TW201833265A - Composition - Google Patents

Abstract

Provided is a composition which exhibits excellent curability in a deep portion. The present invention provides a composition which contains a polymerizable vinyl monomer A, a polymerization initiator B that contains a radical photopolymerization initiator B1, an elastomer C that has a polymerizable unsaturated double bond at an end, and an elastomer D that does not have a polymerizable unsaturated double bond at an end. The elastomer D has a (meth)acrylonitrile content of 10-30% by mole.

Description

Composition

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

From the point of view of labor saving, resource saving and energy saving, as a bonding agent which adheres at a normal temperature for a short time, a composition which is a fast curing type adhesive at room temperature is used. Now, as a composition of a room temperature fast-curing adhesive, it is known that a two-component type fast-curing epoxy-based adhesive composition, an anaerobic adhesive composition, an instant adhesive composition, and the like Second generation acrylic adhesive composition (SGA).

The two-component type fast-curing epoxy-based adhesive is obtained by weighing the main component and the curing agent, mixing and applying to the adherend, and curing by the reaction of the main component and the curing agent. However, two-component type fast curing epoxy adhesives are required to have higher peel strength and impact strength.

Anaerobic adhesives are cured by pressing the adhesive composition between the adherends and blocking the air. However, for the anaerobic adhesive composition, it is required to have a property that, when a part of the adhesive composition is extended from the adherend when pressed, the extended portion is cured even if it is in contact with air. In addition, it is required to have a property of being solidified even when the gap between the adherends is large.

Instant adhesives usually contain cyanoacrylate as a main component and are excellent in handleability. However, higher peel strength and impact strength are required.

SGA is a two-component acrylic adhesive, but does not require precise weighing of the two components, even if the weighing and mixing are not sufficiently accurate, only two minutes of contact can be used at room temperature in a few minutes to several It is cured in a ten-minute period, so it has excellent workability, high peel strength and impact strength, and good curing of the extended portion. Therefore, it is widely used in various fields from electrical and electronic components to civil engineering and construction. . Recently, an SGA that suppresses odor has also been introduced, and work can be performed in a place where ventilation equipment is insufficient. Prior art literature

Patent Document 1: Japanese Laid-Open Patent Publication No. Hei 11-147921 (Patent Document 2: JP-A-2001-55423)

(The problem to be solved by the invention)

Patent Documents 1 and 2 disclose a two-component acrylic adhesive. However, there is no description about the photoradical polymerization initiator.

An object of the present invention is to provide a composition excellent in adhesion at low temperature and deep curability. (means to solve the problem)

The inventors of the present invention have found that when a composition containing a polymerizable vinyl monomer having a specific composition, a photopolymerization initiator, and a specific elastomer is used, it is possible to provide a double group excellent in adhesion at low temperature and deep curability. Type (meth) acrylic adhesive.

That is, according to the present invention, there is provided a composition comprising: a polymerizable vinyl monomer A, a polymerization initiator B containing a photoradical polymerization initiator B1, an elastomer C having a polymerizable unsaturated double bond at the terminal, and an end. The elastomer D having no polymerizable unsaturated double bond has a (meth)acrylonitrile content of the elastomer D of 1 to 30% by mole. Preferably, a composition is provided in which monomer A contains two or more of monomers A1 to A4, monomer A1 is a monofunctional (meth) acrylate having a phenyl group, and monomer A2 has A monofunctional (meth) acrylate of a hydroxyl group, a monomer A3 is a polyfunctional (meth) acrylate having a bisphenol structure, and a monomer A4 is a monofunctional (meth) acrylate having an alkyl group. Preferably, a composition is provided in which monomer A contains three or more of monomers A1 to A4, monomer A1 is a monofunctional (meth) acrylate having a phenyl group, and monomer A2 has A monofunctional (meth) acrylate of a hydroxyl group, a monomer A3 is a polyfunctional (meth) acrylate having a bisphenol structure, and a monomer A4 is a monofunctional (meth) acrylate having an alkyl group. Preferably, a composition is provided in which monomer A contains monomers A1 to A4, monomer A1 is a monofunctional (meth) acrylate having a phenyl group, and monomer A2 is a monofunctional group having a hydroxyl group ( Methyl) acrylate, monomer A3 is a polyfunctional (meth) acrylate having a bisphenol structure, and monomer A4 is a monofunctional (meth) acrylate having an alkyl group. Preferably, a composition having a characteristic that the (meth)acrylonitrile content of the elastomer C is from 10 to 30 mol% is provided. Preferably, a composition is provided which has the following characteristics, that is, the elastomer D is a diene-based copolymer. Preferably, a composition having the following characteristics is provided, that is, the content ratio of the elastomer C and the elastomer D is, in a total of 100 parts by mass of C and D, by mass ratio, C: D = 10 to 90: 90 to 10 . Preferably, the composition is provided in such a manner that the blending amounts of the elastomers C and D are from 1 to 50 parts by mass and from 5 to 35 parts by mass per 100 parts by mass of the monomer A, respectively. Preferably, a composition is provided in which the amount of the monomers A1, A2, A3, and A4 is 10 to 60 parts by mass, 10 to 70 parts by mass, and 1 to 10 parts by mass of the monomer A, respectively. 30 parts by mass, 5 to 40 parts by mass; the content of (meth)acrylonitrile of the elastomer C is 10 to 30% by mole; and the amount of the elastomers C and D is 1 to 50 with respect to 100 parts by mass of the monomer A, respectively. Parts by mass, 5 to 35 parts by mass. Preferably, a composition having the following characteristics is provided, that is, a wax is further contained. Preferably, a composition is provided which has a characteristic that the polymerization initiator B further contains a thermal radical polymerization initiator B2. Preferably, a composition having the following characteristics is provided, that is, further containing a reducing agent E. Preferably, a two-component type composition having the following characteristics is provided, that is, the first component contains at least a thermal radical polymerization initiator B2, and the second component contains at least a reducing agent E. Preferably, a composition is provided which has the following characteristics, that is, the monomer A1 is a compound of the formula (1). General formula (1) ZO-(R ₂ O)pR ₁ wherein Z represents a (meth)acrylonitrile 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 to 10. Preferably, a composition is provided which has the following characteristics, that is, the monomer A2 is a compound of the formula (2). General formula (2) ZO-(R ₂ O)p-H [wherein Z represents a (meth)acryloyl group, and R ₂ represents a -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 of 1 to 10. Preferably, a composition is provided which has the following characteristics, that is, the monomer A3 is a compound of the formula (3). General formula (3) Wherein Z represents a (meth)acryloyl group and R ₂ represents a -C ₂ H ₄ -, -C ₃ H ₆ -, -CH ₂ CH(CH ₃ )-, -C ₄ H ₈ - or -C ₆ H ₁₂ -. R ₃ represents hydrogen or an alkyl group having 1 to 4 carbon atoms, and q represents a number of 0 or more. Preferably, a composition is provided which has the following characteristics, that is, the monomer A4 is a compound of the formula (4). General formula (4) ZOR ₄ [wherein Z represents a (meth) acrylonitrile group, and R ₄ represents an alkyl group having 1 to 16 carbon atoms. Preferably, a curable resin composition containing the above composition is provided. Preferably, an adhesive composition containing the above curable resin composition is provided. Preferably, a bonded body obtained by bonding the adherend using the above-described adhesive composition is provided. Preferably, a bonding method of bonding the adherend using the above-described adhesive composition is provided. Preferably, an adhesive method of irradiating visible light or ultraviolet rays to the adhesive composition existing at the end of the adherend when the adhesive composition is adhered using the adhesive composition is provided. (effect of the invention)

The present invention can provide, for example, a composition excellent in adhesion at low temperatures and deep curability.

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

The composition of one embodiment of the present invention contains: a polymerizable vinyl monomer A, a polymerization initiator B containing a photoradical polymerization initiator B1, an elastomer C having a polymerizable unsaturated double bond at the terminal, and an end No. The elastomer D having a polymerizable unsaturated double bond has a (meth)acrylonitrile content of the elastomer D of 1 to 30% by mole.

1. Monomer A Monomer A can be subjected to radical polymerization as long as it can. Among them, the monomer A is more preferably a polymerizable (meth)acrylic acid derivative from the viewpoint of curing speed and the like. In 100 parts by mass of the monomer A, the polymerizable (meth)acrylic acid derivative is preferably 70 parts by mass or more, and it is more preferable that the monomer A is all a polymerizable (meth)acrylic acid derivative (hereinafter also referred to as (meth)). Acrylate). The (meth) acrylate may be a monofunctional (meth) acrylate or a polyfunctional (meth) acrylate. The monofunctional (meth) acrylate refers to a compound having one (meth) propylene fluorenyloxy group. The polyfunctional (meth) acrylate refers to a compound having two or more (meth) acryloxy groups. Among the polyfunctional (meth) acrylates, compounds having two (meth) propylene fluorenyloxy groups are preferred.

The monomer A preferably contains a part or all of the monomer A1, the monomer A2, the monomer A3 and the monomer A4, and more preferably contains all. The monomer A preferably contains one or more of the monomer A1, the monomer A2, the monomer A3, and the monomer A4, and more preferably contains two or more of the monomer A1, the monomer A2, the monomer A3, and the monomer A4. It is most preferable to contain three or more of the monomer A1, the monomer A2, the monomer A3, and the monomer A4, and it is more preferable to contain all of the monomer A1, the monomer A2, the monomer A3, and the monomer A4. Preferably, 100 parts by mass of the monomer A means 100 parts by mass of the monomers A1 to A4 in total.

1-1. Monomer A1 Monomer A1 is a monofunctional (meth) acrylate having a phenyl group. The phenyl group may also have a substituent. The phenyl group contains a benzoindolyl group. Among the monomers A1, a compound of the formula (1) is preferred.

General formula (1) ZO-(R ₂ O)pR ₁ wherein Z represents a (meth)acrylonitrile 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 to 10. ]

Examples of the compound of the formula (1) include phenoxyethyl (meth) acrylate, phenoxy diethylene glycol (meth) acrylate, and phenoxy polyethylene glycol (meth) acrylate. Ester, phenoxypropyl (meth) acrylate, phenoxy dipropylene glycol (meth) acrylate, phenoxy polypropylene glycol (meth) acrylate, and the like. Among them, phenoxyethyl (meth) acrylate is preferred from the viewpoint of adhesion.

The amount of the monomer A1 to be added is preferably 10 to 60 parts by mass, more preferably 20 to 50 parts by mass, per 100 parts by mass of the monomer A. 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. Monomer A2 The monomer A2 used in the present embodiment is a monofunctional (meth) acrylate having a hydroxyl group. Among the monomers A2 used in the present embodiment, a compound of the formula (2) is preferred.

General formula (2) ZO-(R ₂ O)pH [wherein Z represents a (meth)acryloyl group, and R ₂ represents a -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 of 1 to 10. ]

Examples of the compound of the formula (2) include a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate or 2-hydroxybutyl (meth) acrylate. Alkyl (meth) acrylate, diethylene glycol mono (meth) acrylate, and polypropylene glycol (meth) acrylate, and the like. Among them, a hydroxyalkyl (meth) acrylate is preferred from the viewpoint of adhesion and moisture resistance. Among the hydroxyalkyl (meth) acrylates, 2-hydroxyethyl (meth) acrylate and/or 2-hydroxypropyl (meth) acrylate are preferred, and 2-hydroxyethyl (methyl) is more preferred. Acrylate.

The amount of the monomer A2 to be added is preferably 10 to 70 parts by mass, more preferably 20 to 60 parts by mass, per 100 parts by mass of the monomer A. 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. Monomer A3 The monomer A3 used in the present embodiment is a polyfunctional (meth) acrylate having a bisphenol structure. Among the bisphenol structures, a bisphenol A structure is preferred. Among the monomers A3 used in the present embodiment, a compound of the formula (3) is preferred.

General formula (3) Wherein Z represents a (meth)acryloyl group and R ₂ represents a -C ₂ H ₄ -, -C ₃ H ₆ -, -CH ₂ CH(CH ₃ )-, -C ₄ H ₈ - or -C ₆ H ₁₂ -. 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 a (meth)acrylic monomer include 2,2-bis(4-(methyl)acryloxyphenyl)propane and 2,2-bis(4-(methyl)acrylic acid. Oxyethoxyphenyl)propane, 2,2-bis(4-(methyl)propenyloxydiethoxyphenyl)propane, 2,2-bis(4-(methyl)propene oxime Propyloxyphenyl)propane, 2,2-bis(4-(methyl)propenyloxytetraethoxyphenyl)propane and 2,2-bis(4-(methyl)propenyloxyl Polyethoxyphenyl)propane and the like. Among them, 2,2-bis(4-(methyl)acryloxycarbonylpolyethoxyphenyl)propane is preferred from the viewpoint of adhesion.

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. q is most preferably 5.

The amount of the monomer A3 to be added is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, per 100 parts by mass of the monomer A. 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 or the adhesiveness may be lowered.

1-4. Monomer A4 The monomer A4 used in the present embodiment is a monofunctional (meth) acrylate having an alkyl group. As the alkyl group, an unsubstituted saturated hydrocarbon group is preferred. The alkyl group preferably has 1 to 20 carbon atoms. Among the monomers A4 used in the present embodiment, a compound of the formula (4) is preferred.

General formula (4) ZOR ₄ [wherein Z represents a (meth) acrylonitrile group, and R ₄ represents an alkyl group having 1 to 16 carbon atoms. ]

Examples of the compound of the formula (4) include butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, and n-lauryl (methyl). Acrylate, tridecyl (meth) acrylate, and the like. Among them, 2-ethylhexyl (meth) acrylate is preferred from the viewpoint of adhesiveness, moisture resistance, or low odor.

In the formula, the number of carbon atoms of R ₄ is preferably from 3 to 16, more preferably from 4 to 13. If it is less than three, there is a possibility that moisture resistance or low odor is lowered, and if it exceeds 16, there is a possibility that the adhesion is lowered.

The amount of the monomer A4 to be added is preferably 5 to 40 parts by mass, more preferably 7 to 35 parts by mass, and most preferably 10 to 30 parts by mass per 100 parts by mass of the monomer A. If it is less than 5 parts by mass, the moisture resistance may be lowered. If it exceeds 40 parts by mass, the adhesiveness may be lowered, especially the tensile shear strength of iron may be lowered.

2. Polymerization Initiator B The polymerization initiator B used in the present invention contains a photoradical polymerization initiator B1. 2-1. Photoradical polymerization initiator B1 Examples of the photoradical polymerization initiator B1 include benzophenone and its derivatives, benzoin and its derivatives, hydrazine and its derivatives; benzoin and benzoin A benzoin derivative such as methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, benzoin dimethyl ketal, diethoxyacetophenone, 4-tert-butyltrichlorobenzene An acetophenone derivative such as ethyl ketone; 2-dimethylaminoethyl benzoate, p-dimethylaminoethyl benzoate, diphenyl disulfide, thioxanthone and derivatives thereof, Camphor, 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- Camphorquinone derivatives such as methyl ester, 7,7-dimethyl-2,3-dioxobicyclo[2.2.1]heptane-1-carboxylic acid chloride, 2-methyl-1-[ 4-(methylthio)phenyl]-2-morpholinylpropan-1-ol, 2-phenylisoin-2-dimethylamino-1-(4-morpholinylphenyl)-butanone -1 or the like α-aminoalkanol derivative, benzhydryl diphenylphosphine oxide 2,4,6-trimethylbenzimidyl diphenyl phosphine oxide, benzamidine diethoxy phosphine oxide, 2,4,6-trimethylbenzimidyl dimethoxy phenyl phosphine oxide, Mercapto phosphine oxide derivative such as 2,4,6-trimethylbenzylidene diethoxybenzene phosphine oxide, oxy-phenyl-acetic acid 2-[2-oxo-2-phenyl-ethyl醯oxy-ethoxy]-ethyl ester and oxy-phenyl-acetic acid 2-[2-hydroxy-ethoxy]-ethyl ester and the like. Among them, from the viewpoint of excellent curability, a benzoin derivative and a benzoin derivative are preferably a benzoquinone dimethyl ketal. The amount of use of the photoradical polymerization initiator B1 is preferably 0.5 to 10 parts by mass, and more preferably 1 to 7 parts by mass, per 100 parts by mass of the monomer A. If it is less than 0.5 part by mass, the curing speed may be slow, and if it exceeds 10 parts by mass, the storage stability may be deteriorated.

2-2. Thermal Radical Polymerization Initiator B2 Further, the polymerization initiator B preferably contains a photoradical polymerization initiator B1 and a thermal radical polymerization initiator B2. Among the thermal radical polymerization initiators B2, organic peroxides are preferred. Examples of the organic peroxide include cumene hydroperoxide, hydrogen peroxide to montan, t-butyl hydroperoxide, dicumyl hydroperoxide, methyl ethyl ketone peroxide, benzammonium peroxide, and Oxidized tert-butyl benzoate and the like. One type or two or more types of them can be used. Among them, cumene hydroperoxide is preferred from the viewpoint of reactivity.

The amount of the thermal radical polymerization initiator B2 to be used is preferably 0.5 to 10 parts by mass, more preferably 1 to 7 parts by mass, per 100 parts by mass of the monomer A. If it is less than 0.5 part by mass, the curing speed may be slow, and if it exceeds 10 parts by mass, the storage stability may be deteriorated.

3. Reducing Agent E When the thermal radical polymerization initiator B2 is used, it is preferred to use the reducing agent E at the same time. The reducing agent E used in the present embodiment can be used as long as it is a known reducing agent which reacts with the above polymerization initiator to generate a radical. Typical examples of the reducing agent include a tertiary amine, a sulfur urea derivative, and a transition metal salt.

The tertiary amine may, for example, be triethylamine, tripropylamine, tributylamine or N,N-dimethyl-p-toluidine. Examples of the thiourea derivative include 2-thiol benzimidazole, 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 and a transition metal salt are preferable, and vanadyl oxysulfate is more preferable.

The amount of the reducing agent E used is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 1 part by mass, per 100 parts by mass of the monomer A. If it is less than 0.01 part by mass, the curing speed may be slow, and if it exceeds 5 parts by mass, the storage stability may be lowered.

4. Elastomer C The elastomer C having a polymerizable unsaturated double bond at the end used in the present embodiment is preferably a rubber having a (meth)acrylonitrile content of 10 to 30 mol%, which is the end of the rubber component. A compound having a polymerizable unsaturated double bond. In the elastomer C, 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) acrylonitrile group and/or a vinyl group from the viewpoint of good reactivity, and more preferably a (meth) acryl fluorenyl group.

As the rubber component, a diene (co)polymer is preferred. Examples of the diene-based (co)polymer include a butadiene-(meth)acrylonitrile rubber, a (meth)acrylonitrile-butadiene-(meth)acrylic rubber, and the like. Among the diene (co)polymers, butadiene-(meth)acrylonitrile rubber is preferred from the viewpoint of good flexibility and good compatibility with the above monomers, and a butadiene-acrylonitrile rubber is more preferable.

The (meth)acrylonitrile content is preferably from 10 to 30% by mole, more preferably from 13 to 25% by mole, most preferably from 15 to 20% by mole, from the viewpoint of excellent peeling strength at a low temperature and also resistance to strong impact. . When the (meth)acrylonitrile content is 10% by mole or more, the effect of the present invention is easily obtained, and when it is 30% by mole or less, corrosion is less likely to occur even when a metal such as copper is used as a adherend.

The method of introducing a polymerizable unsaturated double bond to both ends of the molecular chain of the rubber component is, for example, reacting the carboxyl group with glycidyl (meth) acrylate after introducing a carboxyl group to both ends of the rubber component. Alternatively, a method in which the carboxyl group and the hydroxy (meth) acrylate are dehydrated. Further, the diisocyanate may be reacted with a hydroxy (meth) acrylate in advance to react with a liquid rubber having a reactive hydroxyl group at the terminal.

Among them, a rubber obtained by reacting the carboxyl group with glycidyl (meth) acrylate after introducing a carboxyl group to both ends of the rubber component is preferred. For example, a (meth) propylene rubber is used as the rubber component, and an elastomer obtained by reacting the carboxyl group with glycidyl (meth) acrylate after introducing a carboxyl group to both ends of the rubber component is exemplified by An Emerald Performance. "Hypro 1300X33LC VTBNX" manufactured by material company.

The elastomer C is preferably a liquid rubber. The liquid rubber refers to a rubber which is liquid at normal temperature (23 ° C). The (meth)acrylonitrile content of the elastomer C is preferably from 10 to 30 mol% from the viewpoint of excellent peel strength at a low temperature and also resistance to strong impact.

The number average molecular weight of these elastomers C is preferably from 1,000 to 1,000,000, and more preferably from 2,000 to 500,000. If it is less than 1,000, it may affect the peel strength at a low temperature, and if it exceeds 1,000,000, there is a possibility of loss of fluidity.

In the experimental example of the present invention, the number average molecular weight based on polystyrene conversion measured by GPC (gel permeation chromatography) was used. Specifically, tetrahydrofuran was used as a solvent, and a GPC system (SC-8010 manufactured by Tosoh Corporation, Japan) was used, and a calibration curve was prepared based on commercially available standard polystyrene to determine an average molecular weight.

Flow rate: 1.0 ml/min Setting temperature: 40 ° C Column structure: 1 TSK guardcolumn MP (×L) manufactured by Tosoh Corporation of Japan 6.0 mm ID × 4.0 cm, manufactured by two Japanese Tosoh companies "TSK-GELMULTIPOREHXL - M" 7.8mmID × 30.0cm (the number of theoretical plates is 16,000), a total of 3 (as a whole, the number of theoretical plates is 32,000) Sample injection amount: 100μl (sample solution concentration 1mg/ml) Pressure: 39kg/cm ² detector: RI detector

The amount of the elastomer C used is preferably 1 to 50 parts by mass, more preferably 5 to 30 parts by mass, and most preferably 10 to 20 parts by mass, per 100 parts by mass of the monomer A. When the amount is less than 1 part by mass, the peeling strength at a low temperature may be small, and the impact resistance may be poor. When the amount is more than 50 parts by mass, the viscosity may increase, the workability may be deteriorated, and the curability may be insufficient.

5. Elastomer D In the present embodiment, an elastomer D having no polymerizable unsaturated double bond at its end is used.

Examples of the elastomer D include a (meth)acrylonitrile-butadiene-(meth)acrylic acid copolymer and a (meth)acrylonitrile-butadiene-methyl(meth)acrylate copolymer. a benzene such as a methacrylonitrile-butadiene copolymer or a styrene-butadiene copolymer, a benzene-sulfonated polyethylene, or a styrene-polybutadiene-styrene-based synthetic rubber An ethylene-based thermoplastic elastomer, a urethane-based elastomer, or the like. As the elastomer D, an elastomer soluble in the monomer A is preferred.

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

The elastomer D preferably has a (meth)acrylonitrile structure. When having a (meth)acrylonitrile structure, the (meth)acrylonitrile content is preferably from 1 to 30 mol%, more preferably from 10 to 27 mol, from the viewpoint of excellent peel strength at low temperature and strong impact resistance. % is most preferably 13 to 25 mol%, and most preferably 15 to 20 mol%. When the (meth)acrylonitrile content is 1% by mole or more, the effect of the present invention is easily obtained, and when it is 30% by mole or less, corrosion is less likely to occur even when a metal such as copper is used as a adherend.

The amount of the elastomer D used is preferably 5 to 35 parts by mass, more preferably 7 to 33 parts by mass, and most preferably 10 to 30 parts by mass, per 100 parts by mass of the monomer A.

When the elastomer C and the elastomer D are used at the same time, the content ratio thereof is preferably 100:00 by mass, preferably C:D=10 to 90:90 to 10, more preferably 30 to 70:70, in total of 100 parts by mass of C and D. ～30, most preferably 40 to 60: 60 to 40.

In the composition of the present embodiment, various waxes can be used in order to accelerate the curing of the portion in contact with air. Examples of the wax include paraffin wax, microcrystalline wax, palm wax, beeswax, lanolin, cetyl wax, ceresin, and candelilla wax. Among them, paraffin wax is preferred. The melting point of the wax is preferably 40 to 100 °C.

The amount of the wax to be used is preferably 0.1 to 5 parts by mass based on 100 parts by mass of the monomer A. 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 bonding strength may be lowered.

Further, in order to improve storage stability, various antioxidants and the like including a polymerization inhibitor may be used.

Further, in the present embodiment, in order to improve the adhesion and accelerate the curing speed, it is preferred to use phosphate.

Further, in addition to these, a known substance such as a plasticizer, a filler, a colorant, and a rust preventive agent may be used as needed.

Although the components used in the present embodiment have been described above, compounds having less odor other than the above monomers A1 to A4 may be further used.

As an embodiment of the present invention, it is preferably used as a binder composition. When the photoradical polymerization initiator B1 is used, for example, the composition is cured by irradiation with visible light or ultraviolet rays. Examples of the energy irradiation source for illuminating such visible light or ultraviolet light include a deuterium lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a low pressure mercury lamp, a xenon lamp, a helium gas hybrid lamp, a halogen lamp, an excimer lamp, an indium lamp, and a crucible. An energy source for illumination of lamps, LED lamps, electrodeless discharge lamps, and the like. When the thermal radical polymerization initiator B2 is used, for example, it is used as a two-component type binder composition. For the two-component type, the entire composition is not mixed in the storage, and the adhesive composition is divided into the first component and the second component, and the first component contains at least the thermal radical polymerization initiator B2, and the second component At least a reducing agent E is contained, and the first component and the second component are separately stored. At this time, by applying the two components simultaneously or separately, bringing them into contact and curing, it can be used as a two-component type of adhesive composition.

As another embodiment, the polymerizable vinyl monomer and other optional components may be contained in advance by either or both of the first component and the second component, and the two may be mixed as a one-component type upon curing. The composition of the adhesive is used.

In these embodiments, from the viewpoint of good storage stability, it is preferably used as a two-component type adhesive composition. In the present embodiment, when the photoradical polymerization initiator B1 and the thermal radical polymerization initiator B2 are contained, the following effects are obtained. The adhesive composition can be cured by thermal radical polymerization even in the presence of portions where visible light or ultraviolet light cannot enter. When the adhesive composition is adhered to the adherend, the adhesive composition existing at the end of the adherend may be temporarily fixed by irradiating visible light or ultraviolet rays, and then allowed to stand to completely cure the adherend. . By temporarily fixing the visible light or the ultraviolet ray, the adherend can be bonded to a high-precision size.

In the present invention, a bonded body is produced by bonding a adherend using a cured body of a curable resin composition. As for the various materials of the adherend, as long as it is paper, wood, ceramics, glass, pottery, rubber, plastic, mortar, cement and metal, there is no limit, especially when the adherend is metal, especially iron and stainless steel. In the case of the case, it exhibits excellent adhesion. [Experimental example]

Hereinafter, the present invention will be described in more detail by way of experimental examples.

(Experimental Example) The adhesive composition composed of the compositions shown in Table 1 was prepared, and various physical properties were measured. The first component and the second component are mixed in equal amounts. The results are shown in Table 1. The unit of the amount of each substance used is expressed by parts by mass. For each substance, 2,2-bis(4-methylpropenyloxypolyethoxyphenyl)propane is used as q=5, and as a wax, a paraffin wax having a melting point of 40 to 100 ° C is used, and the method described below is used. Various physical properties were determined.

【Table 1】

The following abbreviations are used for each substance described in the table. Liquid NBR: liquid acrylonitrile rubber having a polymerizable unsaturated double bond (methacryl oxime) at the end (manufactured by An Emerald Performance material, Hypro 1300X33LC VTBNX, liquid, number molecular weight 3900) NBR: acrylonitrile-butyl Diene copolymer, elastomer having no polymerizable unsaturated double bond at the end (commercial product) AN amount: liquid NBR having a reactive unsaturated double bond at the end, propylene contained in an acrylonitrile-butadiene copolymer Nitrile content (mol%)

[Tensile Shear Strength (Tensile Shear Bond Strength)] As a test piece, a gauze-treated steel sheet of 100 × 25 × 1.6 mm SPCC - D was used. The first component was coated on one side of one test piece and the second component was coated on the other test piece in accordance with JIS K-6850 at a temperature of 23 ° C and a humidity of 50%. Immediately, the coated surfaces are pasted together with each other. Then, it was cured at room temperature for 24 hours, and it 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 of a temperature of 23 ° C and a humidity of 50%.

[Peel Strength (Peeling Strength)] As a test piece, a gauze wiping treated steel plate of 200 × 25 × 1.6 mm SPCC - D and a gauze wiping treated steel plate of 200 × 25 × 1.5 mm SUS304 were used. The first component was coated on one side of one test piece and the second component was coated on the other test piece in accordance with JIS K-6854 in an environment of a temperature of 23 ° C and a humidity of 50%. The coated surfaces are then immediately adhered to each other in a superposed manner. Then, it was cured at room temperature for 24 hours, and it was used as a sample for measuring the T peel strength. As a confirmation of the low-temperature characteristics, the T-peel strength at a temperature of 23 ° C and a humidity of 50%, a T-peel strength at a tensile speed of 50 mm/min, and a T-peel strength at a temperature of -20 ° C and a tensile speed of 50 mm/min were compared. . In addition, the fracture distance of the peeling in the environment at a temperature of -20 ° C was also compared. The breaking distance of the peeling was measured by the following method. The T-peel strength measurement sample was used, and the chuck section was set to 1 cm, and the upper end portion and the lower end portion of the above-mentioned test piece were fixed, and the test piece was pulled up and down at a temperature of -20 ° C at a tensile speed of 50 mm/min. Stretching, the stretching distance to break was measured. The greater the breaking distance, the greater the peel strength. Further, in Comparative Example 1, since the peeling strength was small and measurement was impossible, it was judged as "undetectable".

[Impact Resistance Test] As a test piece, a gauze wiping treated steel sheet of SUS304 gauze having a plate of 2000 × 500 × 1.5 mm was used, and a gauze wiping treated steel plate of a reinforcing member of 1800 × 20 × 1.5 mm SPCC-D was used. The first component was applied to the central portion of the panel at a temperature of 23 ° C and a humidity of 50%, and the second component was applied to the reinforcing member. Immediately, the coated surfaces are pasted together with each other. Then, it was cured at room temperature for 24 hours, and it was used as a sample for impact test. For the impact test, place the panel with the reinforcing member as the back side, and fix the ends with the support. A 45 kg iron ball was suspended at a height of 800 mm from the surface of the panel and 1000 mm from the end of the panel. Let the iron ball fall naturally and apply an impact to the panel, and observe that the reinforcing member on the back side is peeled off from the panel. The peeling rate of the reinforcing member was calculated by the following formula. Peeling rate (%) of the reinforcing member = (area where the reinforcing member is peeled off) / (area of the adhesive-coated surface to which the adhesive is applied) × 100 (%)

[Deep Curability Test] The deep curability was measured as follows. The adhesive was filled in a black polyurethane tube (length 10 mm) having an inner diameter of 4 mm, and ultraviolet rays were irradiated from the opening. The irradiation conditions are as follows. The ultraviolet irradiation apparatus was cured by irradiating for 60 seconds under the condition of a cumulative irradiation amount of 365 nm of 9000 mJ/cm ² using an LED irradiation machine of HOYA Corporation. After the irradiation, the thickness of the cured product of the adhesive from which the uncured portion was removed was measured with a vernier caliper.

[Odor] The strength of the odor of each curable resin composition was measured as follows. A cured product having a diameter of 10 mm and a thickness of 1 mm was prepared using a resin composition, and the cured product was placed in a glass bottle and sealed, and after standing for 1 hour, the odor was measured using an odor sensor (manufactured by KALMOR Co., Ltd., Japan). In addition, the measurement 室内 in the room where the test was performed was 360. The larger the number, the stronger the odor. The number of odors is preferably 600 or less, and more preferably 500 or less.

The following points were confirmed from Table 1. In the present invention, since the photoradical polymerization initiator B1 is contained, it is excellent in deep curability. The present invention increases the peel strength at a low temperature as the amount of the elastomer C increases. In the second embodiment, the content ratio of the (meth) acrylate containing the monomers A1 to A4 is small in accordance with the total amount of the elastomer C and the elastomer D. Therefore, low odor and low volatility can be achieved. In Comparative Example 1, since the elastomer D had a large acrylonitrile content, the impact resistance was poor. In Comparative Example 2, since the elastomer C was not contained, the peel strength was low. In Comparative Example 3, since the photoradical polymerization initiator B1 was not contained, deep curability was not obtained. ( industrial availability )

According to the adhesive composition of the present invention, a composition excellent in deep curability can be obtained, and for example, a two-component (meth)acrylic adhesive composition which is immediately cured to a deep portion can be obtained. Therefore, it is possible to obtain a fast-curing two-component (meth)acrylic adhesive composition which is easily cured in the cured body. Since the cured adhesive of the adhesive is exposed to the environment under freezing, it is required to have characteristics in a low temperature environment. Under low temperature conditions, the cured product of the adhesive becomes brittle, the bonding strength is lowered, and peeling sometimes occurs. According to the adhesive composition of the present invention, a two-component type (meth)acrylic adhesive composition having a low odor and high peel strength at a low temperature can be obtained. Since the adhesive composition of the present invention does not contain methyl methacrylate, a composition having a low odor and a low volatility can be obtained. Therefore, it is possible to obtain an adhesive that can be used in a place where ventilation is insufficient, and that the adhesive cured product does not peel off in a cold region, and is suitable for a wide range of environments. Further, it is possible to provide a two-component type (meth)acrylic adhesive which is resistant to strong impact, so that it can be used not only in an improved operating environment but also in various industrial fields.

Claims (22)

A composition comprising: a polymerizable vinyl monomer A, a polymerization initiator B containing a photoradical polymerization initiator B1, an elastomer C having a polymerizable unsaturated double bond at the terminal, and a terminal having no polymerizable unsaturated double bond The elastomer D of the bond, wherein the elastomer D has a (meth)acrylonitrile content of from 1 to 30 mol%. The composition according to claim 1, wherein the monomer A contains two or more of the monomers A1 to A4, the monomer A1 is a monofunctional (meth) acrylate having a phenyl group, and the monomer A2 has a hydroxyl group. The monofunctional (meth) acrylate, the monomer A3 is a polyfunctional (meth) acrylate having a bisphenol structure, and the monomer A4 is a monofunctional (meth) acrylate having an alkyl group. The composition according to claim 1, wherein the monomer A contains three or more of the monomers A1 to A4, the monomer A1 is a monofunctional (meth) acrylate having a phenyl group, and the monomer A2 has a hydroxyl group. The monofunctional (meth) acrylate, the monomer A3 is a polyfunctional (meth) acrylate having a bisphenol structure, and the monomer A4 is a monofunctional (meth) acrylate having an alkyl group. The composition according to claim 1, wherein the monomer A contains the monomers A1 to A4, the monomer A1 is a monofunctional (meth) acrylate having a phenyl group, and the monomer A2 is a monofunctional group having a hydroxyl group (A) The acrylate, the monomer A3 is a polyfunctional (meth) acrylate having a bisphenol structure, and the monomer A4 is a monofunctional (meth) acrylate having an alkyl group. The composition according to claim 1, wherein the elastomer C has a (meth)acrylonitrile content of 10 to 30% by mole. The composition according to claim 1, wherein the elastomer D is a diene copolymer. The composition according to claim 5, wherein the content ratio of the elastomer C to the elastomer D is C: D = 10 to 90: 90 to 10 in terms of a mass ratio of 100 parts by mass of C and D. The composition according to claim 5, wherein the blending ratio of the elastomers C and D is 1 to 50 parts by mass and 5 to 35 parts by mass, respectively, per 100 parts by mass of the monomer A. The composition according to claim 4, wherein the amount of the monomers A1, A2, A3, and A4 is 10 to 60 parts by mass, 10 to 70 parts by mass, and 1 to 30, respectively, per 100 parts by mass of the monomer A. Parts by mass, 5 to 40 parts by mass; The content of (meth)acrylonitrile of the elastomer C is 10 to 30% by mole; and the amount of the elastomers C and D is 1 to 50 by mass with respect to 100 parts by mass of the monomer A, respectively. Parts, 5 to 35 parts by mass. The composition according to claim 1, which further contains a wax. The composition according to claim 1, wherein the polymerization initiator B further contains a thermal radical polymerization initiator B2. The composition according to claim 11, which further contains a reducing agent E. The composition according to claim 12, wherein the composition is a two-component type composition containing at least a thermal radical polymerization initiator B2 in the first component and at least a reducing agent E in the second component. The composition according to any one of claims 2 to 4, wherein the monomer A1 is a compound of the formula (1), and the formula (1) ZO-(R ₂ O)pR ₁ wherein Z represents Methyl)propenyl group, R ₁ represents a phenyl group or a phenyl group having an alkyl group having 1 to 3 carbon atoms, 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 of 1 to 10. The composition according to any one of claims 2 to 4, wherein the monomer A2 is a compound of the formula (2), and the formula (2) ZO-(R ₂ O)p-H wherein Z represents (meth)acryloyl group, 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. The composition according to any one of claims 2 to 4, wherein the monomer A3 is a compound of the formula (3), and the formula (3) Wherein Z represents (meth)acrylonyl 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 -, R ₃ represents hydrogen or an alkyl group having 1 to 4 carbon atoms, and q represents a number of 0 or more. The composition according to any one of claims 2 to 4, wherein the monomer A4 is a compound of the formula (4), and in the formula (4) ZOR ₄ , Z represents a (meth) acrylonitrile group. R ₄ represents an alkyl group having 1 to 16 carbon atoms. A curable resin composition containing the composition according to any one of claims 1 to 17. An adhesive composition containing the curable resin composition as described in claim 18. A joint body in which the joint body is bonded to an adherend using the adhesive composition as claimed in claim 19. A bonding method in which an adherend composition as claimed in claim 19 is adhered to an adherend. An adhesive method in which, when the adhesive composition as claimed in claim 19 is adhered to the adherend, the adhesive composition existing at the end of the adherend is irradiated with visible light or ultraviolet rays.