JP2018119113A - Composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition having excellent deep curability. A composition containing the following (1) to (3). (1) Polymerizable vinyl monomer containing (1-1) to (1-3) (1-1) Monofunctional (meth) acrylate having a phenyl group (1-2) Monofunctional (meth) having a hydroxyl group Acrylate (1-3) Polyfunctional (meth) acrylate having a bisphenol structure (2) (2-1) Polymerization initiator containing a photoradical polymerization initiator (3) Having a polymerizable unsaturated double bond at the terminal None of the elastomers with (meth) acrylonitrile content of 1 to 30 mol% [selection diagram]

Description

The present invention relates to a composition having good deep part curability, 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-part type 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.

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

Two-part acrylic adhesives are disclosed in Patent Documents 1 and 2. However, there is no description about a radical photopolymerization initiator.

An object of this invention is to provide the composition excellent in deep part sclerosis | hardenability, for example.

The inventors have used a two-component (meth) acrylic that is excellent in deep-part curability when a composition containing a polymerizable vinyl monomer having a specific composition, a radical photopolymerization initiator, and a specific elastomer is used. It has been found that a system adhesive can be provided.

該組成物を含有してなる硬化性樹脂組成物であり、
該硬化性樹脂組成物を含有してなる接着剤組成物であり、
該接着剤組成物を使用して被着体を接着してなる接合体であり、
該接着剤組成物を使用して被着体を接着してなる接着方法
である。 That is, the present invention
It is a composition comprising the following (1) to (3),
(1) Polymerizable vinyl monomer containing (1-1) to (1-3) (1-1) Monofunctional (meth) acrylate having a phenyl group (1-2) Monofunctional (meth) having a hydroxyl group Acrylic (1-3) Polyfunctional (meth) acrylate having bisphenol structure (2) (2-1) Polymerization initiator containing radical photopolymerization initiator (3) Having a polymerizable unsaturated double bond at the terminal And an elastomer (3) having a (meth) acrylonitrile content of 1 to 30 mol%, having no polymerizable unsaturated double bond at the terminal, and having a (meth) acrylonitrile content of 1 to 30 mol% And the elastomer is a diene copolymer,
Furthermore, the composition comprising paraffins,
(3) The amount of the elastomer having no polymerizable unsaturated double bond at the terminal and having a (meth) acrylonitrile content of 1 to 30 mol% is (1) 100 parts by mass of the polymerizable vinyl monomer. In contrast, the composition is 5 to 35 parts by weight,
(1-1) The amount of the monofunctional (meth) acrylate having a phenyl group is 10 to 70 parts by mass in (1) 100 parts by mass of the polymerizable vinyl monomer, and (1-2) a unit having a hydroxyl group. The amount of the functional (meth) acrylate used is 10 to 80 parts by mass in (1) 100 parts by mass of the polymerizable vinyl monomer, and (1-3) the amount of polyfunctional (meth) acrylate having a bisphenol structure is (1) 1 to 35 parts by mass in 100 parts by mass of the polymerizable vinyl monomer, (3) no polymerizable unsaturated double bond at the terminal, and (meth) acrylonitrile content of 1 to 30 mol %, The composition is used in an amount of 5 to 35 parts by mass with respect to 100 parts by mass of the polymerizable vinyl monomer.
Furthermore, (2) the polymerization initiator is the composition comprising (2-1) a photoradical polymerization initiator and (2-2) a thermal radical polymerization initiator,
And (4) the composition comprising a reducing agent,
The first agent contains at least (2-2) a thermal radical polymerization initiator, and the second agent contains at least (4) a reducing agent.
(1-1) The monofunctional (meth) acrylate having a phenyl group is the composition of the general formula (A),
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. ]
(1-2) The composition in which the monofunctional (meth) acrylate having a hydroxyl group is a compound of the general formula (B),
Formula (B) in _{Z-O- (R 2 O)} p-H [wherein, Z, _{R 2} and p are as defined above. ]
(1-3) The composition in which the polyfunctional (meth) acrylate having a bisphenol structure is a compound of the general formula (C),

A curable resin composition comprising the composition;
An adhesive composition comprising the curable resin composition;
A bonded body obtained by bonding an adherend using the adhesive composition;
This is an adhesion method in which an adherend is adhered using the adhesive composition.

The present invention can provide, for example, a composition having excellent deep part curability.

Hereinafter, embodiments of the present invention will be described in detail.

In one Embodiment of this invention, it is a composition formed by containing following (1)-(4).
(1) Polymerizable vinyl monomer containing (1-1) to (1-3) (1-1) Monofunctional (meth) acrylate having a phenyl group (1-2) Monofunctional (meth) having a hydroxyl group Acrylic (1-3) Polyfunctional (meth) acrylate having a bisphenol structure (2) A polymerization initiator containing a radical photopolymerization initiator (3) No polymerizable unsaturated double bond at the end, and ( An elastomer having a meth) acrylonitrile content of 1 to 30 mol%,

(1) (1-1) to (1-3) are preferably the following compounds.
(1-1) Compound of General Formula (A) General 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. ]
(1-2) Compound of General Formula (B) General Formula (B) Z—O— (R ₂ O) p—H [wherein Z, R ₂ and p are as described above. ]
(1-3) Compound of general formula (C)

In this embodiment, (1-1), (1-2), and (1-3) are contained as a polymerizable vinyl monomer. (1) The polymerizable vinyl monomer only needs to be capable of radical polymerization. Among these, from the viewpoint of curing speed and the like, the polymerizable vinyl monomer is more preferably a polymerizable (meth) acrylic acid derivative. In 100 parts by mass of the polymerizable vinyl monomer, the polymerizable (meth) acrylic acid derivative is preferably 70 parts by mass or more, and all the polymerizable vinyl monomers are polymerizable (meth) acrylic acid derivatives (hereinafter referred to as (meth) acrylates). More preferred). 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).

Monofunctional (meth) acrylate refers to a compound having one (meth) acryloyloxy group. The polyfunctional (meth) acrylate refers to a compound having two or more (meth) acryloyloxy groups. Among polyfunctional (meth) acrylates, compounds having two (meth) acryloyloxy groups are preferred.

(1-1) used in the present embodiment is a monofunctional (meth) acrylate having a phenyl group. The phenyl group may have a substituent. The phenyl group includes a benzyl group.
In (1-1) used by this embodiment, the compound of general formula (A) is preferable.

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 monofunctional (meth) acrylate which has a phenyl group, 10-70 mass parts is preferable in 100 mass parts of (1) polymeric 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.

(1-2) used in the present embodiment is a monofunctional (meth) acrylate having a hydroxyl group.
Among (1-2) used in the present embodiment, the compound of the general formula (B) is preferable.

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) The amount of the monofunctional (meth) acrylate having a hydroxyl group is preferably 10 to 80 parts by mass and more preferably 20 to 70 parts by mass in 100 parts by mass of the polymerizable vinyl monomer (1). 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.

(1-3) used in the present embodiment is a polyfunctional (meth) acrylate having a bisphenol structure. Of the bisphenol structures, the bisphenol A structure is preferred.

In (1-3) used by this embodiment, the compound of general formula (C) is preferable.

Examples of such (meth) acrylic monomers include 2,2-bis (4- (meth) acryloxyphenyl) propane, 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane, 2,2 -Bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypropoxyphenyl) propane, 2,2-bis (4- (meth) acryloxytetraethoxyphenyl) ) Propane and 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane. Among these, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane is preferable from the viewpoint of adhesiveness.

Q is a number of 0 or more. q is preferably 1 or more, and more preferably 3 or more. q is preferably 15 or less, more preferably 10 or less, and most preferably 8 or less. More preferably, q is 5.

(1-3) The amount of the polyfunctional (meth) acrylate having a bisphenol structure is preferably 1 to 35 parts by mass, more preferably 3 to 20 parts by mass, in 100 parts by mass of the polymerizable vinyl monomer (1). If it is less than 1 part by mass, the adhesion may be reduced, and if it exceeds 35 parts by mass, the moisture resistance may be reduced.

The (2) polymerization initiator used in the present invention contains (2-1) a radical photopolymerization initiator.

As radical photopolymerization initiators, benzophenone and derivatives thereof, benzyl and derivatives thereof, enthraquinone and derivatives thereof, benzoin derivatives such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, Acetophenone derivatives such as diethoxyacetophenone, 4-t-butyltrichloroacetophenone, 2-dimethylaminoethylbenzoate, p-dimethylaminoethylbenzoate, diphenyldisulfide, thioxanthone and its derivatives, camphorquinone, 7,7-dimethyl-2,3 -Dioxobicyclo [2.2.1] heptane-1-carboxylic acid, 7,7-dimethyl-2,3-dioxobicyclo [2.2.1] heptane 1-carboxy-2-bromoethyl ester, 7,7-dimethyl-2,3-dioxobicyclo [2.2.1] heptane-1-carboxy-2-methyl ester, 7,7-dimethyl-2,3 -Camphorquinone derivatives such as dioxobicyclo [2.2.1] heptane-1-carboxylic acid chloride, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2 Α-aminoalkylphenone derivatives such as benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, benzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoyldiethoxy Posphine oxide, 2,4,6-trimethylbenzoyldimethoxyphenylphos Phosphine oxide, acyl phosphine oxide derivatives such as 2,4,6-trimethylbenzoyldiethoxyphenylphosphine oxide, oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester and oxy- And phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester. Among these, benzyl dimethyl ketal is preferable in terms of excellent curability.

(2-1) The usage-amount of radical photopolymerization initiator has preferable 0.5-10 mass parts with respect to 100 mass parts of (1) polymerizable vinyl monomers, and 1-7 mass parts is more preferable. 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.

Furthermore, (2) the polymerization initiator preferably contains (2-1) a photoradical polymerization initiator and (2-2) a thermal radical polymerization initiator.

Among the thermal radical polymerization initiators, organic peroxides are preferable. Examples of organic peroxides 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.

(2-2) 0.5-10 mass parts is preferable with respect to (1) 100 mass parts of polymerizable vinyl monomers, and, as for the usage-amount of a thermal radical polymerization initiator, 1-7 mass parts is more preferable. 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.

(2-2) When a thermal radical polymerization initiator is used, it is preferable to use (4) a reducing agent in combination.

As the (4) reducing agent used in the present embodiment, any known reducing agent that reacts with the polymerization initiator and generates radicals can be used. 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.

(4) The use amount of the reducing agent is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 1 part by mass with respect to 100 parts by mass of the (1) polymerizable vinyl monomer. 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.

In the present embodiment, (3) an elastomer having no polymerizable unsaturated double bond at the terminal and having a (meth) acrylonitrile content of 1 to 30 mol% is used.

(3) As an elastomer having no polymerizable unsaturated double bond at the terminal and having a (meth) acrylonitrile content of 1 to 30 mol%, (meth) acrylonitrile-butadiene- (meth) acrylic acid copolymer Examples thereof include diene copolymers such as polymers, (meth) acrylonitrile-butadiene-methyl (meth) acrylate copolymers, (meth) acrylonitrile-butadiene copolymers, styrene-butadiene copolymers, and the like.

(3) As an elastomer having no polymerizable unsaturated double bond at the terminal and having a (meth) acrylonitrile content of 1 to 30 mol%, (1) an elastomer soluble in a polymerizable vinyl monomer is used. 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.

(3) In an elastomer having no polymerizable unsaturated double bond at the terminal and having a (meth) acrylonitrile content of 1 to 30 mol%, the (meth) acrylonitrile content is excellent in peel strength at low temperatures. From the viewpoint of withstanding a strong impact, 1 to 30 mol% is preferable, 10 to 27 mol% is more preferable, 13 to 25 mol% is most preferable, and 15 to 20 mol% is still more preferable. When the (meth) acrylonitrile content is 1 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.

(3) The amount of the elastomer that does not have a polymerizable unsaturated double bond at the terminal and has a (meth) acrylonitrile content of 1 to 30 mol% is (1) 100 parts by mass of the polymerizable vinyl monomer. On the other hand, 5-35 mass parts is preferable, 10-30 mass parts is more preferable, and 15-20 mass parts is the most preferable. If it is less than 5 parts by mass, the peel strength and impact resistance at low temperatures may be small, and if it exceeds 35 parts by mass, the viscosity will increase, the workability will deteriorate, and the curability may be insufficient.

The composition in the present embodiment can use various paraffins in order to quickly cure the 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 this embodiment, it is preferable to use a phosphate in order to improve adhesiveness 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 embodiment was demonstrated, you may use the compound with few odors other than said (1-1), (1-2), and (1-3).

As an embodiment of the present invention, it is preferably used as an adhesive composition. (2-2) When using a thermal radical polymerization initiator, for example, it may be used as a two-component adhesive composition. For the two-component type, all components are not mixed during storage, the adhesive composition is divided into a first agent and a second agent, and at least (2-2) a thermal radical polymerization initiator is added to the first agent. The agent contains at least (4) a reducing agent and, if necessary, a phosphate, and is stored separately. 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.

When this embodiment contains (2-1) a photoradical polymerization initiator and (2-2) a thermal radical polymerization initiator, it has the following effects.
Even if there is a portion where visible light or ultraviolet light cannot enter, the adhesive composition can be cured by thermal radical polymerization.
When adhering an adherend using an adhesive composition, the adhesive composition existing at the end of the adherend is preliminarily fixed by irradiation with visible light or ultraviolet light, and then allowed to stand to adhere. The body can be fully cured. By temporarily fixing by irradiating visible light or ultraviolet light, the adherend can be bonded with high accuracy.

In this invention, a to-be-adhered body is joined with the hardened | cured material 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.

Hereinafter, the present invention will be described in more detail with reference to experimental examples.

(Experimental example)
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. Various physical properties were measured by the methods described below.

For each substance described in the table, the following abbreviations were used.
2,2-bis (4-methacryloxypolyethoxyphenyl) propane: q = 5 is used.
Paraffins: Paraffin having a melting point of 40 to 100 ° C. is used.
Acrylonitrile-butadiene rubber: Acrylonitrile-butadiene copolymer AN amount not having a polymerizable unsaturated double bond at the terminal end: Acrylonitrile content (mol%) contained in acrylonitrile-butadiene rubber

[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 steel plate of panel 2000 × 500 × 1.5 mm and a SPCC-D waste-wiping steel plate of 1800 × 20 × 1.5 mm 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 (%)

[Depth Curability Test] The deep curability was measured as follows.
Adhesive is filled into a black urethane tube (length: 10 mm) having an inner diameter of 4 mm, and ultraviolet rays are irradiated from the opening. The irradiation conditions are as follows. As an ultraviolet irradiation device, an LED irradiation machine manufactured by HOYA was used, and irradiation was carried out for 60 seconds under the condition that an integrated irradiation amount of 365 nm was 9000 mJ / cm ^2, and curing was performed. After irradiation, the thickness of the cured adhesive from which the uncured part was removed was measured with a caliper.

[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. Since the present invention uses (3), the peel strength at low temperature is high and the impact resistance is large. Experimental example 2 using butadiene rubber containing no acrylonitrile cannot be evaluated because butadiene rubber does not dissolve. Experimental Example 1 having a high acrylonitrile content has low peel strength at low temperatures and low impact resistance. Since Experimental Example 5 does not contain (2-1), the deep curability cannot be obtained.

By the adhesive composition of this invention, the composition excellent in deep part sclerosis | hardenability, for example, the 2 agent type (meth) acrylic-type adhesive composition hardened | cured to a deep part immediately is obtained. Therefore, curing inside the cured product easily proceeds, and a fast-curing two-component (meth) acrylic adhesive composition is obtained.
Since the cured adhesive is exposed to a freezing environment, characteristics under a low temperature environment are required. Under low temperature conditions, the cured adhesive becomes brittle, the adhesive strength is lowered, and peeling may occur.
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. Since the adhesive composition of the present invention does not contain methyl methacrylate, a low odor and low volatility composition 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 (15)

A composition comprising the following (1) to (3).
(1) Polymerizable vinyl monomer containing (1-1) to (1-3) (1-1) Monofunctional (meth) acrylate having a phenyl group (1-2) Monofunctional (meth) having a hydroxyl group Acrylic (1-3) Polyfunctional (meth) acrylate having bisphenol structure (2) (2-1) Polymerization initiator containing radical photopolymerization initiator (3) Having a polymerizable unsaturated double bond at the terminal And an elastomer having a (meth) acrylonitrile content of 1 to 30 mol% (3) The composition according to claim 1, wherein the elastomer having no polymerizable unsaturated double bond at the terminal and having a (meth) acrylonitrile content of 1 to 30 mol% is a diene copolymer. The composition according to claim 1 or 2, further comprising paraffins. (3) The amount of the elastomer having no polymerizable unsaturated double bond at the terminal and having a (meth) acrylonitrile content of 1 to 30 mol% is (1) 100 parts by mass of the polymerizable vinyl monomer. The composition according to claim 1, wherein the composition is 5 to 35 parts by mass. (1-1) The amount of the monofunctional (meth) acrylate having a phenyl group is 10 to 70 parts by mass in (1) 100 parts by mass of the polymerizable vinyl monomer, and (1-2) a unit having a hydroxyl group. The amount of the functional (meth) acrylate used is 10 to 80 parts by mass in (1) 100 parts by mass of the polymerizable vinyl monomer, and (1-3) the amount of polyfunctional (meth) acrylate having a bisphenol structure is (1) 1 to 35 parts by mass in 100 parts by mass of the polymerizable vinyl monomer, (3) no polymerizable unsaturated double bond at the terminal, and (meth) acrylonitrile content of 1 to 30 mol The composition according to any one of claims 1 to 4, wherein the amount of the elastomer used is 1 to 5 parts by mass with respect to 100 parts by mass of the polymerizable vinyl monomer (1). Furthermore, (2) polymerization initiator contains (2-1) radical photopolymerization initiator and (2-2) thermal radical polymerization initiator, The composition of any one of Claims 1-5 formed. The composition according to claim 6, further comprising (4) a reducing agent. The composition according to claim 7, wherein the first agent contains at least (2-2) a thermal radical polymerization initiator, and the second agent contains at least (4) a reducing agent. (1-1) The composition according to any one of claims 1 to 8, wherein the monofunctional (meth) acrylate having a phenyl group is a compound of the general formula (A).
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. ] (1-2) The composition according to any one of claims 1 to 9, wherein the monofunctional (meth) acrylate having a hydroxyl group is a compound of the general formula (B).
Formula (B) in _{Z-O- (R 2 O)} p-H [wherein, Z, _{R 2} and p are as defined above. ] (1-3) The composition according to any one of claims 1 to 10, wherein the polyfunctional (meth) acrylate having a bisphenol structure is a compound of the general formula (C).

  A curable resin composition comprising the composition according to claim 1.   An adhesive composition comprising the curable resin composition according to claim 12.   The joined body formed by adhere | attaching a to-be-adhered body using the adhesive composition of Claim 13.   The adhesion method formed by adhere | attaching a to-be-adhered body using the adhesive composition of Claim 13.