TW201710423A - Composition and adhesive composition - Google Patents

Abstract

Provided is a composition with low odor and improved peel strength at low temperatures. The composition is obtained as a result of containing the following: (1) polymerizable vinyl monomers containing (1-1) to (1-4), (1-1) being a compound of general formula (A) (general formula(A) Z-O-(R2O)p-R1)[In the formula, Z represents a (meth)acryloyl group, and R1 represents a phenyl group or a phenyl group having an alkyl group having from 1 to 3 carbon atoms. R2 represents -C2H4-, -C3H6-, -CH2CH(CH3)-, -C4H8-, or -C6H12-, and p represents an integer from 1 to 10.], (1-2) being a compound of general formula (B) (general formula (B) Z-O-(R2O)p-H) [In the formula, Z, R2 and p are as defined above.], (1-3) being a compound of general formula (C) [In the formula, Z and R2 are as defined above. R3 represents hydrogen or an alkyl group having 1 to 4 carbon atoms, and q represents a number of 0 or more.], (1-4) being a compound of general formula (D) (general formula (D) Z-O-R4)[In the formula, Z represents a (meth)acryloyl group, and R4 represents an alkyl group having 3 to 16 carbon atoms.]; (2) a polymerization initiator; (3) a reducing agent; (4) a rubber having a polymerizable unsaturated double bond at an end; and (5) an elastomer not having a polymerizable unsaturated double bond at an end.

Description

Composition and binder composition

The present invention relates to a two-part acrylic pressure-sensitive adhesive composition which is excellent in adhesive strength even at a low temperature.

From the viewpoints of labor saving, resource saving, and energy saving, as a binder which is bonded at a normal temperature for a short period of time, a room temperature quick-curing adhesive composition is being used. Conventionally, as a known room temperature fast-curing adhesive composition, there are a two-pack type fast-curing epoxy-based adhesive composition, an anaerobic adhesive composition, a transient adhesive composition, and a second-generation acrylic acid. A binder composition (SGA).

The two-pack type fast-curing epoxy-based adhesive is a metering main agent and a curing agent, and is mixed and applied to an adherend, and is solidified by a reaction of a main agent and a curing agent. However, the two-part fast cure epoxy adhesive requires higher peel strength and impact strength.

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

The instant adhesive usually has cyanoacrylate as a main component and is excellent in handleability. However, it requires higher peel strength or impact strength.

SGA is a two-component acrylic adhesive, but it does not require accurate measurement of two doses. Even if it is incompletely measured or mixed, it can be cured at room temperature for several minutes to several tens of minutes as long as it is contacted by two doses. Moreover, the peeling strength or the impact strength is high, and the solidification of the overflow portion is also good, so it is widely used in the field of electrical and electronic components to the field of civil engineering and construction. Recently, an SGA capable of suppressing odor has appeared, and it is possible to operate even when the ventilation device is insufficient.

Among the various required characteristics, the characteristics in a low temperature environment are sought, and the cured adhesive is exposed to an environment below the freezing point.

[Prior Art Literature] [Patent Literature]

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

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

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

However, there is no description of a composition which is low in odor and low in volatility by the absence of methyl methacrylate.

Patent Document 2 discloses a composition having a low odor and a low volatility, but is not described for a rubber having a polymerizable unsaturated double bond.

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

That is, the present invention is as follows: a composition comprising: (1) a polymerizable vinyl monomer comprising (1-1) to (1-4)

(1-1) a compound of the formula (A)

General formula (A): ZO-(R ₂ O) _p -R 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. 〕; (1-2) a compound of the formula (B)

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

Wherein 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 formula (D)

General formula (D): ZOR ₄

Wherein Z represents a (meth)acrylonitrile group, and R ₄ represents an alkyl group having 3 to 16 carbon atoms. (2) a polymerization initiator; (3) a reducing agent; (4) a rubber having a polymerizable unsaturated double bond at the terminal; and (5) an elastomer having no polymerizable unsaturated double bond at the terminal, and the composition (4) The rubber having a polymerizable unsaturated double bond at the terminal is a butadiene rubber having a polymerizable unsaturated double bond at the terminal, and the butadiene rubber having a polymerizable unsaturated double bond at the terminal is not having (meth) propylene. a nitrile structure in which the elastomer having no polymerizable unsaturated double bond at the terminal (5) is a diene copolymer, and the first agent contains at least (2) a polymerization initiator and at least a second agent. a two-part type containing (3) a reducing agent, a curable resin composition containing the composition, a binder composition containing the curable resin composition, and (4) a polymerizable unsaturated end The rubber of the double bond is a butadiene rubber having a (meth)acrylonitrile group at both ends and having no (meth)acrylonitrile structure, and the amount of the (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 amount of the (5) used is relative to (1) a polymerizable vinyl group. 100 parts by mass of 5 to 35 parts by mass.

A bonded body obtained by bonding an adherend using the adhesive composition, and a bonding method for bonding an adherend using the adhesive composition.

The pressure-sensitive adhesive composition of the present invention is, for example, a two-part (meth)acrylic pressure-sensitive adhesive composition which can improve the peel strength at a low temperature, and can be applied not only to improve the operating environment but also to various industrial fields.

Hereinafter, the present invention will be described in detail.

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

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

General formula (A): ZO-(R ₂ O) _p -R 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 (1-1) (A) include phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, and phenoxy polyethylene glycol ( Methyl) acrylate, phenoxypropyl (meth) acrylate, phenoxy dipropylene glycol (meth) acrylate, and phenoxy polypropylene glycol (meth) acrylate. Among them, phenoxyethyl (meth)acrylate is preferred from the viewpoint of adhesion.

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

The compound of the formula (B) (B) used in the present invention means the following structure.

General formula (B): ZO-(R ₂ O) _p -H

Wherein Z, R ₂ and p are as described above. 〕

Examples of the compound of the formula (B) (B) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and the like. Hydroxyethyl (meth)acrylate, diethylene glycol mono(meth)acrylate, and polypropylene glycol (meth)acrylate. Among them, hydroxyethyl (meth)acrylate is preferred from the viewpoint of adhesion 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) The amount of the compound of the formula (B) to be used is preferably 10 to 70 parts by mass, more preferably 20 to 60 parts by mass, per 100 parts by mass of the polymerizable vinyl monomer. If it is less than 10 parts by mass, the adhesiveness may be lowered, and if it exceeds 70 parts by mass, the moisture resistance may be lowered.

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

Wherein 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 a (meth)acrylic monomer include 2,2-bis(4-(methyl). Propylene methoxy phenyl) propane, 2,2-bis(4-(methyl) propylene methoxy ethoxy phenyl) propane, 2,2-bis(4-(methyl) propylene oxy 2 Ethoxyphenyl)propane, 2,2-bis(4-(methyl)propenyloxypropoxyphenyl)propane, 2,2-bis(4-(methyl)propenyloxytetraethyl Oxyphenyl)propane and 2,2-bis(4-(methyl)propenyloxypolyethoxyphenyl)propane. 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. 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) The amount of the compound of the formula (C) to be used is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, per 100 parts by mass of the polymerizable vinyl monomer. If it is less than 1 part by mass, the adhesiveness may be lowered, and if it exceeds 30 parts by mass, the moisture resistance may be lowered.

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

General formula (D): ZOR ₄

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

Examples of the compound of the formula (1-4) (D) include butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, and (methyl). N-lauryl acrylate and tridecyl (meth) acrylate. Among them, 2-ethylhexyl (meth)acrylate and/or butyl (meth)acrylate are preferred from the viewpoint of adhesion or moisture resistance, and it is more preferred to use (meth) together. 2-ethylhexyl acrylate and butyl (meth)acrylate. Among the butyl (meth)acrylates, n-butyl (meth)acrylate is preferred.

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

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, the moisture resistance may be lowered, and if it is more than 16, the adhesiveness may be lowered.

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

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 peroxide include cumene hydroperoxide, hydrogen peroxide to montan, tert-butyl hydroperoxide, diisopropylbenzene dihydrobenzene, methyl ethyl ketone peroxide, benzammonium peroxide, and Oxidized tert-butyl benzoate and the like. One type or two or more types can be used. Among them, cumene hydroperoxide is preferred from the viewpoint of reactivity.

(2) The amount of the polymerization initiator used is superior to (1) 100 parts by mass of the polymerizable vinyl monomer It is selected from 0.5 to 10 parts by mass, more preferably from 1 to 7 parts by mass. 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.

The reducing agent (3) used in the present invention 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.

Examples of the tertiary amine include triethylamine, tripropylamine, tributylamine, and N,N-dimethyl-p-toluidine. Examples of the thiourea derivative include 2-mercaptobenzimidazole, methylthiourea, dibutylthiourea, tetramethylthiourea, and ethylenethiourea. Examples of the transition metal salt include cobalt naphthenate, copper naphthenate, and vanadyl acetonate. Among them, a transition metal salt is preferred from the viewpoint of reactivity, and acetonitrile acetone vanadium is more preferable.

(3) The amount of the reducing agent to be 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 polymerizable vinyl monomer. If it is less than 0.01 parts by mass, the curing speed may be slow, and if it exceeds 5 parts by mass, the storage stability may be lowered.

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) acrylonitrile group and/or a vinyl group, and more preferably a (meth) acryl fluorenyl group from the viewpoint of good reactivity.

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

The method of introducing a polymerizable unsaturated double bond at both ends of the molecular chain of the rubber component, for example, by introducing a carboxyl group at both ends of the rubber component, reacting the glycidyl (meth)acrylate with the carboxyl group, or A method of dehydrating a reaction of the carboxyl group with a hydroxy (meth) acrylate. Alternatively, the diisocyanate may be previously reacted with a hydroxy (meth) acrylate to react the reaction product with a liquid rubber having a reactive hydroxyl group at the terminal.

Among them, a rubber obtained by reacting a glycidyl (meth)acrylate with a carboxyl group after introducing a carboxyl group at both ends of the rubber component is preferred.

For example, a rubber obtained by using butadiene rubber as a rubber component and introducing a carboxyl group at both ends of the rubber component, and reacting the glycidyl methacrylate with the carboxyl group, "Hypro VTB2000X168" manufactured by AnEmerald Performance Material Co., Ltd. Wait.

(4) The rubber having a polymerizable unsaturated double bond at its end is preferably a liquid rubber. The liquid rubber refers to a rubber which is liquid at normal temperature (23 ° C).

The number average molecular weight of the rubber having a polymerizable unsaturated double bond at the (4) terminal is preferably from 1,000 to 1,000,000, and more preferably from 2,000 to 500,000. If it is less than 1000, there is a possibility that it has no influence on the peel strength at a low temperature, and if it exceeds 1,000,000, the fluidity may be lost.

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 was determined by using tetrahydrofuran as a solvent and using a GPC system (SC-8010 manufactured by Tosoh Corporation) under the following conditions, and preparing a standard curve using commercially available standard polystyrene.

Flow rate: 1.0ml/min

Set temperature: 40 ° C

Column configuration: "TSK guardcolumn MP (×L)" manufactured by Tosoh Co., Ltd. 6.0 mmID × 4.0 cm 1 and "TSK-GELMULTIPOREHXL-M" manufactured by Tosoh Corporation 7.8 mmID × 30.0 cm (the number of theoretical plates 16,000), totaling 3 (The overall theoretical number of boards is 32,000)

Sample injection amount: 100 μl (sample solution concentration 1 mg/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 from 1 to 50 parts by mass, more preferably from 5 to 30 parts by mass, based on 100 parts by mass of the polymerizable vinyl monomer, most preferably It is 10 to 20 parts by mass. If it is less than 1 part by mass, there is a possibility that 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 (5) an elastomer having no polymerizable unsaturated double bond at its end.

Examples of the elastomer having no polymerizable unsaturated double bond at the (5) terminal include (meth)acrylonitrile-butadiene-(meth)acrylic acid copolymer and (meth)acrylonitrile-butadiene- Methyl (meth) acrylate copolymer, (meth) acrylonitrile-butadiene copolymer, styrene-butadiene copolymer, etc. A styrene-based thermoplastic elastomer such as a diene copolymer, a chlorosulfonated polyethylene, a styrene-polybutadiene-styrene-based synthetic rubber, or a polyurethane-based elastomer.

The elastomer which does not have a polymerizable unsaturated double bond at the (5) terminal is preferably an elastomer which is soluble in (1) a polymerizable vinyl monomer.

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

(5) The amount of the elastomer having no polymerizable unsaturated double bond at the end is preferably 5 to 35 parts by mass, more preferably 10 to 30 parts by mass, per 100 parts by mass of the polymerizable vinyl monomer. .

In the case where a rubber having a polymerizable unsaturated double bond at the terminal (4) and an elastomer having no polymerizable unsaturated double bond at the terminal (4) are used in combination, the content of the mixture is 100 mass in total of (4) and (5). The ratio by mass 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 cure the portion in contact with air, various paraffin waxes can be used for the composition of the present invention. Examples of the paraffin wax include paraffin wax, microcrystalline wax, Brazilian wax palm wax, beeswax, lanolin, cetyl wax, ceresin wax, and candelilla wax. Among them, paraffin wax is preferred. The melting point of the paraffin wax is preferably 40 to 100 °C.

The amount of the paraffin to be used is preferably 0.1 to 5 parts by mass based on 100 parts by mass of the (1) 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 bonding strength may be lowered.

Further, for the purpose of improving storage stability, various antioxidants and the like including a polymerization inhibitor 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 and N-isopropyl-N'-phenyl-p-phenylenediamine. Among them, p-methoxyphenol is preferred.

The amount of the antioxidant to be used is preferably 0.001 to 3 parts by mass based on 100 parts by mass of the (1) polymerizable vinyl monomer. If it is less than 0.001 part by mass, there is a possibility that there is no effect, and if it exceeds 3 parts by mass, the curability of the binder may be lowered.

Further, in the present invention, in order to improve the adhesion and accelerate the curing rate, it is preferred to use a phosphate.

Among the phosphates, an acidic phosphoric acid compound of the formula (E) is preferred from the viewpoint of adhesion or curing speed.

(wherein R represents CH ₂ =CR ₄ CO(OR ₅ ) _m - group (wherein R ₄ represents hydrogen or methyl, and 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, and n represents an integer of 1 or 2.)

Examples of the acidic phosphoric acid compound of the formula (E) include acidic (phosphinyl)ethyl (meth)acrylate, phosphinylpropyl propyl (meth)acrylate, and bis(2-(methyl). Propylene oxyethyl) phosphate and the like. Among them, acidic (meth)acrylic acid phosphinyloxyethyl ester is preferred from the viewpoint of adhesion or curing speed.

The amount of the phosphate added is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 7 parts by mass, per 100 parts by mass of the polymerizable vinyl monomer. If it is less than 0.05 parts by mass, the curing speed may be slow and the adhesiveness may be lowered, and even if it exceeds 10 parts by mass, the adhesiveness may be lowered.

In 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, based on 100 parts by mass of the composition. The amount is most preferably 90 parts by mass or more, and more preferably 95 parts by mass or more.

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, in 100 parts by mass of the composition of the present invention. It is most preferably 65 parts by mass or more, and more preferably 70 parts by mass or more.

In addition to the above components, a plasticizer, a filler, or a plasticizer may be used as needed. Known substances such as colorants and rust inhibitors.

Although the components used in the present invention have been described above, the composition of the present invention may be further used in addition to the above (1-1), (1-2), (1-3), and (1-4). a stinky compound.

As an embodiment of the present invention, it is preferably used as a binder composition. In this case, for example, a two-part type binder composition can be used. For the two dosage forms, the entire essential components of the adhesive composition of the present invention are not mixed during storage, and 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) a reducing agent and a phosphate as needed, and they are separately stored. In this case, the two agents can be used as a two-part type binder composition by simultaneously or separately coating them to be contacted and cured.

In another embodiment, either or both of the first agent and the second agent may contain a polymerizable vinyl monomer and other optional components in advance, and the two may be mixed during curing to serve as a one-component adhesive. The composition is used.

Among these embodiments, from the viewpoint of excellent storage stability, it is preferably used as a two-part type binder composition.

In the present invention, a bonded body is produced by bonding an adherend using a cured body of a curable resin composition. For various materials of the adherend, it can be paper, wood, ceramic, glass, ceramics, There are no restrictions on rubber, plastic, mortar, concrete, metal, etc., but when the adherend is metal, especially tantalum or stainless steel, it can exhibit more excellent adhesion.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples. In addition, the unit of the usage amount of each substance is shown by mass part. In addition, 2,2-bis(4-methylpropenyloxypolyethoxyphenyl)propane of q=5 is used for each substance, and paraffin wax having a melting point of 40 to 100 ° C is used as the paraffin wax, and various The physical properties were determined as follows.

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

[Peel Strength (Peel Bond Strength)] As a test piece, a 200×25×1.6 mm SPCC-D cloth-wipe-treated steel sheet and a 200×25×1.5 mm SUS304 cloth-treated steel sheet were used. The first agent was applied to one side of one test piece in the environment of a temperature of 23 ° C and a humidity of 50% in accordance with JIS K-6854, and the second agent was applied to the other test piece. Immediately thereafter, the coated faces were placed one on top of the other. Thereafter, it was cured at room temperature for 24 hours. This was used as a sample for measuring the T peel strength. As a confirmation of the low-temperature characteristics, the tensile speed was 50 mm in an environment of a temperature of 23 ° C and a humidity of 50%. The T peel strength at the minute was compared with the T peel strength at a tensile speed of 50 mm/min in a temperature of -20 ° C. In addition, the fracture distance of peeling in an environment of a temperature of -20 ° C was also compared.

The peeling distance of the peeling was measured by the following method. The T-peel strength measurement sample was used, and the chuck pitch was set to 1 cm, and the upper end portion and the lower end portion of the test piece were fixed, and the test piece was stretched up and down at a temperature of -20 ° C and a tensile speed of 50 mm/min. The stretching distance of the fracture 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.

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 the mixture was allowed to stand for 1 hour, and then an odor was measured using an odor sensor (manufactured by Karumoa Co., Ltd.). The measured value in the room where the test was conducted was 360. A larger value indicates a stronger odor. The value of the 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 by way of experimental examples. The unit of the amount of each substance used is expressed by parts by mass.

The following abbreviations are used for each substance described in the table.

Liquid butadiene rubber: liquid butadiene rubber having a polymerizable unsaturated double bond at both ends (An Emerald Performance material, Hypro VTB2000X168, liquid, number average molecular weight 4500, group having a polymerizable unsaturated double bond) Is a methacrylonitrile group, the liquid butadiene rubber does not have a (meth)acrylonitrile structure)

NBR: acrylonitrile-butadiene copolymer, elastomer having no polymerizable unsaturated double bond at the end (commercial product)

Phosphate: acid phosphonium oxyethyl methacrylate

The following can be seen from the table. In the present invention, as the amount of (4) increases, peeling at low temperatures Increased strength. In the third embodiment, since the amount of (4) and (5) is large and the content of the (meth) acrylate composed of (1-1) to (1-4) is small, low odor and low can be achieved. volatility. In Comparative Example 3 in which methyl methacrylate was used instead of (1-4), the peel strength at a low temperature was small and there was an odor.

[Industrial availability]

According to the pressure-sensitive adhesive composition of the present invention, a two-part acrylic pressure-sensitive adhesive composition having a low odor and high peel strength at a low temperature can be obtained. Therefore, even in a place where ventilation is insufficient, the operation can be performed, and the adhesive composition does not peel off in a cold area. The adhesive composition has a wide application environment and is therefore industrially beneficial.

Claims (10)

A composition comprising the following (1) a polymerizable vinyl monomer (1-1) containing (1-1) to (1-4): a compound of the formula (A): (a): ZO- (R ₂ O) _{p -} R ₁ wherein Z represents a (meth)acrylinyl 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 from 1 to 10; (1-2) formula (B) Compound of formula (B): ZO-(R ₂ O) _p -H wherein Z, R ₂ and p are as defined above; (1-3) compound of formula (C) In the formula, Z and R _{2 are} as defined above, R ₃ represents hydrogen or an alkyl group having 1 to 4 carbon atoms, q represents a number of 0 or more; (1-4) a compound of the formula (D) has the formula (D) In the formula ZOR ₄ , Z represents a (meth) acrylonitrile group, R ₄ represents an alkyl group having 3 to 16 carbon atoms; (2) a polymerization initiator; (3) a reducing agent; and (4) a terminal polymerizable property. a rubber having a saturated double bond; and (5) an elastomer having no polymerizable unsaturated double bond at its end. The composition according to claim 1, wherein the rubber having a polymerizable unsaturated double bond at the (4) terminal is a butadiene rubber having a polymerizable unsaturated double bond at its end. 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) terminal is a diene copolymer. The composition according to any one of claims 1 to 4, wherein the composition is a first agent containing at least the (2) polymerization initiator, and the second agent contains at least the (3) reduction Two dosage forms of the agent. A curable resin composition containing the composition according to any one of claims 1 to 5. An adhesive composition comprising 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) terminal has a (meth)acryl fluorenyl group at both ends, and has no (methyl group) In the acrylonitrile-structured butadiene rubber, the amount of the (4) used is 1 to 50 parts by mass based on 100 parts by mass of the (1) polymerizable vinyl monomer, and the amount of the (5) used is relative to ( 1) 100 parts by mass of the polymerizable vinyl monomer is 5 to 35 parts by mass. A joined body obtained by bonding an adherend using the adhesive composition described in claim 7 . A bonding method in which the adhesive method is used to bond an adherend using the adhesive composition described in claim 7.