JP6579611B2 - Composition - Google Patents

Description

The present invention relates to a (meth) acrylic adhesive composition having good adhesive strength even at low temperatures, for example.

From the viewpoint of labor saving, resource saving, and energy saving, a room-temperature fast-curing adhesive composition is used as an adhesive that bonds at room temperature in a short time. Conventionally, room-temperature fast-curing adhesive compositions include two-part fast-curing epoxy adhesive compositions, anaerobic adhesive compositions, instantaneous adhesive compositions, and second-generation acrylic adhesive compositions (SGA). )It has been known.

The two-component fast-curing epoxy adhesive is one in which a main agent and a curing agent are measured, mixed, applied to an adherend, and cured by a reaction between the main agent and the curing agent. However, the two-part type fast-curing epoxy adhesive is required to have higher peel strength and impact strength.

The anaerobic adhesive is cured by pressure-bonding the adhesive composition between adherends to block air. However, the anaerobic adhesive composition is required to have a property of curing even if the part of the adhesive composition comes out of the adherend when it is pressure-bonded, even if the part of the adhesive composition comes into contact with air. . In addition, a property of curing even when the clearance between adherends is large is required.

Instant adhesives usually have cyanoacrylate as the main component and are excellent in workability. However, higher peel strength and impact strength are required.

SGA is a two-part acrylic adhesive, but it does not require accurate metering of the two agents, and even if metering or mixing is incomplete, it can be cured at room temperature for several minutes to several tens of minutes just by contacting the two agents. In addition, it has excellent workability, high peel strength, high impact strength, and good curing of the exposed portion, so it is widely used from the electrical / electronic parts field to the civil engineering / architecture field. Recently, SGA with reduced odor has come out, and it is possible to work even in places where ventilation facilities are insufficient.

Among various required characteristics, characteristics under a low temperature environment have been required, and the cured adhesive is also exposed to an environment below freezing point.

Under low temperature conditions, the cured adhesive becomes brittle, the adhesive strength is lowered, and peeling may occur.

Japanese Patent Laid-Open No. 11-147921 JP 2001-55423 A

Patent Document 1 discloses a method for improving the peel strength at a low temperature with a liquid elastomer. However, there is no description that a composition having low odor and low volatility can be obtained by not containing methyl methacrylate. Patent Document 2 discloses a low odor and low volatility composition. However, there is no description about rubber having a polymerizable unsaturated double bond.

An object of the present invention is to provide, for example, a two-component (meth) acrylic adhesive having excellent peel strength at low temperatures.

That is, the present invention
Below (1) (1-1) to polymerizable vinyl monomer containing a (1-3) (1-1) The compound of the general formula (A) (A) Z- O- (R 2 O) p- R ₁
Wherein, Z is shown a (meth) acryloyl group, R ₁ is a phenyl group having a phenyl group or a number from 1 to 3 alkyl groups the carbon. R ₂ represents —C ₂ H ₄ —, —C ₃ H ₆ —, —CH ₂ CH (CH ₃ ) —, —C ₄ H ₈ — or —C ₆ H ₁₂ —, and p is an integer of 1 to 10 Represents. ]
(1-2) Compound of General Formula (B) General Formula (B) Z—O— (R ₂ O) p—H
[Wherein, Z, R ₂ and p are as defined above. ]
(1-3) Compound of General Formula (C) General Formula (C) Z—O—R ₄
[Wherein, Z represents a (meth) acryloyl group, and R ₄ represents an alkyl group having 3 to 16 carbon atoms. ]
(2) a polymerization initiator, (3) a reducing agent, (4) a rubber having a polymerizable unsaturated double bond at the terminal and having a (meth) acrylonitrile content of 10 to 30 mol%, (5) It is a composition comprising an elastomer having no polymerizable unsaturated double bond at the terminal, and (5) an elastomer having no polymerizable unsaturated double bond at the terminal has a (meth) acrylonitrile content of 10 to 10. (5) The composition in which the elastomer having no polymerizable unsaturated double bond at the terminal is a diene copolymer, and the first agent contains at least (2 An adhesive composition comprising a polymerization initiator and a second agent composition containing at least (3) a reducing agent in the second agent, and comprising the curable resin composition. Adhering the adherend using the adhesive composition That a conjugate is a bonding method comprising bonding the adherend using the adhesive composition.

The present invention can provide, for example, a (meth) acrylic adhesive composition with improved peel strength at low temperatures.

Hereinafter, the present invention will be described in detail.

The present invention contains (1-1), (1-2) and (1-3) as polymerizable vinyl monomers. (1) The polymerizable vinyl monomer only needs to be capable of radical polymerization. Among these, the polymerizable vinyl monomer is more preferably a polymerizable (meth) acrylic acid derivative from the viewpoint of curing speed and the like. In 100 parts by weight of the polymerizable vinyl monomer, the polymerizable (meth) acrylic acid derivative is preferably 70 parts by weight or more, and all the polymerizable vinyl monomers are more preferably polymerizable (meth) acrylic acid derivatives. Hereinafter, (1) 100 parts by mass of the polymerizable vinyl monomer is preferably in a total of 100 parts by mass of (1-1), (1-2), and (1-3).

The compound of (1-1) general formula (A) used by this invention means the following structures.
Formula (A) Z—O— (R ₂ O) p—R ₁
Wherein, Z is shown a (meth) acryloyl group, R ₁ is a phenyl group having a phenyl group or a number from 1 to 3 alkyl groups the carbon. R ₂ represents —C ₂ H ₄ —, —C ₃ H ₆ —, —CH ₂ CH (CH ₃ ) —, —C ₄ H ₈ — or —C ₆ H ₁₂ —, and p is an integer of 1 to 10 Represents. ]

(1-1) As a compound of general formula (A), phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, phenoxypropyl (meth) acrylate, phenoxydipropylene glycol (meth) ) Acrylate and phenoxy polypropylene glycol (meth) acrylate. Among these, phenoxyethyl (meth) acrylate is preferable in terms of adhesiveness.

(1-1) As for the usage-amount of the compound of general formula (A), 10-70 mass parts is preferable in 100 mass parts of (1) polymerizable vinyl monomers, and 20-60 mass parts is more preferable. If it is less than 10 parts by mass, the adhesiveness may be lowered, and if it exceeds 70 parts by mass, the adhesiveness may be lowered.

The compound of (1-2) general formula (B) used by this invention means the following structures.

Formula (B) Z—O— (R ₂ O) p—H
[Wherein, Z, R ₂ and p are as defined above. ]

(1-2) As the compound of the general formula (B), hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, Examples include diethylene glycol mono (meth) acrylate and polypropylene glycol (meth) acrylate. Among these, hydroxyalkyl (meth) acrylate is preferable in terms of adhesion and moisture resistance. Among the hydroxyalkyl (meth) acrylates, 2-hydroxyethyl (meth) acrylate and / or 2-hydroxypropyl (meth) acrylate is preferable, and 2-hydroxyethyl (meth) acrylate is more preferable.

(1-2) As for the usage-amount of the compound of general formula (B), 10-80 mass parts is preferable in 100 mass parts of (1) polymerizable vinyl monomers, and 20-80 mass parts is more preferable. If it is less than 10 parts by mass, the adhesion may be reduced, and if it exceeds 80 parts by mass, the moisture resistance may be reduced.

The compound of (1-3) general formula (C) used by this invention means the following structures.

Formula _{(C) Z-O-R} 4
[Wherein, Z represents a (meth) acryloyl group, and R ₄ represents an alkyl group having 3 to 16 carbon atoms. ]

(1-3) As a compound of general formula (C), butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n-lauryl (meth) acrylate and tridecyl (meth) acrylate Etc. Among these, 2-ethylhexyl (meth) acrylate is preferable in terms of adhesion and moisture resistance.

Wherein the carbon number of _{R 4} is preferably 3 to 16 carbon atoms, 4 to 13 pieces is preferable. If it is less than 3, the moisture resistance may be reduced, and if it exceeds 16, the adhesion may be reduced.

(1-3) The amount of the compound of the general formula (C) used is preferably 5 to 45 parts by weight, more preferably 7 to 40 parts by weight, and more preferably 10 to 35 parts by weight in 100 parts by weight of the polymerizable vinyl monomer (1). Part is most preferred. If it is less than 5 parts by mass, the moisture resistance may be reduced, and if it exceeds 45 parts by mass, the adhesion, particularly the tensile shear strength against iron, may be reduced.

The (2) polymerization initiator used in the present invention is preferably a thermal radical polymerization initiator. Among the thermal radical polymerization initiators, organic peroxides are preferable. Examples of the organic peroxide include cumene hydroperoxide, paramentane hydroperoxide, tertiary butyl hydroperoxide, diisopropylbenzene dihydroperoxide, methyl ethyl ketone peroxide, benzoyl peroxide, and tertiary butyl peroxybenzoate. . These 1 type (s) or 2 or more types can be used. Among these, cumene hydroperoxide is preferable in terms of reactivity.

(2) The amount of the polymerization initiator used is preferably 0.5 to 10 parts by mass and more preferably 1 to 7 parts by mass with respect to (1) 100 parts by mass of the polymerizable vinyl monomer. If it is less than 0.5 parts by mass, the curing rate may be slow, and if it exceeds 10 parts by mass, the storage stability may be deteriorated.

The (3) reducing agent used in the present invention can be any known reducing agent that reacts with the polymerization initiator to generate radicals. Representative reducing agents include, for example, tertiary amines, thiourea derivatives and transition metal salts.

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. Among these, in terms of reactivity, transition metal salts are preferable, and vanadyl acetylacetonate is more preferable.

(3) 0.01-5 mass parts is preferable with respect to 100 mass parts of (1) polymerizable vinyl monomers, and, as for the usage-amount of a reducing agent, 0.05-1 mass part is more preferable. If it is less than 0.01 parts by mass, the curing rate may be slow, and if it exceeds 5 parts by mass, the storage stability may be reduced.

The rubber having a polymerizable unsaturated double bond at the terminal (4) and having a (meth) acrylonitrile content of 10 to 30 mol% used in the present invention has a polymerizable unsaturated diester at the terminal of the rubber component. It is a compound having a heavy bond. Among (4), a compound having a polymerizable unsaturated double bond at both ends of the rubber component is preferable.

The polymerizable unsaturated double bond is preferably a (meth) acryloyl group and / or a vinyl group, and more preferably a (meth) acryloyl group in terms of good reactivity.

The rubber component is preferably a diene (co) polymer. Examples of diene (co) polymers include butadiene- (meth) acrylonitrile rubber and (meth) acrylonitrile-butadiene- (meth) acrylic acid rubber. Among the diene (co) polymers, a butadiene- (meth) acrylonitrile rubber is preferable and a butadiene-acrylonitrile rubber is more preferable in terms of good flexibility and good compatibility with the monomer.

The content of (meth) acrylonitrile is preferably 10 to 30% by mole, more preferably 15 to 25% by mole, and most preferably 13 to 20% by mole because it has excellent peel strength at low temperatures and can withstand strong impacts. When the (meth) acrylonitrile content is 10 mol% or more, the effect of the present invention is easily obtained, and when it is 30 mol% or less, corrosion is unlikely to occur even when a metal such as copper is an object to be deposited.

As a method for introducing a polymerizable unsaturated double bond at both ends of the molecular chain of the rubber component, for example, after introducing carboxyl groups at both ends of the rubber component, glycidyl (meth) acrylate is reacted with the carboxyl groups. Or a method of dehydrating the carboxyl group and hydroxy (meth) acrylate. Alternatively, diisocyanate and hydroxy (meth) acrylate may be reacted in advance and reacted with a liquid rubber having a reactive hydroxyl group at the terminal.

Among these, rubbers obtained by introducing carboxyl groups at both ends of the rubber component and then reacting the carboxyl groups with glycidyl (meth) acrylate are preferred.
For example, a rubber obtained by using (meth) acrylonitrile rubber as a rubber component, introducing a carboxyl group at both ends of the rubber component, and then reacting the carboxyl group with glycidyl methacrylate, is manufactured by An Emerald Performance material " Hypro 1300X33LC VTBNX "and the like.

(4) The rubber having a polymerizable unsaturated double bond at the terminal and having a (meth) acrylonitrile content of 10 to 30% by mass is preferably a liquid rubber. Liquid rubber refers to rubber that is liquid at normal temperature (23 ° C.).

The number average molecular weight of the rubber having a polymerizable unsaturated double bond at the terminal (4) and having a (meth) acrylonitrile content of 10 to 30% by mass is preferably 1000 to 1000000, and 2000 to 500000. More preferred. If it is less than 1000, the peel strength at low temperature may be affected, and if it exceeds 1000000, the fluidity may be lost.

In the Example of this invention, the number average molecular weight of polystyrene conversion measured by GPC (gel permeation chromatography) was used. Specifically, the average molecular weight was determined by preparing a calibration curve with commercially available standard polystyrene using tetrahydrofuran as a solvent under the following conditions, using a GPC system (SC-8010 manufactured by Tosoh Corporation). .

Flow rate: 1.0 ml / min
Set temperature: 40 ° C
Column configuration: “TSK guardcolumn MP (× L)” manufactured by Tosoh Corp. 6.0 mm ID × 4.0 cm 1 and “TSK-GELMULTIPOREHXL-M” 7.8 mm ID × 30.0 cm (16,000 theoretical plates) manufactured by Tosoh Corp. 2, 3 in total (32,000 theoretical plates as a whole)
Sample injection volume: 100 μl (sample solution concentration 1 mg / ml)
Liquid feeding pressure: 39 kg / cm ²
Detector: RI detector

(4) The use amount of rubber having a polymerizable unsaturated double bond at the terminal and having a (meth) acrylonitrile content of 10 to 30% by mass is based on (1) 100 parts by mass of the polymerizable vinyl monomer. 1-50 mass parts is preferable, 5-30 mass parts is more preferable, and 10-20 mass parts is the most preferable. If it is less than 1 part by mass, the peel strength and impact resistance at low temperatures may be small, and if it exceeds 50 parts by mass, the viscosity will increase, workability will deteriorate, and curability may be insufficient.

In the present invention, (5) an elastomer having no polymerizable unsaturated double bond at the terminal is used.

(5) As the elastomer having no polymerizable unsaturated double bond at the terminal, (meth) acrylonitrile-butadiene- (meth) acrylic acid copolymer, (meth) acrylonitrile-butadiene-methyl (meth) acrylate copolymer Diene copolymers such as (meth) acrylonitrile-butadiene copolymer and styrene-butadiene copolymer, styrene thermoplastic elastomers such as chlorosulfonated polyethylene and styrene-polybutadiene-styrene synthetic rubber, urethane elastomers, etc. Can be mentioned.
(5) As an elastomer having no polymerizable unsaturated double bond at the terminal, (1) an elastomer soluble in a polymerizable vinyl monomer is preferable.

Among these, a diene copolymer is preferable in terms of solubility and adhesiveness. Among the diene copolymers, (meth) acrylonitrile-butadiene- (meth) acrylic acid copolymers and / or (meth) acrylonitrile-butadiene copolymers are preferable, and (meth) acrylonitrile-butadiene copolymers are more preferable. preferable.

(5) The elastomer having no polymerizable unsaturated double bond at the end preferably has a (meth) acrylonitrile structure. In the case of having a (meth) acrylonitrile structure, the (meth) acrylonitrile content is preferably 10 to 30 mol%, more preferably 15 to 25 mol% in terms of excellent peel strength at low temperatures and withstanding strong impacts. Most preferred is 13 to 20 mol%. When the (meth) acrylonitrile content is 10 mol% or more, the effect of the present invention is easily obtained, and when it is 30 mol% or less, corrosion is unlikely to occur even when a metal such as copper is an object to be deposited.

(5) The usage-amount of the elastomer which does not have a polymerizable unsaturated double bond at the terminal is preferably 5 to 35 parts by mass and more preferably 7 to 33 parts by mass with respect to 100 parts by mass of the polymerizable vinyl monomer. Preferably, 10 to 30 parts by mass is most preferable.

(4) Rubber having a polymerizable unsaturated double bond at the terminal and having a (meth) acrylonitrile content of 10 to 30% by mass and (5) Elastomer having no polymerizable unsaturated double bond at the terminal When using together, the content rate is a mass ratio in a total of 100 mass parts of (4) and (5), (4) :( 5) = 10-90: 90-10 are preferable, 30-70: 70-30 are more preferable, and 40-60: 60-40 are the most preferable.

In the composition of the present invention, various paraffins can be used in order to quickly cure a portion in contact with air. Examples of paraffins include paraffin, microcrystalline wax, carnauba wax, beeswax, lanolin, spermaceti, ceresin and candelilla wax. Of these, paraffin is preferred. The melting point of paraffins is preferably 40 to 100 ° C.

As for the usage-amount of paraffin, 0.1-5 mass parts is preferable with respect to 100 mass parts of (1) polymerizable vinyl monomers. If it is less than 0.1 parts by mass, the portion in contact with air may be hardened, and if it exceeds 5 parts by mass, the adhesive strength may be reduced.

Furthermore, various antioxidants including a polymerization inhibitor can be used for the purpose of improving storage stability.

Furthermore, in the present invention, it is preferable to use a phosphate in order to improve adhesion and increase the curing rate.

In addition to these, known substances such as plasticizers, fillers, colorants, and rust inhibitors may be used as desired.

As mentioned above, although the component used by this invention was demonstrated, even if it uses a compound with few odors other than said (1-1), (1-2), and (1-3) for the composition of this invention. Good.

As an embodiment of the present invention, it is preferably used as an adhesive composition. In this case, for example, use as a two-component adhesive composition can be mentioned. For the two-component type, all the essential components of the adhesive composition of the present invention are not mixed during storage, and the adhesive composition is divided into a first agent and a second agent, and at least (2) polymerization starts in the first agent The agent is stored separately in a second agent containing at least (3) a reducing agent and, optionally, a phosphate. In this case, it can be used as a two-component adhesive composition by applying both agents simultaneously or separately to contact and cure.

In another embodiment, one or both of the first agent and the second agent are preliminarily incorporated with a polymerizable vinyl monomer and other optional components, and are mixed together at the time of curing, whereby one-component adhesive It can be used as an agent composition.

In these embodiments, it is preferable to use it as a two-part adhesive composition in terms of excellent storage stability.

In this invention, a to-be-adhered body is joined with the hardening body of curable resin composition, and a joined body is produced. There are no restrictions on the various materials of the adherend, such as paper, wood, ceramic, glass, ceramics, rubber, plastic, mortar, concrete, and metal, but it is better when the adherend is metal, especially iron or stainless steel. Show good adhesion.

(Experimental example)
Hereinafter, the present invention will be described in more detail with reference to experimental examples. An adhesive composition having the composition shown in Table 1 was prepared, and various physical properties were measured. The results are shown in Table 1.
The unit of the amount used of each substance is shown in parts by mass. For each substance, paraffin was used as the paraffin, and various physical properties were measured as follows.

For each substance described in the table, the following abbreviations were used.
Liquid NBR: Liquid acrylonitrile rubber having a polymerizable unsaturated double bond at the terminal (manufactured by An Emerald Performance material, Hypro 1300X33LC VTBNX, liquid, number average molecular weight 3900)
NBR: Acrylonitrile-butadiene copolymer, elastomer that does not have a polymerizable unsaturated double bond at the end (commercially available)
AN amount: acrylonitrile content (mol%) contained in liquid NBR and acrylonitrile-butadiene copolymer having a reactive unsaturated double bond at the terminal

[Tensile Shear Strength (Tensile Shear Adhesive Strength)] A SPCC-D wiped steel plate of 100 × 25 × 1.6 mm was used as a test piece. In accordance with JIS K-6850 under an environment of a temperature of 23 ° C. and a humidity of 50%, the first agent was applied to one side of one test piece, and the second agent was applied to the other test piece. Immediately thereafter, the coated surfaces were superposed and bonded together. Thereafter, it was cured at room temperature for 24 hours, and this was used as a sample for measuring tensile shear strength. The tensile shear strength (unit: MPa) of the sample was measured in an environment of a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 10 mm / min.

[Peel Strength (Peel Adhesive Strength)] As a test piece, a 200 × 25 × 1.6 mm SPCC-D wiped steel plate and a 200 × 25 × 1.5 mm SUS304 waste wiped steel plate were used. In accordance with JIS K-6854 in an environment of a temperature of 23 ° C. and a humidity of 50%, the first agent was applied to one side of one test piece, and the second agent was applied to one side of the other test piece. Immediately thereafter, the coated surfaces were superposed and bonded together. After that, it was cured at room temperature for 24 hours, and this was used as a sample for measuring T peel strength. Comparison of T peel strength at a tensile rate of 50 mm / min in an environment of temperature 23 ° C. and humidity 50% and T peel strength at a tensile rate of 50 mm / min in an environment of temperature −20 ° C. as confirmation of low temperature characteristics did. Moreover, the breaking distance of the peeling in the environment of temperature-20 degreeC was also compared.
The breaking distance of peeling was measured by the following method. Using a sample for measuring the T peel strength, setting the gap between the chucks to 1 cm, fixing the upper end and lower end of the above test piece, and moving the test piece up and down at a temperature of −20 ° C. and a tensile speed of 50 mm / min. Tensile distances leading to tension and breaking were measured. The greater the breaking distance, the greater the peel strength.

[Impact resistance test] As a test piece, a SUS304 waste wiping treatment panel of panel 2000 × 500 × 1.5 mm and a reinforcing material 1800 × 20 × 1.5 mm SPCC-D waste wiping treatment plate were used. In an environment of a temperature of 23 ° C. and a humidity of 50%, the first agent was applied to the center position of the panel, and the second agent was applied to the reinforcing material. Immediately thereafter, the coated surfaces were superposed and bonded together. Thereafter, it was cured at room temperature for 24 hours, and this was used as a sample for impact resistance test measurement. In the impact resistance test, the panel with the reinforcing material on the back side was leveled, and both ends were fixed with support. A 45 kg iron ball was suspended at a height of 800 mm from the surface of the panel and a position of 1000 mm from the edge of the panel. The steel ball was naturally dropped and an impact was applied to the panel, and the situation where the reinforcing material on the back surface peeled from the panel was observed.
The peeling rate of the reinforcing material was calculated from the following formula.
Peeling rate of reinforcing material (%) = (Area where reinforcing material was peeled) / (Area of adhesive application surface where adhesive was applied) × 100 (%)

[Odor] The odor intensity of each curable resin composition was as follows.
A cured product having a diameter of 10 mm and a thickness of 1 mm was prepared using the resin composition, the cured product was put in a glass bottle, sealed, and allowed to stand for 1 hour, and then the odor was measured using an odor sensor (Calmore). . The measured value in the tested room was 360. The larger the value, the stronger the odor. The numerical value of odor is preferably 1000 or less, more preferably 600 or less, and most preferably 500 or less.

The table shows the following. In the present invention, as the amount of (4) increases, the peel strength at a low temperature increases and the impact resistance increases. Since Experimental Example 1 contains (4), the peel strength is higher than that of Experimental Example 2. However, since Experimental Example 1 has a high acrylonitrile content in (5), impact resistance is small.

With the adhesive composition of the present invention, a two-component (meth) acrylic adhesive composition having a low odor and a high peel strength at low temperatures can be obtained. Therefore, it is possible to work in a place where ventilation is insufficient, and it is possible to obtain an adhesive having a wide adaptable environment in which the cured adhesive is not peeled even in a cold region. Furthermore, since a two-component (meth) acrylic adhesive that can withstand strong impacts can be provided, not only the working environment is improved, but it can be applied to various industrial fields, which is beneficial.

Claims (8)

Below (1) (1-1) to polymerizable vinyl monomer containing a (1-3) (1-1) The compound of the general formula (A) (A) Z- O- (R 2 O) p- R ₁
Wherein, Z is shown a (meth) acryloyl group, R ₁ is a phenyl group having a phenyl group or a number from 1 to 3 alkyl groups the carbon. R ₂ represents —C ₂ H ₄ —, —C ₃ H ₆ —, —CH ₂ CH (CH ₃ ) —, —C ₄ H ₈ — or —C ₆ H ₁₂ —, and p is an integer of 1 to 10 Represents. ]
(1-2) Compound of General Formula (B) General Formula (B) Z—O— (R ₂ O) p—H
[Wherein, Z, R ₂ and p are as defined above. ]
(1-3) Compound of General Formula (C) General Formula (C) Z—O—R ₄
[Wherein, Z represents a (meth) acryloyl group, and R ₄ represents an alkyl group having 3 to 16 carbon atoms. ]
(2) a polymerization initiator, (3) a reducing agent, (4) a rubber having a polymerizable unsaturated double bond at the terminal and having a (meth) acrylonitrile content of 10 to 30 mol%, (5) not be have a polymerizable unsaturated double bond at the terminal, and (meth) acrylonitrile content is a composition comprising 10 to 30 mole% of the elastomer, (1) a polymerizable vinyl monomer 100 parts by weight In (1-1) the usage-amount of the compound of general formula (A) is 10-70 mass parts, (1-2) the usage-amount of the compound of general formula (B) is 10-80 mass parts, (1-3) The usage-amount of the compound of general formula (C) is 5-45 mass parts, (2) The usage-amount of a polymerization initiator is 0 with respect to 100 mass parts of (1) polymeric vinyl monomers. 5 to 10 parts by mass, and (3) the amount of the reducing agent used is (1) part by mass of the polymerizable vinyl monomer. On the other hand, the amount of rubber used is 0.01 to 5 parts by mass, (4) has a polymerizable unsaturated double bond at the terminal, and has a (meth) acrylonitrile content of 10 to 30 mol%. (1) 1 to 50 parts by mass with respect to 100 parts by mass of the polymerizable vinyl monomer, (5) no polymerizable unsaturated double bond at the end, and a (meth) acrylonitrile content of 10 The composition whose usage-amount of an elastomer of -30 mol% is 5-35 mass parts with respect to 100 mass parts of (1) polymerizable vinyl monomers. (4) Rubber having a polymerizable unsaturated double bond at the end and having a (meth) acrylonitrile content of 10 to 30 mol% and (5) No polymerizable unsaturated double bond at the end In addition, the content ratio of the elastomer having a (meth) acrylonitrile content of 10 to 30 mol% is a mass ratio in a total of 100 parts by mass of (4) and (5), and (4) :( 5) = 10 The composition of claim 1, wherein the composition is 90: 90-10. Contains at least a (2) the polymerization initiator in the first agent, at least (3) The composition of claim 1 wherein the two-pack type which comprises a reducing agent to the second agent. A curable resin composition comprising the composition according to any one of claims 1 to 3 . An adhesive composition comprising the curable resin composition according to claim 4 . Further, paraffins are contained in an amount of 0.1 to 5 parts by mass with respect to 100 parts by mass of the polymerizable vinyl monomer (1), the use is for metal bonding, and no methyl methacrylate is contained. Adhesive composition. The joined body formed by adhere | attaching a to-be-adhered body using the adhesive composition of Claim 5 or 6. The adhesion method formed by adhere | attaching a to-be-adhered body using the adhesive composition of Claim 5 or 6.