesive set further containing an elastoma soluble in a compound having a (meth) acryloyl group.

［式（Ｉ）中、Ｒは炭素数１〜５のアルキル基を示し、ｎは０〜４の整数を示す。］

[In the formula (I), R represents an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 4. ]

In the adhesive set, the content of the compound represented by the general formula (I) is 0.005 parts by mass to 5.% by mass with respect to 100 parts by mass of the total amount of the compound having the (meth) acryloyl group and the elastomer. It may be 0 parts by mass.

In the adhesive set, the elastomer may include a polyurethane (meth) acrylate. The polyurethane (meth) acrylate may contain a polyurethane (meth) acrylate having a skeleton derived from a polycarbonate polyol.

In the adhesive set, the reducing agent may contain a copper compound.

In the adhesive set, both the first solution and the second solution may further contain the compound having the (meth) acryloyl group and the elastomer.

In the adhesive set, the second liquid may further contain the compound represented by the general formula (I).

Another aspect of the present invention comprises a first adherend, a second adherend, and an adhesive portion for adhering the first adherend and the second adherend. A structure that is a cured product of a mixture of liquids constituting the adhesive set.

Yet another aspect of the present invention is a method for manufacturing a structure, comprising a step of adhering a first adherend and a second adherend to each other using the adhesive set.

According to one aspect of the present invention, it is possible to provide an adhesive set having a sufficient pot life and a high curing rate.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof. In the present specification, the aliphatic compound means a compound having no aromatic ring, and the aromatic compound means a compound having an aromatic ring. As used herein, the term "(meth) acryloyl group" means an acryloyl group or a corresponding methacryloyl group. The same applies to other similar expressions such as "(meth) acrylic acid".

(Adhesive set)
The adhesive set according to one embodiment includes a first liquid containing an oxidizing agent containing an organic peroxide and a second liquid containing a reducing agent. At least one of the first liquid and the second liquid further contains a compound represented by the following general formula (I). At least one of the first solution and the second solution further contains a compound having a (meth) acryloyl group. At least one of the first solution and the second solution further contains an elastomer (hereinafter, also referred to as "elastomer") which is soluble in a compound having a (meth) acryloyl group.

From the viewpoint of ensuring a sufficient pot life and a high curing rate, the adhesive set further contains compounds and elastomers in which both the first and second liquids have a (meth) acryloyl group. It is preferable that both the first solution and the second solution further contain a compound having a (meth) acryloyl group and an elastomer, and the second solution further contains a compound represented by the following general formula (I). It is more preferable to contain it.

In the adhesive set, by mixing the first liquid and the second liquid, the oxidizing agent contained in the first liquid and the reducing agent contained in the second liquid undergo a redox reaction to generate radicals, and the first A mixture of the liquid and the second liquid can be radically polymerized to form a cured product.

Hereinafter, a compound having a (meth) acryloyl group in an adhesive set (hereinafter, may be referred to as “(a) component”) and an elastomer soluble in a compound having a (meth) acryloyl group (hereinafter, “(b) component”). ”), Oxidizing agent (hereinafter, also referred to as“ (c) component ”), reducing agent (hereinafter, sometimes referred to as“ (d) component ”), and general formula (I). The compound to be used (hereinafter, may be referred to as “component (e)”) will be described in detail.

(A) Component: Compound having (meth) acryloyl group The component (a) has at least one (meth) acryloyl group in the molecule. Since the component (a) has at least one (meth) acryloyl group in the molecule, it can be radically polymerized by radicals generated in the redox reaction between the components (c) and (d) described later. ..

The component (a) may be a monomer having a (meth) acryloyl group or an oligoma having a (meth) acryloyl group. The component (a) includes an ethylenically unsaturated group other than the (meth) acryloyl group, a hydroxy group, a carboxyl group, an ester group, an amide group, a cyano group, a phosphoric acid group, and a phosphonic acid group in addition to the (meth) acryloyl group. , Triazine ring, thiol group and the like may be contained. The component (a) is a monofunctional monomer having one (meth) acryloyl group, a bifunctional monomer having two (meth) acryloyl groups, or a trifunctional or higher polyfunctional monomer having three or more (meth) acryloyl groups. It may be any of.

The component (a) preferably contains a (meth) acrylic monomer having at least one (meth) acryloyl group from the viewpoint of ensuring a sufficient pot life and a high curing rate. The component (a) may contain acrylonitrile and the like. The component (a) may contain a silane compound having a (meth) acryloyloxy group from the viewpoint of high adhesiveness. Examples of the silane compound having a (meth) acryloyloxy group include 3-acryloxypropyltrimethoxysilane.

The (meth) acrylic monomer may be, for example, (meth) acrylic acid, alkyl (meth) acrylate or the like. The number of carbon atoms of the alkyl group in the alkyl (meth) acrylate may be, for example, 1 to 18, 1 to 12, 1 to 10 or 1 to 8. The alkyl group may be linear, branched or cyclic. Alkyl (meth) acrylate includes, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate and the like. May be. The component (a) preferably contains an alkyl (meth) acrylate from the viewpoint of ensuring a sufficient pot life and a high curing rate, and the alkyl group has 1 to 12 carbon atoms. It is more preferable to contain an alkyl (meth) acrylate, further preferably to contain an alkyl (meth) acrylate having an alkyl group having 1 to 10 carbon atoms, and it is selected from methyl (meth) acrylate and dicyclopentenyl (meth) acrylate. It is particularly preferable to contain at least one of these.

The (meth) acrylic monomer may contain a phosphoric acid group. Examples of such (meth) acrylic monomers include acid phosphooxyethyl (meth) acrylate, acid phosphooxypropyl (meth) acrylate, acid phosphooxypolyoxyethylene glycol mono (meth) acrylate, and acid phosphooxypolyoxypropylene. Examples thereof include glycol mono (meth) acrylate, 2,2'-di (meth) acryloyloxydiethyl phosphate, EO (ethylene oxide) -modified di (meth) acrylate, and phosphoric acid-modified epoxy (meth) acrylate. The (meth) acrylic monomer may be, for example, a (meth) acrylic monomer having a triazine ring such as isocyanuric acid-modified (meth) acrylate. The (meth) acrylic monomer may be, for example, a (meth) acrylic monomer having an amino group such as acrylamide.

These components (a) can be used alone or in combination of two or more. When the component (a) is contained in both the first solution and the second solution, the component (a) contained in the first solution and the component (a) contained in the second solution may be the same as each other. They may be different, preferably the same as each other.

The total content of the component (a) in the first and second liquids is 15 parts by mass or more based on 100 parts by mass of the total amount of the (a) and (b) components in the first and second liquids. It may be 20 parts by mass or more, 25 parts by mass or more, 40 parts by mass or more, 50 parts by mass or more, 60 parts by mass or more or 65 parts by mass or more, and 85 parts by mass or less, 80 parts by mass or less or 75 parts by mass or less. There may be.

(B) Component: Elastomer The elastomer may be any soluble in the component (a). Here, "soluble in the component (a)" means that it can be dissolved or dispersed, and 25 g of the elastomer is dispersed in 10 g of the compound having the (meth) acryloyl group which is the component (a). , It is allowed to stand at room temperature, and it is shown that the state after 3 hours is visually uniform. Examples of the elastoma soluble in the component (a) include styrene rubber, olefin rubber, ester rubber, urethane rubber, diene rubber and the like.

The component (b) may include an elastomer having a (meth) acryloyl group (excluding the component (a) described above). Examples of the elastomer having a (meth) acryloyl group include polyurethane (meth) acrylate and the like. Examples of the polyurethane (meth) acrylate include bifunctional aliphatic polyurethane (meth) acrylate (for example, product name: EBECRYL230, manufactured by Daicel Ornex Co., Ltd.), and bifunctional aromatic polyurethane (meth) acrylate (for example, product name: EBECRYL210, manufactured by Daicel Ornex Co., Ltd., trifunctional aliphatic polyurethane (meth) acrylate (for example, product name: EBECRYL8311, manufactured by Daicel Ornex Co., Ltd.), tetrafunctional aliphatic polyurethane (meth) acrylate (for example, product name: EBECRYL8210, manufactured by Daicel Ornex Co., Ltd., hexafunctional aliphatic polyurethane (meth) acrylate (for example, product name: EBECRYL8301R, manufactured by Daicel Ornex Co., Ltd.) and the like can be mentioned.

Polyurethane (meth) acrylate can be obtained, for example, by reacting a polyol, a polyisocyanate, and a (meth) acrylic compound having a hydroxyl group.

Examples of the polyol include polycarbonate polyol, polybutadiene polyol, polyether polyol, and polyester polyol. These polyols can be used alone or in combination of two or more.

The polycarbonate polyol is not particularly limited as long as it has a carbonate skeleton and a hydroxyl group bonded to the carbonate skeleton. The polycarbonate polyol may be a reaction product of the carbonate compound and the alkylene glycol. The number average molecular weight of the polycarbonate polyol may be 500 or more, 800 or more or 1000 or more, and may be 5000 or less, 4000 or less or 3000 or less.

Examples of the polycarbonate polyol include a polycarbonate diol represented by the following formula (1).

In formula (1), R ¹ and R ² each independently represent an alkylene group having 2 to 10 carbon atoms, and R ¹ and R ² may be the same or different. t represents 5 to 120.

The polybutadiene polyol is a compound having a polymer chain derived from butadiene and hydroxyl groups at both ends of the polymer chain. The polybutadiene polyol may be a liquid butadiene copolymer having a hydroxyl group at the molecular terminal. When the polymerized chain contains a structural unit derived from a polybutadiene polyol, the impact resistance and adhesiveness of the adhesive composition after curing tend to be improved. The number average molecular weight of the polybutadiene polyol may be 1000 or more or 1200 or more, and may be 5000 or less, 4000 or less, or 3000 or less.

Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetramethylene glycol, and ethylene oxide-modified polypropylene glycol. The number average molecular weight of the polyether polyol may be 500 or more, 700 or more or 1000 or more, and may be 6000 or less, 5500 or less or 5000 or less.

Examples of the polyisocyanate include diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated xylylene diisocyanate. Examples thereof include isocyanate, hydrogenated diphenylmethane diisocyanate, m-phenylenediisocyanate, biphenylenediisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate. These polyisocyanates can be used alone or in combination of two or more. From the viewpoint of high reactivity with polyol, the polyisocyanate preferably contains an aromatic polyisocyanate, and more preferably contains diphenylmethane diisocyanate.

Examples of the (meth) acrylic compound having a hydroxyl group include 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 6. -Hydroxyhexyl (meth) acrylate and 1,4-cyclohexanedimethanol mono (meth) acrylate can be mentioned. These (meth) acrylic compounds may be used alone or in combination of two or more.

Polyurethane (meth) acrylate is a polyurethane (meth) acrylate having a skeleton derived from a polycarbonate polyol (hereinafter, also referred to as “polycarbonate skeleton”) from the viewpoint of ensuring a sufficient pot life and a high curing rate. , Polyurethane (meth) acrylate having a skeleton derived from polybutadiene polyol (hereinafter, also referred to as "polybutadiene skeleton"), and polyurethane (meth) acrylate having a skeleton derived from polyether polyol (hereinafter, also referred to as "polyether skeleton"). It may contain at least one selected from the group consisting of.

The polyurethane (meth) acrylate preferably contains a polyurethane (meth) acrylate having a polycarbonate skeleton from the viewpoint of adhesiveness of the cured product and suppression of warpage. (B) By containing a polyurethane (meth) acrylate having a polycarbonate skeleton as a component, a cured product capable of achieving both high breaking strength and high elongation can be obtained, and warpage suppression and high adhesiveness are required. An adhesive set applied to the adhesion of the adherend is obtained. (B) When polyurethane (meth) acrylate having a polycarbonate skeleton is contained as a component, the total content of polyurethane (meth) acrylate having a polycarbonate skeleton in the first liquid and the second liquid is the total content in the first liquid and the second liquid. Based on 100 parts by mass of the total amount of the component (a) and the component (b), it may be 50 parts by mass or more, 60 parts by mass or more or 65 parts by mass or more, and 85 parts by mass or less, 80 parts by mass or less or 75 parts by mass. It may be:

The weight average molecular weight of the polyurethane (meth) acrylate is not particularly limited, but may be 1000 or more, 2000 or more or 3000 or more, and may be 30,000 or less, 20000 or less or 10000 or less. The weight average molecular weight of the polyurethane (meth) acrylate can be adjusted, for example, by the molar ratio of polyol to polyisocyanate or their molecular weight. In the present specification, the weight average molecular weight (Mw) is a value converted from a calibration curve using standard polystyrene by a gel permeation chromatography (GPC) method.

These components (b) can be used alone or in combination of two or more. When the component (b) is contained in both the first solution and the second solution, the component (b) contained in the first solution and the component (b) contained in the second solution may be the same as each other. They may be different, preferably the same as each other.

The total content of the component (b) in the first and second liquids is 15 parts by mass or more based on 100 parts by mass of the total amount of the (a) and (b) components in the first and second liquids. It may be 20 parts by mass or more or 25 parts by mass or more, and is 85 parts by mass or less, 80 parts by mass or less, 75 parts by mass or less, 60 parts by mass or less, 50 parts by mass or less, 40 parts by mass or less, or 35 parts by mass or less. There may be.

Component (c): Oxidizing agent The component (c) reacts with the component (d) described later to generate radicals, and has a role as a polymerization initiator of the component (a).

The component (c) contains an organic peroxide. Examples of the organic peroxide include hydroperoxide, peroxydicarbonate, peroxyester, peroxyketal, dialkyl peroxide, diacyl peroxide and the like. The organic peroxide preferably contains a hydroperoxide from the viewpoint of ensuring a sufficient pot life and a high curing rate. Examples of the hydroperoxide include aromatic hydroperoxides such as cumene hydroperoxide and diisopropylbenzene hydroperoxide; t-butyl hydroperoxide, paramentan hydroperoxide, 1,1,3,3-tetramethylbutyl. Examples thereof include aliphatic hydroperoxides such as hydroperoxide.

These components (c) can be used alone or in combination of two or more. The content of the component (c) in the first liquid is 0.1 part by mass or more and 0.25 mass with respect to 100 parts by mass of the total amount of the (a) and (b) components in the first liquid and the second liquid. It may be 10 parts by mass or less, 0.5 parts by mass or more, 5 parts by mass or less, or 3 parts by mass or less.

Component (d): Reducing agent The component (d) may be any as long as it can carry out a redox reaction with the above-mentioned component (c). Examples of the component (d) include copper compounds such as organic acid copper salts and copper acetylacetonate. Examples of the organic acid copper salt include copper naphthenate, copper acetate and the like.

The component (d) preferably contains a copper compound, and more preferably contains an organic acid copper salt, from the viewpoint of ensuring a sufficient pot life and a high curing rate.

The component (d) may contain, for example, a tertiary amine, a thiourea derivative, a transition metal salt, or the like, in addition to the above-mentioned copper compound. Examples of the tertiary amine include triethylamine, tripropylamine, tributylamine, N, N-dimethylparatoluidine and the like. Examples of the thiourea derivative include 2-mercaptobenzimidazole, methylthiourea, dibutylthiourea, tetramethylthiourea, ethylenethiourea and the like. Examples of the transition metal salt include cobalt naphthenate, vanadyl acetylacetonate and the like.

These components (d) can be used alone or in combination of two or more. The content of the component (d) in the second liquid is 0.1 part by mass or more and 0.25 mass with respect to 100 parts by mass of the total amount of the (a) and (b) components in the first liquid and the second liquid. It may be 10 parts by mass or less, 0.5 parts by mass or more, 5 parts by mass or less, or 3 parts by mass or less.

Component (e): Compound represented by the general formula (I) The component (e) is a compound represented by the following general formula (I). By containing the component (e), the adhesive set can sufficiently secure the pot life of the mixture obtained by mixing the first solution and the second solution, and the mixture is polymerized. The curing rate of the obtained cured product can be improved.

In formula (I), R represents an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 4. R may be an alkyl group having 1 to 3 carbon atoms. n is preferably 0 from the viewpoint of ensuring a sufficient pot life and a high curing rate. That is, the compound represented by the formula (I) preferably contains o-sulfobenzimide.

When the component (e) is contained in both the first solution and the second solution, the component (e) contained in the first solution and the component (e) contained in the second solution may be the same as each other. They may be different, preferably the same as each other. The total content of the component (e) in the first and second liquids is 0.005 parts by mass with respect to 100 parts by mass of the total contents of the (a) and (b) components in the first and second liquids. As mentioned above, it may be 0.008 parts by mass or more or 0.01 parts by mass or more, 5.0 parts by mass or less, 4.0 parts by mass or less, 3.0 parts by mass or less, 2.0 parts by mass or less, 1 It may be 0.5 parts by mass or less or 1.0 parts by mass or less.

Other Ingredients The adhesive set may further contain other components other than the components (a) to (e), if necessary. 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, phenothiazine and the like.

The other component may be a filler for the purpose of preventing dripping, imparting chilliness, improving adhesive strength, and the like. Examples of the shape of the filler include a fibrous filler and a spherical filler. Examples of the filler components include metal fillers such as silver powder, gold powder, copper powder, and nickel powder, alumina, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, and 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.

From the viewpoint of improving workability, the adhesive set preferably has a pot life of 8 to 120 minutes as a mixture obtained by mixing the first liquid and the second liquid. As used herein, the pot life is the time from when each component in the adhesive set is mixed until the mixture begins to cure. The pot life can be measured by the method of measuring the pot time described later.

From the viewpoint of improving the adhesive strength and the stability of the adhesiveness of the adhesive set, the final curing rate of the cured product of the mixture obtained by mixing the first liquid and the second liquid is 95% or more. Is preferable. The curing rate can be measured by the method for measuring the curing rate described later.

The adhesive set according to the present embodiment is excellent in workability and can be used under various conditions because the pot life of the mixture obtained by mixing the first liquid and the second liquid can be easily controlled. be able to. Further, since the adhesive set according to the present embodiment can form a cured product having a high curing rate, it is possible to form a cured product having excellent adhesive strength and adhesive stability.

(Structure using adhesive set and its manufacturing method)
A structure using the above-mentioned adhesive set can be manufactured by a manufacturing method including a step (adhesion step) of adhering adherends to each other using the above-mentioned adhesive set. The method for manufacturing a structure according to an embodiment includes a step of adhering a first adherend and a second adherend to each other using the above-mentioned adhesive set.

In the bonding step, the first liquid and the second liquid may be arranged between the adherends. The adherend is made of, for example, a metal such as steel, iron, copper, tinplate, aluminum, or stainless steel, a resin, or carbon fiber reinforced plastic. 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, the first adherend and the second adherend are arranged with a predetermined gap, and the first liquid is placed in the gap by using a device such as a mixing nozzle. And inject the second solution. 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 cured and the adherends are adhered to each other.

Since the adhesive set used in this production method can be cured at room temperature (25 ° C.), the temperature at which the bonding step is carried out may be, for example, 100 ° C. or lower, 80 ° C. or lower, or 50 ° C. or lower. The temperature may be 10 ° C or higher or 20 ° C or higher. The bonding step may be carried out while changing the temperature stepwise. For example, after bonding at a temperature of 50 ° C. or lower, aftercure may be performed at a temperature of 100 ° C. or lower.

The structure obtained by the above manufacturing method includes a first adherend, a second adherend, and an adhesive portion for adhering the first adherend and the second adherend. The adhesive portion is a cured product of a mixture of liquids (for example, a mixture of the first liquid and the 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 these Examples.

<Synthesis of polyurethane acrylate>
(Synthesis Example 1: Synthesis of Polyurethane Acrylate A)
100 g of polycarbonate diol (product name: DURANOL T-5652, manufactured by Asahi Kasei Corporation) was added to a 500 mL separable flask, and the mixture was stirred at 100 ° C. and 0.1 Pa for 1 hour and then cooled to 70 ° C. To this, 28.2 g of diphenylmethane diisocyanate (product name: Millionate MT, manufactured by Tosoh Corporation) and 0.5 g of urethane catalyst (product name: U-CAT 660M, manufactured by Sun Appro Co., Ltd.) are added, and the temperature at 70 ° C. The mixture was stirred for 1 hour. Then, 22.1 g of 4-HBA (4-hydroxybutyl acrylate) was added, and the mixture was stirred at 70 ° C. for 1.5 hours under a nitrogen atmosphere to obtain polyurethane acrylate A having a polycarbonate skeleton.

(Synthesis Example 2: Synthesis of Polyurethane Acrylate B)
A polyurethane acrylate B having a polybutadiene skeleton was obtained in the same manner as in Synthesis Example 1 except that 100 g of a polybutadiene polyol (product name: POLYVEST HT, manufactured by Evonik Industries, Inc.) was used instead of the polycarbonate diol.

(Synthesis Example 3: Synthesis of Polyurethane Acrylate C)
A polyurethane acrylate C having a polyether skeleton was obtained in the same manner as in Synthesis Example 1 except that 100 g of polypropylene glycol (product name: PPG2000, manufactured by Asahi Kasei Corporation) was used instead of the polycarbonate diol.

<Making an adhesive set>
The component (a) and the component (b) were mixed and stirred for 30 minutes to divide the obtained mixture into two parts, the component (c) was added to one of them, and the mixture was stirred for 30 minutes to prepare a first solution. On the other hand, component (d) and component (e) were added and stirred for 30 minutes to prepare a second solution. The blending amount (unit: parts by mass) of each component is shown in Tables 1 and 2 below.

Details of each component shown in Tables 1 and 2 are as follows.
* 1: Dicyclopentenyl acrylate (Product name: FA-511AS, manufactured by Hitachi Kasei Co., Ltd.)
* 2: Unsaturated fatty acid hydroxyalkyl ester-modified ε-caprolactone (Product name: Praxel FA2D, manufactured by Daicel Corporation)
* 3: Aliphatic urethane acrylate (Product name: EBECRYL230, manufactured by Daicel Ornex Co., Ltd.)
* 4: Cumene hydroperoxide (Product name: Park Mill H-80, manufactured by NOF CORPORATION)
* 5: Copper naphthenate (8% copper naphthenate manufactured by Toei Kako Co., Ltd.)
* 6: o-sulfobenzimide (product name: saccharin (insoluble), manufactured by Daiwa Kasei Co., Ltd.)
* 7: Methyl methacrylate * 8: 3-Acryloxipropyltrimethoxysilane (Product name: KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.)

<Evaluation>
The first solution and the second solution are mixed at a mixing ratio of 1: 1 (volume ratio) between the first solution and the second solution, and the obtained mixture is cured after 24 hours of pot life by the following method. The ratio, shear bond strength, warpage after heating, and bulk physical properties (physical properties of the cured mixture) were measured. The results are shown in Tables 3 and 4.

[Measurement method of pot life]
Immediately after mixing the first solution and the second solution, the time measurement was started with a timer. The stirring rod was inserted vertically into the mixture at regular intervals, and then the stirring rod was lifted to a position about 10 mm away from the surface of the mixture in the vertical direction, and the threads of the mixture were pulled apart. When the thread of the mixture could not be pulled well and became brittle and brittle, the timer was stopped and this was set as the pot life.

[Measurement method of curing rate]
The first solution and the second solution were mixed and a film was formed immediately. It was allowed to stand for 24 hours to prepare a film-like cured product (thickness: about 500 μm). The film-like cured product was cut into a size of 30 mm × 30 mm to obtain a test piece for measuring the curing rate. The weight of the test piece was measured and used as the weight before immersion. The test piece was immersed in 50 mL of acetone for 24 hours, thoroughly washed with acetone, and dried at 60 ° C. for 1 hour. After allowing the dried test piece to cool to room temperature, the weight was measured again and used as the weight after immersion. The curing rate was calculated from the following formula (II).
Curing rate (%) = (weight after immersion) / (weight before immersion) x 100 formula (II)

As shown in Examples 1 to 6, it was confirmed that the adhesive set can achieve both a sufficient pot life and a high curing rate by using the component (e). On the other hand, it was confirmed that the adhesive set of Comparative Example 1 to which the component (e) was not added had a long pot life, but the curing rate after 24 hours was insufficient.

[Measurement method of shear adhesive strength]
A test piece for measuring shear adhesive strength was prepared by the following method. First, two steel sheets (product number: SPCC-SD, size: 25 mm × 100 mm, thickness: 2.0 mm) degreased with acetone and IPA (isopropyl alcohol) were prepared. Two silicone rubber sheets (size: 10 mm × 30 mm; thickness: 1 mm) were arranged as spacers on one of the steel plates so that the adhesive area was 25 mm × 12.5 mm. On the steel sheet, the adhesive set of Examples 4 and 5 was used, and a mixture of the first liquid and the second liquid mixed at a volume ratio of 1: 1 was applied between the spacers, and the other liquid was applied thereto. The steel plates were pasted together. The mixture was then allowed to stand at room temperature for 30 minutes and then heated at 195 ° C. for 30 minutes to cure the mixture. After allowing to cool, the spacer was removed to obtain a test piece (SPCC-SPCC) for measuring shear adhesive strength.

A tensile shear test was performed using a test piece for measuring shear bond strength. For the tensile shear test, an autograph (manufactured by Shimadzu Corporation, model number: AGS-X Plus, load cell: 50 kN) was used, and the test piece was attached to the device with a distance between chucks of 100 mm, a tensile speed of 1 mm / min, and a tensile angle of 180. Measured at °. The maximum point stress of the obtained stress-strain curve was taken as the shear bond strength. The stress was calculated from the measured load and the bonding area (25 mm × 12.5 mm).

A test piece (PC-PC) for measuring the shear adhesive strength was prepared in the same manner as above except that the steel plate SPCC was changed to a PC (polycarbonate) plate, and the shear adhesive strength was measured.

[Measurement method of warpage after heating]
A test piece for warpage measurement was prepared by the following method. First, two PP (polypropylene) spacers (thickness: 0.5 mm) were fixed on an SPCC plate (size: 300 mm × 25 mm, thickness: 0.6 mm) so that the distance between the spacers was 10 mm. .. Next, using the adhesive set of Examples 4 to 6, a mixture of the first liquid and the second liquid mixed at a volume ratio of 1: 1 was applied between the spacers, and an Al plate (large) was applied thereto. (S: 300 mm × 25 mm, thickness: 0.6 mm) were overlapped and fixed with a clip. After allowing to stand at room temperature for 24 hours to cure the mixture, the spacer was removed to prepare a test piece for warpage measurement.

The test piece was heated in a dryer at 180 ° C. for 30 minutes, the test piece was taken out from the dryer and allowed to cool to room temperature, and then the warp was measured.

[Measurement method of Young's modulus, breaking strength and elongation]
Using the adhesive set of Examples 4 to 6, a mixture of the first liquid and the second liquid mixed at a volume ratio of 1: 1 was applied onto a release sheet to form a film-like cured product having a thickness of 100 μm. Then, a laminated sheet of a release sheet and a film-like cured product was obtained. After punching the laminated sheet into a dumbbell shape, the release sheet was peeled off to prepare a test piece. Using an autograph (manufactured by Shimadzu Corporation, model number: AGS-X Plus, load cell: 50 kN), the Young's modulus, breaking strength and elongation of the test piece are measured under the conditions of a tensile speed of 1 mm / min and a tensile angle of 180 °. did.

Claims (9)

A first solution containing an oxidizing agent containing an organic peroxide,
With a second solution containing a reducing agent,
At least one of the first liquid and the second liquid further contains a compound represented by the following general formula (I).
At least one of the first solution and the second solution further contains a compound having a (meth) acryloyl group.
An adhesive set in which at least one of the first solution and the second solution further contains an elastomer soluble in the compound having the (meth) acryloyl group.

[In the formula (I), R represents an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 4. ] The content of the compound represented by the general formula (I) is 0.005 parts by mass to 5.0 parts by mass with respect to 100 parts by mass of the total amount of the compound having the (meth) acryloyl group and the elastomer. The adhesive set according to claim 1. The adhesive set according to claim 1 or 2, wherein the elastomer comprises a polyurethane (meth) acrylate. The adhesive set according to claim 3, wherein the polyurethane (meth) acrylate contains a polyurethane (meth) acrylate having a skeleton derived from a polycarbonate polyol. The adhesive set according to any one of claims 1 to 4, wherein the reducing agent contains a copper compound. The adhesive set according to any one of claims 1 to 5, wherein both the first liquid and the second liquid further contain the compound having the (meth) acryloyl group and the elastomer. The adhesive set according to claim 6, wherein the second liquid further contains the compound represented by the general formula (I). It includes a first adherend, a second adherend, and an adhesive portion for adhering the first adherend and the second adherend.
A structure in which the adhesive portion is a cured product of a mixture of liquids constituting the adhesive set according to any one of claims 1 to 7. A method for producing a structure, comprising a step of adhering a first adherend and a second adherend to each other using the adhesive set according to any one of claims 1 to 7.