JP6823475B2 - 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 type 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-part 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 during crimping, the squeezed out portion is cured even if it comes into contact with air. .. Further, the property of curing is required even when the clearance between the 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 in the fields of electrical and electronic parts as well as 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 a place with insufficient ventilation equipment.

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 based adhesives.

That is, the present invention
A composition containing the following (1) to (4).
(1) Polymerizable vinyl monomer containing (1-1) to (1-3) Monofunctional (meth) acrylate having a phenyl group (1-2) Polyfunctional (meth) having a bisphenol structure Acrylate (1-3) Monofunctional (meth) acrylate having an alkyl group (2) (2-1) Polymerization initiator containing a photoradical polymerization initiator (3) butadiene having a polymerizable unsaturated double bond at the terminal Rubber (4) Acrylate having no polymerizable unsaturated double bond at the end (3) A butadiene rubber having a polymerizable unsaturated double bond at the end is the composition having no (meth) acrylonitrile structure.
(4) The composition in which the elastomer having no polymerizable unsaturated double bond at the terminal is a diene-based copolymer.
Further, the composition is composed of paraffins.
(3) The butadiene rubber having a polymerizable unsaturated double bond at the end is a butadiene rubber having a (meth) acryloyl group at both ends and not having a (meth) acrylonitrile structure, and the use of (3). The amount is (1) 1 to 50 parts by mass with respect to 100 parts by mass of the polymerizable vinyl monomer, and the amount of (4) used is 5 to 35 parts by mass with respect to (1) 100 parts by mass of the polymerizable vinyl monomer. The composition, which is a part,
(1-1) The amount of the monofunctional (meth) acrylate having a phenyl group used is 15 to 90 parts by mass in (1) 100 parts by mass of the polymerizable vinyl monomer, and (1-2) many having a bisphenol structure. The amount of the functional (meth) acrylate used is (1) 2 to 50 parts by mass in 100 parts by mass of the polymerizable vinyl monomer, and (1-3) the amount of the monofunctional (meth) acrylate having an alkyl group is used. (1) 5 to 45 parts by mass of 100 parts by mass of the polymerizable vinyl monomer, and (3) the amount of butadiene rubber having a polymerizable unsaturated double bond at the terminal is (1) 100 parts by mass of the polymerizable vinyl monomer. The amount of the elastomer which is 5 to 45 parts by mass and does not have a polymerizable unsaturated double bond at the terminal (4) is 5 to 35 parts by mass with respect to (1) 100 parts by mass of the polymerizable vinyl monomer. The composition, which is a part by mass,
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, (5) 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 (5) 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 polyfunctional (meth) acrylate having a bisphenol structure is the composition which is a compound of the general formula (B).

(1-3) The monofunctional (meth) acrylate having an alkyl group is the composition which is a compound of the general formula (C).
General formula (C) 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 (1-3) Monofunctional (meth) acrylate having a phenyl group (1-2) Polyfunctional (meth) having a bisphenol structure Acrylate (1-3) Monofunctional (meth) acrylate having an alkyl group (2) Polymerization initiator containing a photoradical polymerization initiator (3) butadiene rubber having a polymerizable unsaturated double bond at the terminal (4) Terminal Acrylate that does not have a polymerizable unsaturated double bond

(1) The following compounds are preferable for (1-1) to (1-3).
(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)

(1-3) Compound of general formula (C) General formula (C) Z-OR 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) and (1-3) 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. Of 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 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) and (1-3).

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.

Reference numeral (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.

Among (1-1) used in the present 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, 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 15 to 90 parts by mass, more preferably 30 to 80 parts by mass, out of 100 parts by mass of (1) the polymerizable vinyl monomer. If it is less than 15 parts by mass, the adhesiveness may be lowered, and if it exceeds 90 parts by mass, the adhesiveness may be lowered.

(1-2) used in this embodiment is a polyfunctional (meth) acrylate having a bisphenol structure. Among the bisphenol structures, the bisphenol A structure is preferable.

Among (1-2) used in the present embodiment, the compound of the general formula (B) 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.

(1-2) The amount of the polyfunctional (meth) acrylate having a bisphenol structure to be used is preferably 2 to 50 parts by mass, more preferably 5 to 30 parts by mass, out of 100 parts by mass of (1) the polymerizable vinyl monomer. If it is less than 2 parts by mass, the adhesiveness may be lowered, and if it exceeds 50 parts by mass, the moisture resistance may be lowered.

(1-3) 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 (1-3) used in this embodiment, the compound of the general formula (C) is preferable.
General formula (C) Z-OR ₄
Wherein, Z is shown a (meth) acryloyl group, _{R 4} represents from 1 to 20 alkyl group carbon atoms. ]

(1-3) Examples of the compound of the general formula (C) 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.

(1-3) The amount of the monofunctional (meth) acrylate having an alkyl group to be used is preferably 5 to 45 parts by mass, more preferably 7 to 40 parts by mass, out of 100 parts by mass of (1) the polymerizable vinyl monomer. ~ 35 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 45 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 and tertiary butyl peroxybenzoate. .. 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 (5) a reducing agent in combination.

The (5) 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.

(5) 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.

The (3) butadiene rubber having a polymerizable unsaturated double bond at the end (hereinafter, may be referred to as a rubber having a polymerizable unsaturated double bond at the end) used in the present embodiment is polymerizable at the end of the rubber component. It is a compound having an unsaturated double bond. Among (3), a compound having a polymerizable unsaturated double bond at both ends of the rubber component is preferable.

As the polymerizable unsaturated double bond, a (meth) acryloyl group and / or a vinyl group is preferable, and a (meth) acryloyl group is more preferable, in that the reactivity is good.

As the rubber component, butadiene rubber is preferable. The butadiene rubber preferably does not have a (meth) acrylonitrile structure.

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 a carboxyl group at both ends of the rubber component, glycidyl (meth) acrylate is reacted with the carboxyl group. A method of allowing the carboxyl group to undergo a dehydration reaction with the hydroxy (meth) acrylate can be mentioned. Alternatively, the diisocyanate may be reacted with a hydroxy (meth) acrylate in advance, and this may be reacted with a liquid rubber having a reactive hydroxyl group at the terminal.

Among these, rubber obtained by introducing carboxyl groups into both ends of the rubber component and then reacting the carboxyl groups with glycidyl (meth) acrylate is preferable.
For example, a rubber obtained by using butadiene rubber as a rubber component, introducing carboxyl groups at both ends of the rubber component, and then reacting the carboxyl groups with glycidyl methacrylate is "Hypro VTB2000X168" manufactured by An Emerald Performance material. And so on.
(3) As the rubber having a polymerizable unsaturated double bond at the terminal, a liquid rubber is preferable. Liquid rubber refers to rubber that is liquid at room temperature (23 ° C).

The number average molecular weight of the rubber having a polymerizable unsaturated double bond at the terminal (3) is preferably 1000 to 1000000, more preferably 2000 to 500000. If it is less than 1000, the peel strength at low temperature may not be affected, and if it exceeds 1,000,000, the fluidity may be lost.

In the experimental example of the present invention, a polystyrene-equivalent number average molecular weight 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 and using a GPC system (SC-8010 manufactured by Tosoh Corporation) under the following conditions.
Flow velocity: 1.0 ml / min
Set temperature: 40 ° C
Column configuration: Tosoh's "TSK guardcolum MP (xL)" 6.0 mm ID x 4.0 cm 1 piece, Tosoh's "TSK-GELMULTIPOREHXL-M" 7.8 mm ID x 30.0 cm (theoretical plate number 16,000) 2 pieces, 3 pieces in total (32,000 theoretical plates as a whole)
Sample injection volume: 100 μl (sample solution concentration 1 mg / ml)
Liquid transfer pressure: 39 kg / cm ²
Detector: RI detector

(3) The amount of rubber having a polymerizable unsaturated double bond at the terminal is preferably 1 to 50 parts by mass, more preferably 5 to 30 parts by mass with respect to 100 parts by mass of (1) the polymerizable vinyl monomer. Most preferably 10 to 20 parts by mass. If it is less than 1 part by mass, the peel strength at low temperature is not affected, and if it exceeds 50 parts by mass, the curability may be insufficient.

The present invention uses (4) an elastomer that does not have a polymerizable unsaturated double bond at the end.
(4) Examples of the elastomer having no polymerizable unsaturated double bond at the terminal include (meth) acrylonitrile-butadiene- (meth) acrylic acid copolymer and (meth) acrylonitrile-butadiene-methyl (meth) acrylate copolymer. , (Meta) acrylonitrile-butadiene copolymers, diene-based copolymers such as styrene-butadiene copolymers, styrene-based thermoplastic elastomers such as chlorosulfonated polyethylene, styrene-polybutadiene-styrene-based synthetic rubber, and urethane-based elastomers. Be done.

(4) As the 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-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.

(4) The amount of the elastomer having no polymerizable unsaturated double bond at the terminal is preferably 5 to 35 parts by mass, more preferably 10 to 30 parts by mass with respect to 100 parts by mass of (1) the polymerizable vinyl monomer. preferable.

When a rubber having a polymerizable unsaturated double bond at the end (3) and an elastomer not having a polymerizable unsaturated double bond at the end (4) are used in combination, the content ratios of (3) and (4) are In terms of mass ratio out of 100 parts by mass in total, (3): (4) = 10 to 90:90 to 10, more preferably 30 to 70:70 to 30, and most preferably 40 to 60:60 to 40.

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 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.

Although the components used in the present embodiment have been described above, compounds having less odor other than the above (1-1), (1-2) and (1-3) may be used.

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-dosage form, do not mix all the components during storage, divide the adhesive composition into first and second agents, and add at least (2-2) thermal radical polymerization initiator to the first agent. The agent contains at least (5) reducing agent 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 the present 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, adherends are joined 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.
Liquid butadiene rubber: Liquid butadiene rubber having a polymerizable unsaturated double bond at both ends (manufactured by An Emerald Performance material, Hyper VTB2000X168, liquid, number average molecular weight 4500, the group having a polymerizable unsaturated double bond is a methacryloyl group. Liquid butadiene rubber does not have a (meth) acrylonitrile structure)
NBR: Acrylonitrile-butadiene copolymer, elastomer without polymerizable unsaturated double bond at the end (commercially available)

[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. Then, 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. 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 a temperature of 23 ° C and a humidity of 50% with the T-peeling strength at a tensile speed of 50 mm / min under an environment of a temperature of -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 chuck distance 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.

[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. Since (3) and (4) are used in the present invention, the peel strength at low temperature is high. In Experimental Example 1 and Experimental Example 3 in which (3) or (4) is not used, the peel strength at low temperature is low. Since Experimental Example 4 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 is useful not only for improving the working environment but also for applying it to various industrial fields.

Claims (16)

A composition containing the following (1) to (4).
(1) Polymerizable vinyl monomer containing (1-1) to (1-3) Monofunctional (meth) acrylate having a phenyl group (1-2) Polyfunctional (meth) having a bisphenol structure Acrylate (1-3) Monofunctional (meth) acrylate having an alkyl group (2) (2-1) Polymerization initiator containing a photoradical polymerization initiator (3) butadiene having a polymerizable unsaturated double bond at the terminal Rubber (4) Elastomer without polymerizable unsaturated double bond at the end
However, the amount of (3) used is 1 to 30 parts by mass with respect to 100 parts by mass of (1) polymerizable vinyl monomer. (3) The composition according to claim 1, wherein the butadiene rubber having a polymerizable unsaturated double bond at the terminal does not have a (meth) acrylonitrile structure. (4) The composition according to claim 1 or 2, wherein the elastomer having no polymerizable unsaturated double bond at the terminal is a diene-based copolymer. The composition according to any one of claims 1 to 3, further comprising paraffins. (3) ends butadiene rubber having a polymerizable unsaturated double bond, at both ends has a (meth) acryloyl group and a butadiene rubber having no (meth) acrylonitrile structure, use of (4) The adhesive composition according to any one of claims 1 to 4, wherein the amount is (1) 5 to 35 parts by mass with respect to 100 parts by mass of the polymerizable vinyl monomer. (1-1) The amount of the monofunctional (meth) acrylate having a phenyl group used is 15 to 90 parts by mass in (1) 100 parts by mass of the polymerizable vinyl monomer, and (1-2) many having a bisphenol structure. The amount of the functional (meth) acrylate used is (1) 2 to 50 parts by mass in 100 parts by mass of the polymerizable vinyl monomer, and (1-3) the amount of the monofunctional (meth) acrylate having an alkyl group is used. The amount of butadiene rubber (1) 5 to 45 parts by mass in 100 parts by mass of the polymerizable vinyl monomer and (3) having a polymerizable unsaturated double bond at the terminal is (1) 100 parts by mass of the polymerizable vinyl monomer. The amount of the elastomer used, which is 1 to 50 parts by mass with respect to parts and (4) does not have a polymerizable unsaturated double bond at the terminal, is 5 to 5 parts by mass with respect to (1) 100 parts by mass of the polymerizable vinyl monomer. The composition according to any one of claims 1 to 5, which is 35 parts by mass. The composition according to any one of claims 1 to 6, 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 7, further comprising (5) a reducing agent. The composition according to claim 8, wherein the first agent contains at least (2-2) a thermal radical polymerization initiator, and the second agent contains at least (5) a reducing agent. (1-1) The composition according to any one of claims 1 to 9, wherein the monofunctional (meth) acrylate having a phenyl group is a compound of the 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) 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 (B).
(1-3) 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 (C).
General formula (C) 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.