JP6955411B2 - Composition - Google Patents

Description

The present invention relates to a composition having excellent adhesiveness.

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

The two-agent type fast-curing epoxy adhesive measures and mixes the main agent and the curing agent, applies the adhesive to the adherend, and cures by the reaction between the main agent and the curing agent. However, the two-part fast-curing epoxy adhesive is required to have higher peel strength and impact strength.

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

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

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

However, recently, it has been required to withstand a large load for a long period of time. For that purpose, it is necessary that not only the tensile shear strength but also the peel strength is high. Further, since aluminum is used for weight reduction in airplanes and the like, it is necessary to have high adhesiveness to aluminum in addition to iron. By satisfying these high requirements, it becomes possible to have high strength characteristics under various operating environment conditions as a structural adhesive used for joining structural members.

Patent Document 1 discloses a composition having a low odor and low volatility. However, there is no description about (1-1) of the present invention.

Japanese Unexamined Patent Publication No. 2001-55423

An object of the present invention is, for example, to provide a two-agent type (meth) acrylic adhesive having excellent adhesiveness.

（１−２）一般式（Ｂ）の化合物
一般式（Ｂ） Ｚ−Ｏ−（Ｒ^２Ｏ）ｐ−Ｈ
〔一般式中、Ｚは（メタ）アクリロイル基を示す。Ｒ^２はアルキレン基を示す。ｐは１〜１０の数を示す。〕
（１−３）一般式（Ｃ）の化合物

（１−４）一般式（Ｄ）の化合物
一般式（Ｄ） Ｚ−Ｏ−Ｒ^５
〔一般式中、Ｚは（メタ）アクリロイル基を示し、Ｒ^５はアルキル基を示す。〕
（２）重合開始剤
（３）還元剤
＜２＞更に、（４）エラストマーを含有する＜１＞記載の組成物。
＜３＞（４）エラストマーの（メタ）アクリロニトリル含有量が１〜５０モル％である＜２＞記載の組成物。
＜４＞（１）重合性ビニルモノマー１００質量部中、（１−１）１０〜６０質量部、（１−２）１０〜７０質量部、（１−３）１〜３０質量部、（１−４）５〜４０質量部を含有する＜１＞〜＜３＞のうちの１項記載の組成物。
＜５＞更に、（５）リン酸塩を含有する＜１＞〜＜４＞のうちの１項記載の組成物。
＜６＞更に、パラフィン類を含有する＜１＞〜＜５＞のうちの１項記載の組成物。
＜７＞更に、酸化防止剤を含有する＜１＞〜＜６＞のうちの１項記載の組成物。
＜８＞（３）還元剤が、第３級アミン及び遷移金属塩を含有する＜１＞〜＜７＞のうちの１項記載の組成物。
＜９＞＜１＞〜＜８＞のうちの１項記載の組成物を含有する硬化性樹脂組成物。
＜１０＞＜１＞〜＜８＞のうちの１項記載の組成物を含有する接着剤組成物。
＜１１＞請求項１〜８のうちの１項記載の組成物を第一剤と第二剤に分け、第一剤が少なくとも（２）重合開始剤を含有し、第二剤が少なくとも（３）還元剤を含有する二剤型の組成物。
＜１２＞＜１＞〜＜８＞のうちの１項記載の組成物を使用して被着体を接合する接合体。
＜１３＞＜１＞〜＜８＞のうちの１項記載の組成物を使用して被着体を接合する接合体の製造方法。 That is, the present invention is as follows.
<1> A composition containing the following (1) to (4).
(1) A compound of the polymerizable vinyl monomer (1-1) general formula (A) containing (1-1) to (1-4).

(1-2) The compound of the general formula (B) (B) Z- O- (R 2 O) p-H
[In the general formula, Z represents a (meth) acryloyl group. R ² represents an alkylene group. p represents a number from 1 to 10. ]
(1-3) Compound of general formula (C)

(1-4) Compound of general formula (D) General formula (D) ZOR ⁵
[In the formula, Z is shown a (meth) acryloyl group, R ⁵ represents an alkyl group. ]
(2) The composition according to <1>, which further contains (4) an elastomer (2) a polymerization initiator (3) a reducing agent <2>.
<3> (4) The composition according to <2>, wherein the (meth) acrylonitrile content of the elastomer is 1 to 50 mol%.
<4> (1) In 100 parts by mass of the polymerizable vinyl monomer, (1-1) 10 to 60 parts by mass, (1-2) 10 to 70 parts by mass, (1-3) 1 to 30 parts by mass, (1). -4) The composition according to item 1 of <1> to <3>, which contains 5 to 40 parts by mass.
<5> The composition according to item 1 of <1> to <4>, which further contains (5) phosphate.
<6> The composition according to item 1 of <1> to <5>, which further contains paraffins.
<7> The composition according to item 1 of <1> to <6>, which further contains an antioxidant.
<8> (3) The composition according to item 1 of <1> to <7>, wherein the reducing agent contains a tertiary amine and a transition metal salt.
<9> A curable resin composition containing the composition according to item 1 of <1> to <8>.
<10> An adhesive composition containing the composition according to item 1 of <1> to <8>.
<11> The composition according to claim 1 of claims 1 to 8 is divided into a first agent and a second agent, the first agent containing at least (2) a polymerization initiator, and the second agent at least (3). ) A two-part composition containing a reducing agent.
<12> A bonded body for joining an adherend using the composition according to item 1 of <1> to <8>.
<13> A method for producing a bonded body in which an adherend is bonded using the composition according to item 1 of <1> to <8>.

The present invention can provide a composition that improves adhesiveness.

Hereinafter, the present embodiment will be described in detail.

This embodiment contains (1-1), (1-2), (1-3) and (1-4) as polymerizable vinyl monomers. (1) The polymerizable vinyl monomer may be radically polymerizable. Above all, the polymerizable vinyl monomer is more preferably a polymerizable (meth) acrylic acid derivative from the viewpoint of curing speed and the like. It is preferable that the polymerizable (meth) acrylic acid derivative is 70 parts by mass or more in 100 parts by mass of the polymerizable vinyl monomer, and it is more preferable that all the polymerizable vinyl monomers are the polymerizable (meth) acrylic acid derivative. Hereinafter, (1) 100 parts by mass of the polymerizable vinyl monomer is preferably 100 parts by mass in total of (1-1), (1-2), (1-3) and (1-4). .. Unless otherwise specified, the amount used is preferably the amount used based on the total of the first agent and the second agent. The total amount of the (1) polymerizable vinyl monomer and (4) elastomer used is preferably 50 parts by mass or more, more preferably 75 parts by mass or more, based on 100 parts by mass of the composition.

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

Examples of the (meth) acrylate of the general formula (A) include benzyl (meth) acrylate, methylbenzyl (meth) acrylate, ethylbenzyl (meth) acrylate, propylbenzyl (meth) acrylate, methoxybenzyl (meth) acrylate, and chlorobenzyl (meth). Meta) acrylate and the like can be mentioned. Among the (meth) acrylates of the general formula (A), benzyl (meth) acrylate is preferable.

(1-1) The amount of the compound of the general formula (A) to be used is preferably 10 to 60 parts by mass, more preferably 20 to 50 parts by mass, out of 100 parts by mass of (1) the polymerizable vinyl monomer. If it is 10 parts by mass or more, the adhesiveness is improved, and if it is 60 parts by mass or less, the adhesiveness is improved.

The compound of the (1-2) general formula (B) used in the present embodiment means the following structure.

Formula ^{(B) Z-O- (R} 2 O) p-H
[In the general formula, Z represents a (meth) acryloyl group. R ² represents an alkylene group. p represents a number from 1 to 10. ]
R ² is preferably one or more consisting of −C ₂ H ₄ −, −C ₃ H ₆ −, −CH ₂ CH (CH ₃ ) −, −C ₄ H ₈ − or −C ₆ H _{12 −.} p is preferably an integer.

(1-2) Examples of the compound of the general formula (B) include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. Examples thereof include diethylene glycol mono (meth) acrylate and polypropylene glycol (meth) acrylate. Among these, hydroxyalkyl (meth) acrylate is preferable from the viewpoint of adhesiveness and moisture resistance. Among the hydroxyalkyl (meth) acrylates, 2-hydroxyethyl (meth) acrylate and / or 2-hydroxypropyl (meth) acrylate is preferable, and 2-hydroxypropyl (meth) acrylate is more preferable.

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

The compound of the general formula (C) used in the present embodiment (1-3) has the following structure.

^{R 3,} R ³ 'is _{-C 2 H 4 -, - C} 3 H 6 -, - CH 2 CH (CH 3) -, - C 4 H 8 - or _-C 6 _{H 12} - 1 or more is composed of preferable. Integers are preferable for q and q'. ^{R 4,} R ⁴ 'is preferably a methyl group.

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

Further, q and q'are numbers of 0 or more. q and q'are preferably 1 or more, and more preferably 3 or more. q and q'are preferably 15 or less, more preferably 10 or less, and most preferably 8 or less. 5 is even more preferable for q and q'.

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

The compound of the general formula (D) used in the present embodiment (1-4) has the following structure.

General formula (D) Z-OR ⁵
[In the formula, Z is shown a (meth) acryloyl group, R ⁵ represents an alkyl group. ]
R ⁵ is more preferably an alkyl group having 3 to 16 carbon atoms. The alkyl group is preferably a saturated hydrocarbon group.

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

In the formula, the carbon number of ^{R 5} is preferably 1 or more, more preferably 3 to 16, most preferably 4 to 13. If it is 1 or more, the moisture resistance is improved, and if it is 16 or less, the adhesiveness is improved.

(1-4) The amount of the compound of the general formula (D) to be used is preferably 5 to 40 parts by mass, more preferably 7 to 35 parts by mass, and 10 to 30 parts by mass out of 100 parts by mass of the (1) polymerizable vinyl monomer. The part is most preferable. If it is 5 parts by mass or more, the moisture resistance is improved, and if it is 40 parts by mass or less, the adhesiveness, particularly the tensile shear strength against iron is improved.

As the (2) polymerization initiator used in the present embodiment, a thermal radical polymerization initiator is preferable. Among the thermal radical polymerization initiators, organic peroxides are preferable. Examples of the organic peroxide include cumene hydroperoxide, paramentan hydroperoxide, tertiary butyl hydroperoxide, diisopropylbenzene dihydroperoxide, methyl ethyl ketone peroxide, benzoyl peroxide, tertiary butyl peroxide and the like. .. One or more of these can be used. Of these, cumene hydroperoxide is preferable in terms of reactivity.

The amount of the (2) polymerization initiator used is preferably 0.5 to 10 parts by mass, more preferably 1 to 7 parts by mass with respect to 100 parts by mass of the (1) polymerizable vinyl monomer. If it is 0.5 parts by mass or more, the curing rate becomes high, and if it is 10 parts by mass or less, the storage stability is improved.

The (3) reducing agent used in the present embodiment can be any known reducing agent that reacts with the polymerization initiator to generate radicals. Typical reducing agents include, for example, tertiary amines, thiourea derivatives, transition metal salts and the like.

Examples of the tertiary amine include aromatic amines such as N, N-dimethylaniline and N, N-dimethylparatoluidine, triethylamine, tripropylamine and tributylamine. Examples of the thiourea derivative include 2-mercaptobenzimidazole, methylthiourea, dibutylthiourea, tetramethylthiourea, ethylenethiourea and the like. Examples of the transition metal salt include cobalt naphthenate, copper naphthenate, vanadyl acetylacetonate and the like. Among these, in terms of reactivity, a tertiary amine and / or a transition metal salt is preferable, and it is more preferable to contain a tertiary amine and a transition metal salt.
When a tertiary amine and a transition metal salt are contained, the content ratio of the tertiary amine and the transition metal salt is a mass ratio of the total of 100 parts by mass of the tertiary amine and the transition metal salt, and the tertiary amine: Transition metal salts = 1-99: 1-99 are preferred, 10-50: 50-90 are more preferred, and 20-40: 60-80 are most preferred.
Among the tertiary amines, aromatic amines are preferred. Among the aromatic amines, N, N-dimethylaniline is preferable. Among the transition metal salts, vanadyl acetylacetonate is preferable.

(3) The amount of the reducing agent used is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 1 part by mass with respect to 100 parts by mass of the (1) polymerizable vinyl monomer. If it is 0.01 part by mass or more, the curing rate becomes fast, and if it is 5 parts by mass or less, the storage stability is improved.

In this embodiment, it is preferable to use (4) an elastomer in order to improve the peel strength and the impact strength.
The elastomer used in the present embodiment refers to a polymer substance having rubber-like elasticity at room temperature, and is preferably one that can be dissolved or dispersed in a polymerizable vinyl monomer.
As the elastomer, elastomers other than (1) are preferable.

Examples of such elastomers include (meth) acrylonitrile-butadiene- (meth) acrylic acid copolymer, (meth) acrylonitrile-butadiene-methyl (meth) acrylate copolymer, and methyl (meth) acrylate-butadiene-styrene copolymer. Combined (MBS) and (meth) acrylonitrile-butadiene rubber (NBR, sometimes referred to as (meth) acrylonitrile-butadiene rubber copolymer), linear polyurethane, various synthetic rubbers such as styrene-butadiene, natural rubber, various Examples thereof include thermoplastic elastomers. One or more of these elastomers may be used as long as there is no problem in compatibility.

Among these, an elastomer having no polymerizable unsaturated double bond at the terminal is preferable in terms of good solubility and adhesiveness to the polymerizable vinyl monomer. Examples of the elastomer having no polymerizable unsaturated double bond at the terminal include (meth) acrylonitrile-butadiene- (meth) acrylic acid copolymer, (meth) acrylonitrile-butadiene-methyl (meth) acrylate copolymer, and (meth). ) Diene-based copolymers such as acrylonitrile-butadiene copolymers and styrene-butadiene copolymers, styrene-based thermoplastic elastomers such as chlorosulfonated polyethylene and styrene-polybutadiene-styrene synthetic rubber, urethane-based elastomers and the like can be mentioned. As the elastomer having no polymerizable unsaturated double bond at the terminal, (1) an elastomer soluble in a polymerizable vinyl monomer is preferable.

Among these, a diene-based copolymer is preferable in terms of solubility and adhesiveness. Among the diene-based copolymers, (meth) acrylonitrile-butadiene- (meth) acrylic acid copolymer and / or (meth) acrylonitrile-butadiene copolymer is preferable, and (meth) acrylonitrile-butadiene copolymer is more preferable. preferable.

Elastomers that do not have a polymerizable unsaturated double bond at the end preferably have a (meth) acrylonitrile structure. When having a (meth) acrylonitrile structure, the (meth) acrylonitrile content is preferably 10 to 50 mol%, more preferably 13 to 25 mol%, in that it has excellent peel strength at low temperatures and can withstand a strong impact. Most preferably 15 to 20 mol%. When the (meth) acrylonitrile content is 10 mol% or more, the effect of the present embodiment is likely to be obtained, and when it is 50 mol% or less, corrosion is unlikely to occur even when a metal such as copper is the object to be adhered.

The amount of the elastomer 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 with respect to 100 parts by mass of (1) the polymerizable vinyl monomer. If it is 5 parts by mass or more, the adhesiveness is improved, and if it is 35 parts by mass or less, the adhesiveness and workability are improved.

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

The amount of paraffin used is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of (1) the polymerizable vinyl monomer. If it is 0.1 part by mass or more, the curing of the portion in contact with air is improved, and if it is 5 parts by mass or less, the adhesive strength does not decrease.

Further, various antioxidants and the like containing a polymerization inhibitor can be used for the purpose of improving storage stability.
Antioxidants include hydroquinone, hydroquinone monomethyl ether, 2,6-ditershally butyl-p-cresol, 2,2'-methylenebis (4-methyl-6-tershally butylphenol), triphenylphosphite, phenothiazine and N. -Isopropyl-N'-phenyl-p-phenylenediamine and the like can be mentioned.

The amount of the antioxidant used is preferably 0.001 to 3 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of (1) the polymerizable vinyl monomer. If it is 0.001 part by mass or more, the effect is obtained, and if it is 3 parts by mass or less, the adhesiveness is improved.

Further, in the present embodiment, it is preferable to use (5) phosphate in order to improve the adhesiveness and increase the curing rate.

Among the phosphates, the acidic phosphoric acid compound of the general formula (E) is preferable in terms of adhesiveness and curing rate.

Integers are preferable for m and n.

Examples of the acidic phosphoric acid compound of the general formula (E) include acid phosphooxyethyl (meth) acrylate, acid phosphooxypropyl (meth) acrylate and bis (2- (meth) acryloyloxyethyl) phosphate. Among these, acid phosphooxyethyl (meth) acrylate is preferable in terms of adhesiveness and curing rate.

The amount of (5) phosphate used is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 7 parts by mass, based on 100 parts by mass of (1) the polymerizable vinyl monomer. If it is 0.05 parts by mass or more, the curing rate becomes high, and in particular, the adhesiveness to aluminum is improved, and if it is 10 parts by mass or less, the adhesiveness is improved.

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

Although the components used in the present embodiment have been described above, the composition of the present embodiment has odors other than the above (1-1), (1-2), (1-3) and (1-4). Compounds with less amount may be used.

In this embodiment, it is preferable to use it as a curable resin composition.
In this embodiment, it is preferable to use it as an adhesive composition. In this case, for example, it may be used as a two-agent type adhesive composition. For the two-part type, all the essential components of the adhesive composition of the present embodiment are not mixed during storage, the adhesive composition is divided into a first agent and a second agent, and at least (2) polymerization is carried out on the first agent. The initiator is stored separately, with the second agent containing at least (3) reducing agent and optionally (5) phosphate. In this case, both agents can be applied simultaneously or separately, contacted and cured to be used as a two-part adhesive composition.

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

Among these embodiments, it is preferable to use it as a two-part adhesive composition in terms of excellent storage stability.

In the present embodiment, the adherend is joined with the cured product of the curable resin composition to prepare a bonded body. There are no restrictions on various materials of the adherend such as paper, wood, ceramic, glass, ceramics, rubber, plastic, mortar, concrete and metal, but it is better when the adherend is metal, especially iron and stainless steel. Shows adhesiveness.

(Experimental example)
The present embodiment will be described in more detail below with reference to experimental examples. An adhesive composition having the composition shown in Table 1 was prepared, and various physical properties were measured. The results are shown in Table 1.
Various physical properties were measured as follows.
The unit of the amount of each substance used is indicated by the mass part.

(Material used)
As 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, those having q = 5 and q'= 5 were used.
Paraffin was used as the paraffin.
Hydroquinone monomethyl ether was used as the antioxidant.
The following abbreviations were used for each substance listed in the table.
NBR: Acrylonitrile-butadiene rubber, elastomer without polymerizable unsaturated double bond at the end (commercially available) (AN amount 19.5 mol%)
AN content: Acrylonitrile content (mol%) contained in the acrylonitrile-butadiene copolymer

[Tensile shear strength]
A 100 × 25 × 1.6 mm SPCC-D sandblasted steel sheet was used as a test piece. In an environment of a temperature of 23 ° C. and a humidity of 50%, the first agent was applied to one side of one test piece and the second agent was applied to the other test piece according to JISK-6850. Immediately after that, the coated surfaces were overlapped and bonded together. After that, it was cured at room temperature for 24 hours, and this was used as a sample for measuring tensile shear strength. The tensile shear strength (unit: MPa) of the sample was measured at a tensile speed of 10 mm / min in an environment of a temperature of 23 ° C. and a humidity of 50%.

[Peeling strength]
As a test piece, a 100 × 25 × 0.3 mm SPCC-D sandblasted steel sheet or a 100 × 25 × 0.5 mm aluminum A-5052 sandblasted steel sheet was used. In an environment of a temperature of 23 ° C. and a humidity of 50%, the first agent was applied to one side of one test piece and the second agent was applied to the other test piece according to JISK-6854. Immediately after that, the coated surfaces were overlapped and bonded together. After that, it was cured at room temperature for 24 hours, and this was used as a sample for measuring peel strength. In order to make the thickness of the curable resin composition layer uniform, a small amount of glass beads having a particle size of 100 μm was added to the SPCC-D sandblasted steel sheet, and a small amount of 100 μm glass beads were added to the aluminum A-5052 sandblasted steel sheet. bottom. The peel strength (unit: kN / m) of the sample is such that the sandblasted steel sheet of SPCC-D has a tensile speed of 50 mm / min and the sandblasted steel sheet of aluminum A-5052 is tensioned under an environment of a temperature of 23 ° C. and a humidity of 50%. The T peel strength was measured at a speed of 100 mm / min.

[Moisture resistance tensile shear strength retention rate]
Moisture resistance tensile shear strength retention rate was measured as an evaluation item of adhesive durability. A 100 × 25 × 2.0 mm aluminum A-5052 sandblasted steel sheet was used as a test piece. A sample for measuring the tensile shear strength of aluminum was left in an environment of a temperature of 50 ° C. and a humidity of 98% for one week, and then taken out and measured in a tensile speed of 10 mm / min in an environment of a temperature of 23 ° C. and a humidity of 50%. bottom. Moisture-resistant tensile shear strength retention rate (unit:%) is the ratio of the tensile shear strength exposed to an environment of temperature 50 ° C. and humidity of 98% to the tensile shear strength exposed to an environment of temperature 23 ° C. and humidity 50%. ).

[Fixing time]
According to JISK-6856, one of the test pieces (100 mm × 25 mm × 1.6 mm, sandblasting of SPCC-D) was coated with an equal amount of the first agent and the second agent, and then the other test was performed immediately. The sample was obtained by stacking the pieces and pasting them together. The fixing time (unit: minutes) of the sample is 0.1 MPa or more immediately after the sample is pulled by a push-pull gauge (ModelS, manufactured by Komura) in an environment of temperature 23 ° C. and humidity 50%. The time until measurement was measured.

[Odor]
The strength of the odor of each curable resin composition was as follows.
A cured product having a diameter of 10 mm and a thickness of 1 mm was prepared using the resin composition, the cured product was placed in a glass bottle, sealed, left for 1 hour, and then the odor was measured using an odor sensor (manufactured by Calmore). .. The measured value in the tested room was 360. The larger the value, the stronger the odor. The numerical value of the odor is preferably 1000 or less, more preferably 600 or less.

The following can be seen from the table. In this embodiment, the peel strength and the tensile shear strength are high, and the adhesiveness is high.

The present embodiment provides a curable resin composition or an adhesive composition which has a low odor and is excellent in adhesiveness, storage stability, curability and moisture resistance including peel strength to aluminum and iron.
Further, if water enters the interface between the adherend and the adhesive, the adherend may peel off. However, this embodiment has moisture resistance to the extent that the adhesiveness does not decrease even under moisture conditions such as high humidity.
The composition of the present embodiment provides a two-part (meth) acrylic adhesive composition having low odor and high peel strength at low temperature. Therefore, it is possible to work even in a place where ventilation is insufficient, and an adhesive having a wide range of adaptation environments can be obtained in which the cured product of the adhesive does not peel off even in a cold region. Furthermore, since it is possible to provide a two-part (meth) acrylic adhesive that can withstand a strong impact, it can be applied not only to the improvement of the working environment but also to various industrial fields, which is beneficial.

Claims (12)

A composition containing the following (1) to (4).
(1) A compound of the polymerizable vinyl monomer (1-1) general formula (A) containing (1-1) to (1-4).

(1-2) The compound of the general formula (B) (B) Z- O- (R 2 O) p-H
[In the general formula, Z represents a (meth) acryloyl group. R ² represents an alkylene group. p represents a number from 1 to 10. ]
(1-3) Compound of general formula (C)

(1-4) Compound of general formula (D) General formula (D) ZOR ⁵
[In the formula, Z is shown a (meth) acryloyl group, R ⁵ represents an alkyl group. ]
(2) Polymerization initiator (3) Reducing agent
(4) Elastomer (4) the elastomer (meth) composition of claim 1 wherein the acrylonitrile content is 50 mol%. (1) Of 100 parts by mass of the polymerizable vinyl monomer, (1-1) 10 to 60 parts by mass, (1-2) 10 to 70 parts by mass, (1-3) 1 to 30 parts by mass, (1-4). The composition according to claim 1 or 2, which contains 5 to 40 parts by mass. Furthermore, (5) 1 wherein composition according to one of claims 1 to 3, which contains a phosphate. Furthermore, first term composition according to one of claims 1-4 containing paraffins. Furthermore, first term composition according to one of claims 1 to 5 which contains an antioxidant. (3) reducing agent, first term composition according to one of claims 1 to 6 containing a tertiary amine and a transition metal salt. 1 Section curable resin composition containing a composition according to one of claims 1 to 7. The adhesive composition containing the composition according one of claims 1-7. The composition according to claim 1 of claims 1 to 7 is divided into a first agent and a second agent, the first agent containing at least (2) a polymerization initiator, and the second agent at least (3) a reducing agent. A two-part composition containing. A bonded body for joining an adherend using the composition according to claim 1 of claims 1 to 7. Method for producing a joined body of bonding adherends using a composition according one of claims 1-7.