JP6842935B2 - Composition - Google Patents

Description

The present invention relates to, for example, a composition having good deep curability.

In terms of labor saving, resource saving, and energy saving, a room temperature fast-curing adhesive composition is used as an adhesive that adheres in a short time at room temperature. Conventionally, as a normal temperature fast-curing adhesive composition, a two-part fast-curing epoxy adhesive composition, an anaerobic adhesive composition, an instant adhesive composition and a second-generation acrylic adhesive composition (SGA) have been used. )It has been known.

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

The anaerobic adhesive is cured by crimping the adhesive composition between the adherends to block air. However, the anaerobic adhesive composition is required to have a property that when a part of the adhesive composition is squeezed out from the adherend at the time of crimping, the squeezed out portion is cured even if it comes into contact with air. .. Further, it is required to have a property of hardening even when the clearance between adherends is large.

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

SGA is a two-part acrylic adhesive, but it does not require accurate weighing of the two agents, and even if the weighing and mixing are incomplete, it cures in minutes to tens of minutes at room temperature with just the contact of the two agents. In addition, it is widely used from the fields of electrical and electronic parts to the fields of civil engineering and construction because it has excellent workability, high peel strength and impact strength, and good hardening of the exposed part. Recently, SGA that suppresses odor has come out, and it is possible to work even in places where ventilation equipment is inadequate.

Japanese Unexamined Patent Publication No. 11-147921 Japanese Unexamined Patent Publication No. 2001-55423

The two-part acrylic adhesive is disclosed in Patent Documents 1 and 2. However, there is no description about the photoradical polymerization initiator.

An object of the present invention is, for example, to provide a composition having excellent deep curability.

The inventors have stated that when a composition containing a polymerizable vinyl monomer having a specific composition, a photoradical polymerization initiator, and a specific elastomer is used, a two-agent type (meth) acrylic having excellent deep curability is used. We have found that we can provide radical adhesives.

That is, the present invention
A composition containing the following (1) to (4).
(1) Polymerizable vinyl monomer containing (1-1) to (1-4) (1-1) Monofunctional (meth) acrylate having a phenyl group (1-2) Monofunctional (meth) having a hydroxyl group A polymerization initiator containing a polyfunctional (meth) acrylate having an acrylate (1-3) bisphenol structure, a monofunctional (meth) acrylate having an (1-4) alkyl group, and (2) (2-1) photoradical polymerization initiators. (3) Elastomer having no polymerizable unsaturated double bond at the terminal and having a (meth) acrylonitrile content of 1 to 30 mol% (3) No polymerizable unsaturated double bond at the end The composition in which the elastomer having a (meth) acrylonitrile content of 1 to 30 mol% is a diene-based copolymer.
Further, the composition is composed of paraffins.
(3) The amount of the elastomer used, which does not have a polymerizable unsaturated double bond at the terminal and has a (meth) acrylonitrile content of 1 to 30 mol%, is reduced to (1) 100 parts by mass of the polymerizable vinyl monomer. On the other hand, the composition is 5 to 35 parts by mass.
(1-1) The amount of the monofunctional (meth) acrylate having a phenyl group used is 10 to 60 parts by mass in (1) 100 parts by mass of the polymerizable vinyl monomer, and (1-2) a simple having a hydroxyl group. The amount of the functional (meth) acrylate used is (1) 10 to 70 parts by mass in 100 parts by mass of the polymerizable vinyl monomer, and (1-3) the amount of the polyfunctional (meth) acrylate having a bisphenol structure is used. (1) 1 to 30 parts by mass of 100 parts by mass of the polymerizable vinyl monomer, and (1-4) the amount of the monofunctional (meth) acrylate having an alkyl group used is (1) 100 parts by mass of the polymerizable vinyl monomer. The amount of the elastomer used is (3) 5 to 40 parts by mass, does not have a polymerizable unsaturated double bond at the terminal, and has a (meth) acrylonitrile content of 1 to 30 mol%. 1) The composition is 5 to 35 parts by mass with respect to 100 parts by mass of the polymerizable vinyl monomer.
Further, the composition in which (2) the polymerization initiator contains (2-1) a photoradical polymerization initiator and (2-2) a thermal radical polymerization initiator.
Further, (4) the composition containing a reducing agent.
The composition is a two-part formulation containing at least (2-2) a thermal radical polymerization initiator in the first agent and at least (4) a reducing agent in the second agent.
(1-1) The monofunctional (meth) acrylate having a phenyl group is the composition which is a compound of the general formula (A).
General formula (A) Z-O- (R ₂ O) p-R ₁
[In the formula, Z represents a (meth) acryloyl group, and R ₁ represents a phenyl group or a phenyl group having an alkyl group having 1 to 3 carbon atoms. R ₂ is _{-C 2 H 4 -, - C} 3 H 6 -, - CH 2 CH (CH 3) -, - C 4 H 8 - or _-C 6 _{H 12} - indicates, p is an integer from 1 to 10 Represents. ]
(1-2) The monofunctional (meth) acrylate having a hydroxyl group is the composition which is a compound of the general formula (B).
General formula (B) Z-O- (R ₂ O) p-H [In the formula, Z, R ₂ and p are as described above. ]
(1-3) The polyfunctional (meth) acrylate having a bisphenol structure is the composition which is a compound of the general formula (C).

(1-4) The monofunctional (meth) acrylate having an alkyl group is the composition which is a compound of the general formula (D).
General formula (D) Z-OR ₄
Wherein, Z is shown a (meth) acryloyl group, _{R 4} represents from 1 to 20 alkyl group carbon atoms. ]
A curable resin composition containing the composition.
An adhesive composition containing the curable resin composition.
It is a bonded body formed by adhering an adherend using the adhesive composition.
It is an adhesion method formed by adhering an adherend using the adhesive composition.

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

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

In one embodiment of the present invention, the composition contains the following (1) to (4).
(1) Polymerizable vinyl monomer containing (1-1) to (1-4) (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 (1-4) Monofunctional (meth) acrylate having an alkyl group (2) Polymerization initiator containing a photoradical polymerization initiator (3) At the terminal An elastomer that does not have a polymerizable unsaturated double bond and has a (meth) acrylonitrile content of 1 to 30 mol%.

(1) The following compounds are preferable for (1-1) to (1-4).
(1-1) Compound of general formula (A) General formula (A) ZO- (R ₂ O) p-R ₁
[In the formula, Z represents a (meth) acryloyl group, and R ₁ represents a phenyl group or a phenyl group having an alkyl group having 1 to 3 carbon atoms. R ₂ is _{-C 2 H 4 -, - C} 3 H 6 -, - CH 2 CH (CH 3) -, - C 4 H 8 - or _-C 6 _{H 12} - indicates, p is an integer from 1 to 10 Represents. ]
(1-2) Compound of general formula (B) General formula (B) Z-O- (R ₂ O) pH [In the formula, Z, R ₂ and p are as described above. ]
(1-3) Compound of general formula (C)

(1-4) Compound of general formula (D) General formula (D) ZOR ₄
Wherein, Z is shown a (meth) acryloyl group, _{R 4} represents from 1 to 20 alkyl group carbon atoms. ]

In the present embodiment, (1-1), (1-2), (1-3) and (1-4) are contained as the polymerizable vinyl monomer. (1) The polymerizable vinyl monomer may be radically polymerizable. Above all, from the viewpoint of curing speed and the like, the polymerizable vinyl monomer is more preferably a polymerizable (meth) acrylic acid derivative. It is preferable that the polymerizable (meth) acrylic acid derivative is 70 parts by mass or more in 100 parts by mass of the polymerizable vinyl monomer, and all the polymerizable vinyl monomers are the polymerizable (meth) acrylic acid derivative (hereinafter referred to as (meth) acrylate). There is also). Hereinafter, (1) 100 parts by mass of the polymerizable vinyl monomer is preferably 100 parts by mass in total of (1-1), (1-2), (1-3) and (1-4). ..

The 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 the polyfunctional (meth) acrylates, a compound having two (meth) acryloyloxy groups is preferable.

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

General formula (A) Z-O- (R ₂ O) p-R ₁
[In the formula, Z represents a (meth) acryloyl group, and R ₁ represents a phenyl group or a phenyl group having an alkyl group having 1 to 3 carbon atoms. R ₂ is _{-C 2 H 4 -, - C} 3 H 6 -, - CH 2 CH (CH 3) -, - C 4 H 8 - or _-C 6 _{H 12} - indicates, p is an integer from 1 to 10 Represents. ]

(1-1) Examples of the compound of the general formula (A) include phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, phenoxypropyl (meth) acrylate, and phenoxydipropylene glycol (meth). ) Acrylate and phenoxypolypropylene glycol (meth) acrylate and the like can be mentioned. Of these, phenoxyethyl (meth) acrylate is preferable in terms of adhesiveness.

The amount of the monofunctional (meth) acrylate having (1-1) phenyl group to be used is preferably 10 to 60 parts by mass, more preferably 20 to 50 parts by mass, out of 100 parts by mass of (1) the polymerizable vinyl monomer. If it is less than 10 parts by mass, the adhesiveness may be lowered, and if it exceeds 60 parts by mass, the adhesiveness may be lowered.

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

Formula _{(B) Z-O- (R} 2 O) p-H
[In the formula, Z, R ₂ and p are as described above. ]

(1-2) Examples of the compound of the general formula (B) include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. Examples thereof include diethylene glycol mono (meth) acrylate and polypropylene glycol (meth) acrylate. Among these, hydroxyalkyl (meth) acrylate is preferable from the viewpoint of adhesiveness 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 to be used is preferably 10 to 70 parts by mass, more preferably 20 to 60 parts by mass, out of 100 parts by mass of (1) the polymerizable vinyl monomer. If it is less than 10 parts by mass, the adhesiveness may be lowered, and if it exceeds 70 parts by mass, the moisture resistance may be lowered.

(1-3) used in this embodiment is a polyfunctional (meth) acrylate having a bisphenol structure. Among the bisphenol structures, the bisphenol A structure is preferable.
Among (1-3) used in this embodiment, the compound of the general formula (C) is preferable.

Examples of such (meth) acrylic monomers include 2,2-bis (4- (meth) acryloxyphenyl) propane, 2,2-bis (4- (meth) acryloxiethoxyphenyl) propane, and 2,2. -Bis (4- (meth) acryloxidiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxipropoxyphenyl) propane, 2,2-bis (4- (meth) acryloxitetraethoxyphenyl) ) Propane and 2,2-bis (4- (meth) acryloxipolyethoxyphenyl) propane and the like. Among these, 2,2-bis (4- (meth) acryloxipolyethoxyphenyl) propane is preferable in terms of adhesiveness.

Further, 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. The q is even more preferably 5.

(1-3) The amount of the polyfunctional (meth) acrylate having a bisphenol structure to be used is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, out of 100 parts by mass of (1) the polymerizable vinyl monomer. If it is less than 1 part by mass, the adhesiveness may be lowered, and if it exceeds 30 parts by mass, the moisture resistance may be lowered.

(1-4) used in this embodiment is a monofunctional (meth) acrylate having an alkyl group. As the alkyl group, an unsubstituted saturated hydrocarbon group is preferable. The alkyl group preferably has 1 to 20 carbon atoms.

Among (1-4) used in this embodiment, the compound of the general formula (D) is preferable.
General formula (D) Z-OR ₄
Wherein, Z is shown a (meth) acryloyl group, _{R 4} represents from 1 to 20 alkyl group carbon atoms. ]

(1-4) Examples of the compound of the general formula (D) include butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n-lauryl (meth) acrylate and tridecylic (meth) acrylate. And so on. Among these, 2-ethylhexyl (meth) acrylate is preferable in terms of adhesiveness and moisture resistance.

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

(1-4) The amount of the monofunctional (meth) acrylate having an alkyl group to be used is preferably 5 to 40 parts by mass, more preferably 7 to 35 parts by mass, out of 100 parts by mass of (1) the polymerizable vinyl monomer. ~ 30 parts by mass is most preferable. If it is less than 5 parts by mass, the moisture resistance may be lowered, and if it exceeds 40 parts by mass, the adhesiveness, particularly the tensile shear strength against iron may be lowered.

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

Examples of the photoradical polymerization initiator include benzoin derivatives such as benzophenone and its derivatives, benzyl and its derivatives, entraquinone and its derivatives, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal. Acetphenone derivatives such as diethoxyacetophenone and 4-t-butyltrichloroacetonone, 2-dimethylaminoethylbenzoate, p-dimethylaminoethylbenzoate, diphenyldisulfide, thioxanthone and its derivatives, phenylquinone, 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-dioxobicyclo [2.2.1] ] Phenylquinone derivatives such as heptane-1-carboxylic acid chloride, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- Α-Aminoalkylphenone derivative such as (4-morpholinophenyl) -butanone-1, benzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoyldiethoxyposphine oxide, 2,4,6- Acylphosphine oxide derivatives such as trimethylbenzoyldimethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyldiethoxyphenylphosphine oxide, oxy-phenyl-acetylacid 2- [2-oxo-2-phenyl-acetoxy-ethoxy]- Examples thereof include ethyl ester and oxy-phenyl-acetylic acid 2- [2-hydroxy-ethoxy] -ethyl ester. Among these, benzyldimethyl ketal is preferable because it has excellent curability.

The amount of the (2-1) photoradical polymerization initiator used is preferably 0.5 to 10 parts by mass, more preferably 1 to 7 parts by mass with respect to 100 parts by mass of the (1) 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.

Further, the (2) 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 the organic peroxide include cumene hydroperoxide, paramentan hydroperoxide, tertiary butyl hydroperoxide, diisopropylbenzene dihydroperoxide, methyl ethyl ketone peroxide, benzoyl peroxide, tertiary butyl peroxybenzoate and the like. .. One or more of these can be used. Of these, cumene hydroperoxide is preferable in terms of reactivity.

The amount of the (2-2) thermal radical polymerization initiator used is preferably 0.5 to 10 parts by mass, more preferably 1 to 7 parts by mass with respect to 100 parts by mass of the (1) 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.

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

The (4) reducing agent used in the present embodiment can be any known reducing agent that reacts with the polymerization initiator to generate radicals. Typical reducing agents include, for example, tertiary amines, thiourea derivatives, transition metal salts and the like.

Examples of the tertiary amine include triethylamine, tripropylamine, tributylamine and N, N-dimethylparatoluidine. Examples of the thiourea derivative include 2-mercaptobenzimidazole, methylthiourea, dibutylthiourea, tetramethylthiourea, ethylenethiourea and the like. Examples of the transition metal salt include cobalt naphthenate, copper naphthenate, vanadyl acetylacetonate and the like. Of these, transition metal salts are preferred and vanadyl acetylacetonate is more preferred in terms of reactivity.

(4) The amount of the reducing agent used 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 lowered.

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

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

(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-based copolymer is preferable in terms of solubility and adhesiveness. Among the diene-based copolymers, (meth) acrylonitrile-butadiene- (meth) acrylic acid copolymer and / or (meth) acrylonitrile-butadiene copolymer is preferable, and (meth) acrylonitrile-butadiene copolymer is 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 peeling strength at low temperatures. In terms 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 even more preferable. When the (meta) acrylonitrile content is 1 mol% or more, the effect of the present invention is likely to be obtained, and when it is 30 mol% or less, corrosion is unlikely to occur even when a metal such as copper is the object to be adhered.

(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. On the other hand, 5 to 35 parts by mass is preferable, 10 to 30 parts by mass is more preferable, and 15 to 20 parts by mass is most preferable. If it is less than 5 parts by mass, the peel strength and impact resistance at low temperature may be small, and if it exceeds 35 parts by mass, the viscosity may increase, workability may deteriorate, and curability may be insufficient.

The composition in this embodiment can use various paraffins in order to accelerate the curing of the portion in contact with air. Examples of paraffins include paraffin, microcrystalline wax, carnauba wax, beeswax, lanolin, whale wax, selecin and candelilla wax. Of these, paraffin is preferred. The melting point of paraffins is preferably 40 to 100 ° C.

The amount of paraffin used is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of (1) the polymerizable vinyl monomer. If it is less than 0.1 part by mass, the curing of the portion in contact with air may be deteriorated, and if it exceeds 5 parts by mass, the adhesive strength may be lowered.

Further, various antioxidants and the like containing a polymerization inhibitor can be used for the purpose of improving storage stability.

Further, in this embodiment, it is preferable to use a phosphate in order to improve the adhesiveness and increase the curing rate.

In addition to these, already known substances such as plasticizers, fillers, colorants and rust preventives can be used if desired.

The components used in the present embodiment have been described above, but even if compounds having less odor other than the above (1-1), (1-2), (1-3) and (1-4) are used. Good.

As an embodiment of the present invention, it is preferable to use it as an adhesive composition. (2-2) When a thermal radical polymerization initiator is used, for example, it may be used as a two-agent type adhesive composition. For the two-part type, do not mix all the components during storage, divide the adhesive composition into the first agent and the second agent, and add at least (2-2) thermal radical polymerization initiator to the first agent. The agent contains at least (4) reducing agent and, if necessary, phosphate, and is stored separately. In this case, both agents can be applied simultaneously or separately, contacted and cured to be used as a two-part adhesive composition.

In another embodiment, one or both of the first agent and the second agent are pre-contained with a polymerizable vinyl monomer and any other component, and both are mixed at the time of curing to form a one-agent type adhesion. It can be used as an agent composition.

Among 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.
The adhesive composition can be cured by thermal radical polymerization even if there is a portion where visible light or ultraviolet rays cannot enter.

When adhering an adherend using an adhesive composition, the adhesive composition existing at the end of the adherend is temporarily fixed by irradiating it with visible light or ultraviolet rays, and then allowed to stand for adhesion. The body can be fully cured. By irradiating with visible light or ultraviolet rays and temporarily fixing the adherend, the adherend can be adhered with high precision dimensions.

In the present invention, an adherend is bonded with a cured product of a curable resin composition to prepare a bonded body. There are no restrictions on 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 and stainless steel. Shows adhesiveness.

The present invention will be described in more detail below 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 of each substance used is indicated by the mass part. Various physical properties were measured by the methods described below.

The following abbreviations were used for each substance listed in the table.
2,2-Bis (4-methacryloxypolyethoxyphenyl) propane: q = 5 is used.
Paraffins: Paraffin with a melting point of 40 to 100 ° C is used.
Acrylonitrile-butadiene rubber: Acrylonitrile-butadiene copolymer without a polymerizable unsaturated double bond at the end AN amount: Acrylonitrile content (mol%) contained in the acrylonitrile-butadiene rubber

[Tensile Shear Strength (Tensile Shear Adhesive Strength)] A 100 × 25 × 1.6 mm SPCC-D waste-wipe steel sheet was used as a test piece. 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 the other test piece according to JIS K-6850. Immediately after that, the coated surfaces were overlapped and bonded together. After that, 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 at a tensile speed of 10 mm / min in an environment of a temperature of 23 ° C. and a humidity of 50%.

[Peeling Strength (Peeling Adhesive Strength)] As test pieces, a 200 × 25 × 1.6 mm SPCC-D waste wiped steel sheet and a 200 × 25 × 1.5 mm SUS304 waste wiped steel sheet were used. 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 according to JIS K-6854. Immediately after that, the coated surfaces were overlapped and bonded together. Then, it was cured at room temperature for 24 hours, and this was used as a sample for measuring T peel strength. To confirm the low temperature characteristics, compare the T-peeling strength at a tensile speed of 50 mm / min under an environment of temperature 23 ° C. and humidity of 50% with the T-peeling strength at a tensile speed of 50 mm / min under an environment of temperature -20 ° C. did. The breaking distance of peeling in an environment of −20 ° C. was also compared.

The breaking distance of peeling was measured by the following method. Using a sample for measuring T peel strength, set the distance between chucks to 1 cm, fix the upper and lower ends of the above test piece, and move the test piece up and down at a tensile speed of 50 mm / min at a temperature of -20 ° C. The tension and the tensile distance to break were measured. The larger the breaking distance, the greater the peel strength.

[Impact resistance test] As test pieces, a SUS304 waste-wipe steel plate having a panel of 2000 × 500 × 1.5 mm and an SPCC-D waste-wiping steel plate having a reinforcing material of 1800 × 20 × 1.5 mm were used. The first agent was applied to the central portion of the panel in an environment of a temperature of 23 ° C. and a humidity of 50%, and the second agent was applied to the reinforcing material. Immediately after that, the coated surfaces were overlapped and bonded together. Then, 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 supports. A 45 kg iron ball was hung at a height of 800 mm from the surface of the panel and 1000 mm from the edge of the panel. The iron ball was naturally dropped to give an impact to the panel, and the reinforcing material on the back surface was observed to peel off from the panel.
The peeling rate of the reinforcing material was calculated by the following formula.
Reinforcing material peeling rate (%) = (area where the reinforcing material was peeled off) / (area of the adhesive-coated surface to which the adhesive was applied) x 100 (%)

[Deep curability test] The deep curability was measured as follows.

The adhesive is filled in 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 irradiator manufactured by HOYA Corporation was used, and irradiation was performed for 60 seconds under the condition ^{that the integrated irradiation amount at 365 nm was 9000 mJ / cm 2, and the mixture was cured.} After irradiation, the thickness of the cured adhesive product from which the uncured portion was removed was measured with a caliper.

[Odor] The strength of the odor 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 placed in a glass bottle, sealed, left for 1 hour, and then the odor was measured using an odor sensor (manufactured by Calmore). .. The measured value in the tested room was 360. The larger the value, the stronger the odor. The value of odor is preferably 1000 or less, more preferably 600 or less, and most preferably 500 or less.

The following can be seen from the table. In the present invention, the peel strength at low temperature increases as the amount of (3) increases. In Experimental Example 6, since the amount of (3) is large and the content ratio of the (meth) acrylate consisting of (1-1) to (1-4) is small, low odor and low volatility can be achieved. As (1-4), Experimental Example 1 using methyl methacrylate has high peel strength and high impact resistance, but has a high odor. Since Experimental Example 9 does not contain (2-1), deep curability cannot be obtained.

The adhesive composition of the present invention provides a composition having excellent deep curability, for example, a two-part (meth) acrylic adhesive composition that instantly cures deeply. Therefore, the inside of the cured product is easily cured, and a fast-curing two-part (meth) acrylic adhesive composition can be obtained.

Since the cured adhesive is exposed to a sub-zero environment, properties in a low temperature environment are required. Under low temperature conditions, the cured adhesive may become brittle, the adhesive strength may decrease, and peeling may occur.

The adhesive composition of the present invention provides a two-part (meth) acrylic adhesive composition having low odor and high peel strength at low temperature. Since the adhesive composition of the present invention does not contain methyl methacrylate, a composition having low odor and low volatility can be obtained. Therefore, it is possible to work even in a place where ventilation is insufficient, and an adhesive having a wide range of adaptation environments can be obtained in which the cured adhesive does not peel off even in a cold region.

Furthermore, since it is possible to provide a two-part (meth) acrylic adhesive that can withstand a strong impact, it can be applied not only to the improvement of the working environment but also to various industrial fields, which is beneficial.

Claims (16)

A composition containing the following (1) to ( 3).
(1) Polymerizable vinyl monomer containing (1-1) to (1-4) (1-1) Monofunctional (meth) acrylate having a phenyl group (1-2) Monofunctional (meth) having a hydroxyl group A polymerization initiator containing a polyfunctional (meth) acrylate (1-4) alkyl group having an acrylate (1-3) bisphenol structure and a monofunctional (meth) acrylate (2) (2-1) photoradical polymerization initiator. (3) An elastomer having no polymerizable unsaturated double bond at the terminal and 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-based copolymer. The composition according to claim 1 or 2, further comprising paraffins. (3) The amount of the elastomer used, which does not have a polymerizable unsaturated double bond at the terminal and has a (meth) acrylonitrile content of 1 to 30 mol%, is reduced to (1) 100 parts by mass of the polymerizable vinyl monomer. The composition according to claim 1 or 2, which is 5 to 35 parts by mass. (1-1) The amount of the monofunctional (meth) acrylate having a phenyl group used is 10 to 60 parts by mass in (1) 100 parts by mass of the polymerizable vinyl monomer, and (1-2) a simple having a hydroxyl group. The amount of the functional (meth) acrylate used is (1) 10 to 70 parts by mass in 100 parts by mass of the polymerizable vinyl monomer, and (1-3) the amount of the polyfunctional (meth) acrylate having a bisphenol structure is used. (1) 1 to 30 parts by mass of 100 parts by mass of the polymerizable vinyl monomer, and (1-4) the amount of the monofunctional (meth) acrylate having an alkyl group used is (1) 100 parts by mass of the polymerizable vinyl monomer. The amount of the elastomer used is (3) 5 to 40 parts by mass, does not have a polymerizable unsaturated double bond at the terminal, and has a (meth) acrylonitrile content of 1 to 30 mol%. 1) The composition according to any one of claims 1 to 4, which is 5 to 35 parts by mass with respect to 100 parts by mass of the polymerizable vinyl monomer. The composition according to any one of claims 1 to 5, wherein (2) the polymerization initiator contains (2-1) a photoradical polymerization initiator and (2-2) a thermal radical polymerization initiator. 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).
General formula (A) Z-O- (R ₂ O) p-R ₁
[In the formula, Z represents a (meth) acryloyl group, and R ₁ represents a phenyl group or a phenyl group having an alkyl group having 1 to 3 carbon atoms. R ₂ is _{-C 2 H 4 -, - C} 3 H 6 -, - CH 2 CH (CH 3) -, - C 4 H 8 - or _-C 6 _{H 12} - indicates, p is an integer from 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) Z-O- (R} 2 O) p-H
Wherein, Z is shown a (meth) acryloyl group, _{R 2} is _{-C 2 H 4 -, - C} 3 H 6 -, - CH 2 CH (CH 3) -, - C 4 H 8 - or -C ₆ H ₁₂ −, and p represents an integer of 1 to 10 . ] (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).
(1-4) The composition according to any one of claims 1 to 11, wherein the monofunctional (meth) acrylate having an alkyl group is a compound of the general formula (D).
General formula (D) Z-OR ₄
Wherein, Z is shown a (meth) acryloyl group, _{R 4} represents from 1 to 20 alkyl group carbon atoms. ] A curable resin composition comprising the composition according to any one of claims 1 to 12. An adhesive composition comprising the curable resin composition according to claim 13. A bonded body obtained by adhering an adherend using the adhesive composition according to claim 14. An adhesive method for adhering an adherend using the adhesive composition according to claim 14.