TWI695051B - Composition and adhesive composition - Google Patents

Abstract

The present invention provides a composition with low odor and improved peel strength at low temperature. The composition contains: (1) The following polymerizable vinyl monomers containing (1-1) to (1-4)

(1-1) Compound of general formula (A)

General formula (A): ZO-(R ₂ 0) _p -R ₁

[In the formula, Z represents a (meth)acryl acetyl group, and R ₁ represents a phenyl group or a phenyl group having an alkyl group having 1 to 3 carbon atoms. 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 represents an integer of 1-10. ] (1-2) Compounds of general formula (B)

General formula (B): ZO-(R ₂ O) _p -H [wherein, Z, R ₂ and p are as described above. ] (1-3) Compounds of general formula (C)

[In the formula, Z and R _{2 are} as described above. R ₃ represents hydrogen or an alkyl group having 1 to 4 carbon atoms, and q represents a number of 0 or more]; (1-4) a compound of the general formula (D)

Formula (D): ZOR ₄

[In the formula, Z represents a (meth)acryl acetyl group, and R ₄ represents an alkyl group having 3 to 16 carbon atoms. ] (2) Polymerization initiator; (3) Reducing agent; (4) Rubber having polymerizable unsaturated double bond at the terminal; and (5) Elastomer having no polymerizable unsaturated double bond at the terminal.

Description

Composition and adhesive composition

The present invention relates to a two-component acrylic adhesive composition that has good adhesive strength even at low temperatures.

From the viewpoint of labor saving, resource saving, and energy saving, as an adhesive to be bonded at room temperature in a short time, a room temperature rapid curing adhesive composition is being used. Conventionally, as the known room temperature rapid curing adhesive composition, there are two-component rapid curing epoxy adhesive composition, anaerobic adhesive composition, instant adhesive composition and second generation acrylic acid System adhesive composition (SGA).

The two-component fast-curing epoxy adhesive is a metering main agent and a curing agent, which are mixed and applied to the adherend and cured by the reaction of the main agent and the curing agent. However, the two-part fast curing epoxy adhesive requires higher peel strength and impact strength.

The anaerobic adhesive is cured by pressing the adhesive composition between the adherends to isolate the air. However, the anaerobic adhesive composition requires the property that when a part of the adhesive composition overflows from the adherend during pressing, the overflowed portion can be cured even if it comes into contact with air. In addition, a property that can be cured even when the interval between adherends is large is also required.

Instant adhesives usually contain cyanoacrylate as the main component and have excellent handling properties. However, it requires higher peel strength or impact strength.

SGA is a two-component acrylic adhesive, but it does not require accurate measurement of the two-component, even if the measurement or mixing is not complete, as long as the two-component contact, it can be cured at room temperature for several minutes to several tens of minutes, so it is excellent in handling And the peel strength or impact strength is high, and the overflow part is also cured well, so it is widely used in the field of electrical and electronic components to the field of civil engineering and construction. Recently, there has been an SGA that can suppress odor, which can be operated even when the ventilation equipment is insufficient.

Among the various required characteristics, we began to seek the characteristics under low temperature environment, and the adhesive cured product will also be exposed to the environment below freezing point.

【Prior Art Literature】 【Patent Literature】

[Patent Document 1] Japanese Patent Laid-Open No. 11-147921

[Patent Document 2] Japanese Patent Laid-Open No. 2001-55423

Patent Document 1 discloses a method for improving the peel strength at low temperature using a liquid elastomer.

However, there is no description that a composition with low odor and low volatility can be obtained by not containing methyl methacrylate.

Patent Document 2 discloses a composition with low odor and low volatility, but there is no description of a rubber having a polymerizable unsaturated double bond.

An object of the present invention is to provide, for example, a two-component acrylic adhesive excellent in peel strength at low temperature.

That is, the present invention is as follows: a composition comprising: (1) the following polymerizable vinyl monomer including (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)acryl acetyl group, and R ₁ represents a phenyl group or a phenyl group having an alkyl group having 1 to 3 carbon atoms. 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 represents an integer of 1-10. ] (1-2) Compounds of general formula (B)

General formula (B): ZO-(R ₂ O) _p -H [wherein, Z, R ₂ and p are as described above. ] (1-3) Compounds of general formula (C):

[In the formula, Z and R _{2 are} as described above. R ₃ represents hydrogen or an alkyl group having 1 to 4 carbon atoms, and q represents a number of 0 or more]; (1-4) a compound of the general formula (D)

Formula (D): ZOR ₄

[In the formula, Z represents a (meth)acryloyl group, and R ₄ represents an alkyl group having 3 to 16 carbon atoms. ] (2) Polymerization initiator; (3) Reducing agent; (4) Rubber with polymerizable unsaturated double bond at the end; and (5) Elastomer without polymerizable unsaturated double bond at the end, in the composition , (4) The rubber having a polymerizable unsaturated double bond at the end is a butadiene rubber having a polymerizable unsaturated double bond at the end, and the butadiene rubber having a polymerizable unsaturated double bond at the end is not (meth)propylene Nitrile structure, in this composition, (5) the elastomer having no polymerizable unsaturated double bond at the end is a diene copolymer, and the first agent contains at least (2) a polymerization initiator and at least a second agent A two-component type containing (3) a reducing agent, a curable resin composition containing the composition, and an adhesive composition containing the curable resin composition, (4) having a polymerizable unsaturated end The double bond rubber is a butadiene rubber having a (meth)acryloyl group at both ends, and does not have a (meth)acrylonitrile structure. The amount of (4) used is relative to (1) polymerizable ethylene 100 parts by mass of the base monomer is 1 to 50 parts by mass, and the usage amount of (5) is 5 to 35 parts by mass relative to 100 parts by mass of the (1) polymerizable vinyl monomer.

An joined body formed by bonding an adherend using the adhesive composition, and a bonding method that uses the adhesive composition to adhere the adherend.

The adhesive composition of the present invention is, for example, a two-component (meth)acrylic adhesive composition that can improve the peel strength at a low temperature. It can be used not only to improve the operating environment but also in various industrial fields, which is beneficial.

Hereinafter, the present invention will be described in detail.

The present invention contains (1-1), (1-2), (1-3) and (1-4) as (1) polymerizable vinyl monomers. (1) The polymerizable vinyl monomer may be any monomer as long as it can undergo radical polymerization. Among them, 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 polymerizable vinyl monomer, polymerizable (meth)propylene The acid derivative is preferably 70 parts by mass or more, and more preferably all polymerizable vinyl monomers are polymerizable (meth)acrylic acid derivatives. Hereinafter, among (100) parts by mass of (1) polymerizable vinyl monomer, it is preferably 100 parts by mass in total of (1-1), (1-2), (1-3), and (1-4).

The compound of general formula (A) (1-1) used in the present invention refers to the following structure.

General formula (A): ZO-(R ₂ O) _p -R ₁

[In the formula, Z represents a (meth)acryl acetyl group, and R ₁ represents a phenyl group or a phenyl group having an alkyl group having 1 to 3 carbon atoms. 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 represents an integer of 1-10. 〕

As the compound of (1-1) general formula (A), phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol ( Meth)acrylate, phenoxypropyl (meth)acrylate, phenoxydipropylene glycol (meth)acrylate, phenoxy polypropylene glycol (meth)acrylate, etc. Among them, phenoxyethyl (meth)acrylate is preferred from the viewpoint of adhesiveness.

(1-1) The use amount of the compound of the general formula (A) is preferably 10 to 60 parts by mass, and more preferably 20 to 50 parts by mass, out of 100 parts by mass of the (1) polymerizable vinyl monomer. If it is less than 10 parts by mass, the adhesiveness may decrease, and even if it exceeds 60 parts by mass, the adhesiveness may decrease.

The compound of the general formula (B) (1-2) used in the present invention refers to the following structure.

General formula (B): ZO-(R ₂ O) _p -H

[In the formula, Z, R ₂ and p are as described above. 〕

As the compound of (1-2) general formula (B), 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, etc. may be mentioned. Hydroxyethyl (meth)acrylate, diethylene glycol mono(meth)acrylate, polypropylene glycol (meth)acrylate, etc. Among them, hydroxyethyl (meth)acrylate is preferred from the viewpoint of adhesiveness or moisture resistance. Among the hydroxyethyl (meth)acrylates, 2-hydroxyethyl (meth)acrylate and/or 2-hydroxypropyl (meth)acrylate are preferred, and 2-hydroxypropyl (meth)acrylate is more preferred.

(1-2) The use amount of the compound of the general formula (B) is preferably 10 to 70 parts by mass, and more preferably 20 to 60 parts by mass, out of 100 parts by mass of the (1) polymerizable vinyl monomer. If it is less than 10 parts by mass, the adhesiveness may decrease, and if it exceeds 70 parts by mass, the moisture resistance may decrease.

The compound (1-3) of the general formula (C) used in the present invention refers to the following structure.

[In the formula, Z and R _{2 are} as described above. R ₃ represents hydrogen or an alkyl group having 1 to 4 carbon atoms, and q represents a number of 0 or more]; Examples of such (meth)acrylic monomers include 2,2-bis(4-(methyl) Acryloyloxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydioxy Ethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypropoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytetraethyl Oxyphenyl)propane and 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane etc. Among them, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane is preferred from the viewpoint of adhesiveness.

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

(1-3) The use amount of the compound of the general formula (C) is preferably 1 to 30 parts by mass, and more preferably 3 to 20 parts by mass, out of (1) 100 parts by mass of the polymerizable vinyl monomer. If it is less than 1 part by mass, the adhesiveness may decrease, and if it exceeds 30 parts by mass, the moisture resistance may decrease.

The compound of (1-4) general formula (D) used in the present invention refers to the following structure.

Formula (D): ZOR ₄

[In the formula, Z represents a (meth)acryl acetyl group, and R ₄ represents an alkyl group having 3 to 16 carbon atoms. 〕

Examples of the compound of formula (1-4) (D) include butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, (methyl) N-lauryl acrylate and tridecyl (meth) acrylate, etc. Among them, 2-ethylhexyl (meth)acrylate and/or butyl (meth)acrylate are preferred from the viewpoint of adhesiveness or moisture resistance, and (meth) is more preferably used in combination 2-ethylhexyl acrylate and butyl (meth)acrylate. Among butyl (meth)acrylates, n-butyl (meth)acrylate is preferred.

When 2-ethylhexyl (meth)acrylate and butyl (meth)acrylate are used together, the content ratio is 100 parts by mass of the total of 2-ethylhexyl (meth)acrylate and butyl (meth)acrylate In terms of mass ratio, it is preferably 2-ethylhexyl (meth)acrylate: butyl (meth)acrylate = 10 to 90: 90 to 10, more preferably 20 to 60: 80 to 40, and most preferably 30~50: 70~50.

In the formula, the number of carbon atoms of R ₄ is preferably 3 to 16, and more preferably 4 to 13. If it is less than 3, the moisture resistance may decrease, and if it is more than 16, the adhesiveness may decrease.

(1-4) The use amount of the compound of the general formula (D) is preferably 5 to 40 parts by mass, and more preferably 10 to 30 parts by mass, out of 100 parts by mass of the (1) polymerizable vinyl monomer. If it is less than 5 parts by mass, the moisture resistance may decrease, and if it exceeds 40 parts by mass, the adhesiveness, particularly the tensile shear strength to iron may decrease.

As the (2) polymerization initiator used in the present invention, a thermal radical polymerization initiator is preferred. Among the thermal radical polymerization initiators, organic peroxides are preferred. Examples of the organic peroxides include cumene hydroperoxide, hydrogen peroxide p-montane, t-butyl hydroperoxide, dicumyl hydroperoxide, methyl ethyl ketone peroxide, benzophenone peroxide, and peroxide. Oxidized tert-butyl benzoate, etc. One or more of them can be used. Among them, cumene hydroperoxide is preferred from the viewpoint of reactivity.

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

The (3) reducing agent used in the present invention can be used as long as it is a known reducing agent that reacts with the polymerization initiator to generate radicals. Typical reducing agents include tertiary amines, thiourea derivatives, and transition metal salts.

Examples of tertiary amines include triethylamine, tripropylamine, tributylamine, N,N-dimethylp-toluidine, and the like. Examples of the thiourea derivatives include 2-mercaptobenzimidazole, methylthiourea, dibutylthiourea, tetramethylthiourea, and ethylenethiourea. Examples of the transition metal salt include cobalt naphthenate, copper naphthenate, and vanadyl acetonate. Among them, from the viewpoint of reactivity, a transition metal salt is preferred, and vanadium acetonate is more preferred.

(3) The use amount of the reducing agent is preferably 0.01 to 5 parts by mass, and more preferably 0.05 to 1 part by mass with respect to (1) 100 parts by mass of the polymerizable vinyl monomer. If it is less than 0.01 parts by mass, the curing speed may become slow, and if it exceeds 5 parts by mass, the storage stability may be reduced.

The rubber having a polymerizable unsaturated double bond at the terminal (4) used in the present invention is a compound having a polymerizable unsaturated double bond at the terminal of the rubber component. In (4), a compound having a polymerizable unsaturated double bond at both ends of the rubber component is preferred.

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

As the rubber component, a diene-based (co)polymer is preferred. Examples of the diene-based (co)polymer include vinyl polybutadiene, isoprene rubber, butadiene rubber, butadiene-(meth)acrylonitrile rubber, chloroprene rubber, (methyl ) Acrylonitrile-butadiene-(meth)acrylic rubber and styrene-butadiene rubber. Among them, butadiene-(meth)acrylonitrile rubber and/or butadiene rubber are preferable from the viewpoint of good flexibility and good compatibility with the above monomers, but more preferably butadiene rubber. The butadiene rubber preferably does not have a (meth)acrylonitrile structure.

As a method of 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, or A method of dehydrating the carboxyl group and hydroxy (meth)acrylate. Alternatively, the diisocyanate and hydroxy (meth) acrylate may be reacted in advance, and the reaction product may be reacted with the liquid rubber having a reactive hydroxyl group at the terminal.

Among them, rubbers obtained by introducing carboxyl groups at both ends of the rubber component and reacting glycidyl (meth)acrylate with the carboxyl groups are preferred.

For example, as a rubber component, butadiene rubber is used, and after introducing a carboxyl group at both ends of the rubber component, a rubber obtained by reacting glycidyl methacrylate with the carboxyl group may include "Hypro VTB2000X168" manufactured by An Emerald Performance Material Wait.

(4) The rubber having a polymerizable unsaturated double bond at the terminal is preferably a liquid rubber. Liquid rubber refers to rubber that is liquid at normal temperature (23°C).

The number average molecular weight of the rubber having a polymerizable unsaturated double bond at these (4) ends is preferably 1,000 to 1,000,000, and more preferably 2,000 to 500,000. If it is less than 1,000, it may have no effect on the peel strength at a low temperature, and if it exceeds 1000000, it may lose fluidity.

In the examples of the present invention, the number average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography) was used. Specifically, the average molecular weight is determined by using tetrahydrofuran as a solvent under the following conditions, using a GPC system (SC-8010 manufactured by Tosoh Corporation), and creating a standard curve using commercially available standard polystyrene.

Flow rate: 1.0ml/min

Set temperature: 40℃

Column configuration: 1 "TSK guardcolumn MP (×L)" manufactured by Tosoh Corporation 6.0mmID×4.0cm and 2 “TSK-GELMULTIPOREHXL-M” manufactured by Tosoh Corporation 7.8mmID×30.0cm (theoretical plate number 16,000), a total of 3 (The overall number of theoretical boards is 32,000)

Sample injection volume: 100μl (sample solution concentration 1mg/ml)

Inlet pressure: 39kg/cm ²

Detector: RI detector

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

The present invention uses (5) an elastomer having no polymerizable unsaturated double bond at the end.

(5) The elastomer which does not have a polymerizable unsaturated double bond at the terminal includes (meth)acrylonitrile-butadiene-(meth)acrylic acid copolymer, (meth)acrylonitrile-butadiene- Meth (meth)acrylate copolymer, (meth)acrylonitrile-butadiene copolymer, styrene-butadiene copolymer, etc. Styrene-based thermoplastic elastomers such as diene-based copolymers such as chlorosulfonated polyethylene, styrene-polybutadiene-styrene-based synthetic rubber, and polyurethane-based elastomers.

As the (5) elastomer having no polymerizable unsaturated double bond at the terminal, an elastomer soluble in (1) a polymerizable vinyl monomer is preferred.

Among them, a diene-based copolymer is preferred from the viewpoint of solubility and adhesiveness. Among the diene copolymers, (meth)acrylonitrile-butadiene-(meth)acrylic acid copolymers and/or (meth)acrylonitrile-butadiene copolymers are preferred, and (meth)acrylonitrile is more preferred -Butadiene copolymer.

(5) The amount of the elastomer which does not have a polymerizable unsaturated double bond at the terminal is preferably 5 to 35 parts by mass, and more preferably 10 to 30 parts by mass relative to (1) 100 parts by mass of the polymerizable vinyl monomer. .

When (4) a rubber having a polymerizable unsaturated double bond at the end and (5) an elastomer having no polymerizable unsaturated double bond at the end are used, the content ratio is 100 mass in total of (4) and (5) Based on the mass ratio, the portion is preferably (4): (5)=10 to 90: 90 to 10, more preferably 30 to 70: 70 to 30, and most preferably 40 to 60: 60 to 40.

In order to rapidly solidify the part exposed to air, the composition of the present invention can use various paraffins. Examples of paraffins include paraffin wax, microcrystalline wax, carnauba wax, beeswax, lanolin, spermaceti wax, ozokerite, candelilla wax, and the like. Among them, 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 relative to (1) 100 parts by mass of the polymerizable vinyl monomer. If it is less than 0.1 parts by mass, the curing of the part in contact with air may deteriorate, and if it exceeds 5 parts by mass, the adhesive strength may be reduced.

In addition, for the purpose of improving storage stability, various antioxidants including polymerization inhibitors and the like can be used. Examples of the antioxidant include p-methoxyphenol, hydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl p-cresol, and 2,2′-methylenebis(4-methyl 6 -Tert-butylphenol), triphenyl phosphite, phenothiazine, N-isopropyl-N'-phenyl-p-phenylenediamine, etc. Among them, p-methoxyphenol is preferred.

The amount of the antioxidant used is preferably 0.001 to 3 parts by mass with respect to (1) 100 parts by mass of the polymerizable vinyl monomer. If it is less than 0.001 parts by mass, there may be no effect, and if it exceeds 3 parts by mass, the curability of the adhesive may decrease.

In addition, in the present invention, in order to improve the adhesiveness and accelerate the curing speed, it is preferable to use phosphate.

Among phosphates, acidic phosphoric acid compounds of the general formula (E) are preferred from the viewpoint of adhesiveness and curing speed.

，m表示1~10的整數)，n表示1或2的整數) (In the formula, R represents CH ₂ =CR ₄ CO(OR ₅ ) _m -group (wherein R ₄ represents hydrogen or methyl, R ₅ represents -C ₂ H ₄ -, -C ₃ H ₆ -, -CH ₂ CH(CH ₃ )-, -C ₄ H ₈ -, -C ₆ H ₁₂ -or

, M represents an integer from 1 to 10), n represents an integer of 1 or 2)

Examples of the acidic phosphoric acid compound of the general formula (E) include acidic (meth)acrylic acid phosphinyloxyethyl ester, acidic (meth)acrylic acid phosphinyloxypropyl ester and bis(2-(methyl ) Propylene oxyethyl) phosphate etc. Among them, acidic (meth)acrylic acid phosphinyloxyethyl is preferred from the viewpoint of adhesiveness and curing speed.

The amount of phosphate added is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 7 parts by mass relative to (1) 100 parts by mass of the polymerizable vinyl monomer. If it is less than 0.05 parts by mass, the curing speed may be slowed and the adhesiveness may be reduced. Even if it exceeds 10 parts by mass, the adhesiveness may be reduced.

For the composition of the present invention, the total of (1), (2), (3), (4), and (5) is preferably 80 parts by mass or more, and more preferably 85 parts by mass or more, out of 100 parts by mass of the composition It is most preferably 90 parts by mass or more, and still more preferably 95 parts by mass or more.

In 100 parts by mass of the composition of the present invention, the total of (1-1), (1-2), (1-3), and (1-4) is preferably 50 parts by mass or more, and more preferably 60 parts by mass or more, It is most preferably 65 parts by mass or more, and still more preferably 70 parts by mass or more.

In addition, in addition to the above components, plasticizers, fillers, Known substances such as colorants and rust inhibitors.

The components used in the present invention have been described above, but the composition of the present invention may be further used in addition to the above (1-1), (1-2), (1-3) and (1-4) Compound with less odor.

As an embodiment of the present invention, it is preferably used as an adhesive composition. In this case, for example, it can be used as a two-component type adhesive composition. For the two-component form, all the necessary components of the adhesive composition of the present invention are not mixed during storage, but the adhesive composition is divided into a first agent and a second agent, and the first agent contains at least (2) a polymerization initiator The second agent contains at least (3) the reducing agent and the phosphate used as needed, and store them separately. In this case, it can be used as a two-component type adhesive composition by applying or curing two components simultaneously or separately.

As another embodiment, either one or both of the first agent and the second agent may contain a polymerizable vinyl monomer and any other components in advance, and the two are mixed during curing to serve as a one-pack adhesive Use of composition.

In these embodiments, from the viewpoint of excellent storage stability, it is preferably used as a two-component type adhesive composition.

In the present invention, the adherend is joined using a cured body of the curable resin composition to produce a joined body. For the various materials of the adherend, it can be paper, wood, ceramics, glass, ceramics, There are no restrictions on rubber, plastic, mortar, concrete, metal, etc., but when the adherend is metal, especially metal or stainless steel, it can show more excellent adhesion.

【Example】

Hereinafter, the present invention will be described in more detail through examples. It should be noted that the unit of the amount of each substance used is expressed in parts by mass. In addition, for each substance, 2,2-bis(4-methacryloxypolyethoxyphenyl)propane with q=5 is used, and as the paraffins, paraffin wax having a melting point of 40 to 100° C. is used. Physical properties are measured as follows.

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

[Peeling Strength (Peeling Adhesive Strength)] As a test piece, a 200×25×1.6 mm SPCC-D cloth wiping treatment steel plate and a 200×25×1.5 mm SUS304 cloth wiping treatment steel plate were used. In an environment with a temperature of 23° C. and a humidity of 50%, in accordance with JIS K-6854, the first agent was applied to one side of one test piece, and the second agent was applied to another test piece. Immediately thereafter, the coated surfaces were overlapped and bonded to each other. Thereafter, it was cured at room temperature for 24 hours. This was used as a sample for T peel strength measurement. As a confirmation of the low-temperature characteristics, the stretching speed under an environment of a temperature of 23°C and a humidity of 50% is 50 mm/ The T peel strength in minutes was compared with the T peel strength at a tensile speed of 50 mm/min in an environment at a temperature of -20°C. In addition, the rupture distance of peeling under the environment of temperature -20°C was also compared.

The breaking distance of peeling is measured by the following method. Using a sample for T peel strength measurement, the chuck pitch was set to 1 cm, the upper and lower ends of the test piece were fixed, and the test piece was stretched up and down at a temperature of -20°C and a stretching speed of 50 mm/min to measure The tensile distance to break is reached. The greater the breaking distance, the greater the peel strength.

[Odor] The odor intensity of each curable resin composition was measured as follows.

Using the resin composition, a cured product having a diameter of 10 mm and a thickness of 1 mm was prepared. The cured product was placed in a glass bottle and capped tightly. After standing for 1 hour, the odor was measured using an odor sensor (manufactured by Karumoa). In addition, the measured value in the room where the test was performed 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.

Hereinafter, the present invention will be described in further detail through experimental examples. The unit of the amount of each substance used is expressed in parts by mass.

The following abbreviations are used for the substances listed in the table.

Liquid butadiene rubber: liquid butadiene rubber with polymerizable unsaturated double bonds at both ends (An Emerald Performance Material, Hypro VTB2000X168, liquid, number average molecular weight 4500, group with polymerizable unsaturated double bonds It is a methacryloyl group, but liquid butadiene rubber does not have a (meth)acrylonitrile structure)

NBR: acrylonitrile-butadiene copolymer, elastomer with no polymerizable unsaturated double bond at the end (commercially available product)

Phosphate: Acid Phosphatoxyethyl Methacrylate

The table below shows the following. In the present invention, as the amount of (4) increases, the peeling at low temperature Strength increased. In Example 3, the amount of (4) and (5) is large, and the content ratio of (meth)acrylate composed of (1-1) to (1-4) is small, so low odor and low volatility. Comparative Example 3 using methyl methacrylate instead of (1-4) had low peel strength at low temperature and smelly.

[Industry availability]

With the adhesive composition of the present invention, a two-component acrylic adhesive composition with low odor and high peel strength at low temperature can be obtained. Therefore, the operation can be performed even in a place where ventilation is insufficient, and the adhesive composition does not peel off in cold areas. Since the adhesive composition has a wide application environment, it is industrially beneficial.

Claims (10)

A composition comprising: the following (1) a compound containing the polymerizable vinyl monomers (1-1) to (1-4) (1-1) 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, R ₁ represents a phenyl group or a phenyl group having a C 1-3 alkyl group, and 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 -, p represents an integer from 1 to 10; (1-2) general formula (B ) Compound general formula (B): ZO-(R ₂ O) _p -H formula, Z, R ₂ and p are as described above; (1-3) compound of general formula (C)

In the formula, Z and R _{2 are} as described above, R ₃ represents hydrogen or an alkyl group having 1 to 4 carbon atoms, and q represents a number of 0 or more; (1-4) Compound of the general formula (D) ：In the ZOR ₄ formula, Z represents (meth)acryloyl group, R ₄ represents alkyl group with 3 to 16 carbon atoms; (2) polymerization initiator; (3) reducing agent; (4) the terminal has Saturated double bond rubber; and (5) an elastomer that does not have a polymerizable unsaturated double bond at the end , and the amount of the compound of the formula (1-4) (D) relative to the (1) polymerizability 100 parts by mass of vinyl monomer is 5 to 40 parts by mass . The composition according to claim 1, wherein the rubber having a polymerizable unsaturated double bond at the terminal (4) is a butadiene rubber having a polymerizable unsaturated double bond at the terminal. The composition according to claim 2, wherein the butadiene rubber having a polymerizable unsaturated double bond at the terminal does not have a (meth)acrylonitrile structure. The composition according to claim 1, wherein the elastomer having no polymerizable unsaturated double bond at the (5) end is a diene-based copolymer. The composition according to any one of claims 1 to 4, wherein the composition contains a first agent and a second agent, and the first agent contains at least the (2) polymerization initiator, And the second dosage form contains at least the reducing agent of (3). A curable resin composition containing the composition according to any one of claims 1 to 5. An adhesive composition containing the curable resin composition according to claim 6. The adhesive composition according to claim 7, wherein the rubber having a polymerizable unsaturated double bond at the (4) end has a (meth)acryloyl group at both ends and does not have a (meth) ) Butadiene rubber with an acrylonitrile structure, the amount of (4) is 1 to 50 parts by mass relative to (1) 100 parts by mass of the polymerizable vinyl monomer, and the amount of (5) is relative to ( 1) 100 parts by mass of polymerizable vinyl monomer is 5~35 Quality parts. A joined body obtained by bonding an adherend using the adhesive composition according to claim 7. A bonding method, wherein the bonding method uses the adhesive composition according to claim 7 to bond an adherend.