JP7132316B2 - Two-component curable composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a two-part curable composition used for adhesives, sealants, coating materials, and the like.

Acrylic or epoxy two-part curable compositions are used as adhesives, sealants, or coating materials in various fields such as construction, civil engineering, electronic and electrical equipment, vehicles, automobiles, and aircraft. there is In recent years, these two-component curable compositions are not only capable of strong adhesion, but also repeatedly expand and contract between the materials themselves or between materials due to temperature changes over a long period of time. There is a need for improved reliability that allows adhesive performance to be maintained even under strain and stress.

In response to this demand, for example, a two-component curable composition containing a modified silicone polymer and an epoxy resin has been proposed (eg, Patent Document 1). Furthermore, a two-part curable composition containing a modified silicone polymer and an acrylic monomer has also been proposed (for example, Patent Document 2). These two-component curable compositions exhibit rubber-like elasticity in cured products, and are expected to improve reliability.

JP-A-58-47054 JP-A-5-331447

However, although the two-component curable composition containing the modified silicone polymer can be expected to improve reliability, it has the problem that the curing speed is slow, the curing takes a long time, and the workability is poor.

Accordingly, an object of the present invention is to provide a two-component curable composition that is highly reliable and can be cured in a shorter time.

In order to solve the above problems, the two-component curable composition of the present invention is a two-component curable composition comprising an A agent and a B agent, wherein the A agent contains a hydrolyzable silyl group. B The agent comprises 100 parts by weight of a (meth)acrylic monomer containing 0.5 to 30 parts by weight of a carboxyl group-containing (meth)acrylic monomer, 0.01 to 5 parts by weight of a vanadium compound, and 0.1 part by weight of an acidic phosphorus compound. ~10 parts by weight.

According to the present invention, it is possible to provide a two-component curable composition that is highly reliable and can be cured in a shorter time.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail.

The two-component curable composition according to the present embodiment is a two-component curable composition consisting of agent A and agent B, wherein agent A is a polyalkylene oxide-based compound containing a hydrolyzable silyl group. 100 parts by weight of a polymer, 0.1 to 10 parts by weight of an organic peroxide, and 0.01 to 5 parts by weight of α-hydroxyketones and/or α-hydroxyesters, and agent B contains a carboxyl group 100 parts by weight of a (meth)acrylic monomer containing 0.5 to 30 parts by weight of a (meth)acrylic monomer, 0.01 to 5 parts by weight of a vanadium compound, and 0.1 to 10 parts by weight of an acidic phosphorus compound is characterized by including
In the present invention, unless otherwise specified, "(meth)acryl" represents acrylic or methacrylic, and "(meth)acrylate" represents acrylate or methacrylate.

In the present invention, the reliability of the curable composition means not only that the initial adhesive strength is high, but also the durability that the adhesive strength is not easily reduced even by changes in the surrounding environment over a long period of time, specifically temperature changes and humidity changes. It means having sex.

(Polyalkylene oxide polymer containing hydrolyzable silyl group)
Polyalkylene oxide-based polymer containing a hydrolyzable silyl group contained in agent A is a polyalkylene oxide as a main chain, and two or more hydrolyzable hydrolyzable It is a polymer having a silyl group (hereinafter also referred to as a modified silicone polymer). Examples of the alkylene group of the polyalkylene oxide include ethylene group, propylene group, isobutylene group, tetramethylene group and the like, and two or more different alkylene groups may be present in the molecule. The molecular weight of the polyalkylene oxide is not particularly limited, but the number average molecular weight is several hundreds to several tens of thousands, preferably several thousand to several tens of thousands.

The hydrolyzable silyl groups can include one or more of dialkylmonoalkoxysilyl groups, monoalkyldialkoxysilyl groups, and trialkoxysilyl groups. Examples of the alkyl group include methyl group, ethyl group, n-propyl group and the like. Examples of alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, and isobutoxy groups.

The modified silicone polymer is not particularly limited, but among organic polymers, it has low viscosity, excellent flexibility even at low temperatures, and good curability and adhesiveness. Polypropylene oxide-based liquid polymers containing methoxysilyl groups at their terminals are preferred. Examples of these commercially available products include Exester series from AGC, Cyryl series from Kaneka, and the like. These modified silicone polymers may be used alone or in combination of two or more.

((meth)acrylic monomer)
As the (meth)acrylic monomer contained in the B agent,
(Meth) acrylic acid, carboxyethyl (meth) acrylate, (meth) acrylic acid ω-carboxy-polycaprolactone, (meth) acryloyloxyethyl phthalate, (meth) acryloyloxyethyl succinate, (meth) acryloyloxyethyl malein Acids, carboxyl group-containing (meth)acrylates such as (meth)acryloyloxyethylhexahydrophthalic acid;
Alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, and lauryl (meth)acrylate;
2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxyisobutyl (meth)acrylate, hydroxyhexyl (meth)acrylate, hydroxyoctyl (meth)acrylate, Hydroxyalkyl (meth)acrylates such as hydroxydecyl (meth)acrylate and hydroxyllauryl (meth)acrylate;
Alicyclic (meth)acrylates such as isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate;
aromatic ring-containing (meth)acrylates such as benzyl (meth)acrylate and phenoxyethyl (meth)acrylate;
Heterocycle-containing (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate and glycidyl (meth)acrylate;
Vinyl group-containing (meth)acrylates such as allyl (meth)acrylate;
Alkoxy (meth) acrylates such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate;
Ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,3-butyglycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, etc. Alkylene oxide-modified di- and tri(meth)acrylates of
alkylene oxide-modified bisphenol A di(meth)acrylate such as ethylene oxide-modified bisphenol A di(meth)acrylate; and alkylene oxide-modified hydrogenated bisphenol A di(meth)acrylate such as ethylene oxide-modified hydrogenated bisphenol A di(meth)acrylate, etc. can be mentioned.

The (meth)acrylic monomer contains 0.5 to 30 parts by weight, more preferably 1 to 25 parts by weight of a carboxyl group-containing (meth)acrylic monomer in 100 parts by weight thereof. If the content of the carboxyl group-containing (meth)acrylic monomer is less than 0.5 parts by weight, the curing speed will be slow and the adhesive strength will be low. However, the adhesion strength is not so improved. In addition, the (meth)acrylic monomer includes, as the balance, monomers other than the carboxyl group-containing (meth)acrylic monomer, such as the above alkyl (meth)acrylates, hydroxyalkyl (meth)acrylates, alicyclic (meth)acrylates, Aromatic ring-containing (meth)acrylates, heterocyclic ring-containing (meth)acrylates, vinyl group-containing (meth)acrylates, alkoxy (meth)acrylates, alkylene oxide-modified di- and tri-(meth)acrylates, alkylene oxide-modified bisphenol A di(meth) One or more monomers selected from the group consisting of acrylates and alkylene oxide-modified hydrogenated bisphenol A di(meth)acrylates may be included. Monomers other than carboxyl group-containing (meth)acrylic monomers are preferably hydroxyalkyl (meth)acrylates, alicyclic (meth)acrylates, aromatic ring-containing (meth)acrylates, and alkylene oxide-modified bisphenol A di(meth)acrylates. is.

In addition, A agent may also contain a (meth)acrylic-type monomer as needed. For example, if the viscosities of agent A and agent B are significantly different and it is difficult to mix them, from the viewpoint of facilitating mixing and improving workability, by adding a (meth)acrylic monomer to agent A, A The viscosity of the agent can be adjusted to the same extent as the viscosity of the B agent. At that time, the type and amount of the (meth)acrylic monomer added to the A agent can be appropriately set according to the viscosity of the B agent to be matched.

(organic peroxide)
Examples of organic peroxides contained in Agent A include hydroperoxides such as t-butyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide, and diisopropylbenzene hydroperoxide, t-butyl peroxybenzoate, Alkyl peroxyesters such as t-butyl peroxydecanoate can be mentioned. Among these, hydroperoxides are preferred from the viewpoint of reactivity. These organic peroxides may be used alone or in combination.

The content of the organic peroxide is 1-10 parts by weight, preferably 2-7 parts by weight, per 100 parts by weight of the modified silicone polymer. This is because if the amount is less than 1 part by weight, the curing rate is slow and the adhesive strength is lowered, and if the amount exceeds 10 parts by weight, the curing rate is not improved.

(α-hydroxyketones and/or α-hydroxyesters)
The α-hydroxyketones and α-hydroxyesters contained in Agent A act on the redox catalyst system between the vanadium compound and the organic peroxide together with the acidic phosphorus compound described below to accelerate the curing of the (meth)acrylic monomer. It is a compound that Examples of α-hydroxyketones include hydroxyacetone, dihydroxyacetone, acetoin, benzoin, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropanone, 1-[4-(2 -hydroxyethoxy)phenyl]-2-hydroxymethylpropanone and the like. Preferred α-hydroxyketones are hydroxyacetone and benzoin.

Examples of α-hydroxy esters include methyl lactate, ethyl lactate, propyl lactate, methyl glycolate, and ethyl tartrate. Preferred α-hydroxy esters are ethyl lactate and methyl glycolate.

The blending amount of α-hydroxyketones and/or α-hydroxyesters is 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight, per 100 parts by weight of the modified silicone polymer. This is because if the amount is less than 0.1 part by weight, the curing rate is slow, and if the amount exceeds 5 parts by weight, no improvement in the curing rate is observed. In addition, it is also possible to use a plurality of α-hydroxyketones and α-hydroxyesters instead of just one.

Incidentally, α-hydroxyketones and α-hydroxyesters are included in broadly defined α-hydroxycarbonyl compounds, and α-hydroxycarboxylic acids such as lactic acid and glycolic acid are also included in the α-hydroxycarbonyl compounds. α-Hydroxycarboxylic acid, like α-hydroxyketones and α-hydroxyesters, acts on the redox catalyst system of the vanadium compound and the organic peroxide together with the acidic phosphorus compound described below to cure the (meth)acrylic monomer. However, according to the findings of the present inventors, when used in agent A, it causes gelation during storage, so it cannot be used. Moreover, even if it is used for the B agent, it cannot be used for the B agent because it reacts with the vanadium compound described later and causes gelation.

(vanadium compound)
The vanadium compound contained in the B agent forms a redox catalyst system with the organic peroxide used in the A agent, promoting radical generation of the organic peroxide. Vanadium compounds include, but are not limited to, oxides such as vanadium pentoxide, metal soaps such as vanadyl octenoate, vanadyl naphthenate, and vanadyl stearate, and metal chelates such as vanadyl acetylacetonate and vanadium acetylacetonate. etc. can be mentioned. The vanadium compound is preferably vanadyl acetylacetonate.

The content of the vanadium compound is 0.1 to 5 parts by weight, preferably 0.2 to 2 parts by weight, per 100 parts by weight of the (meth)acrylic monomer. This is because if the amount is less than 0.1 part by weight, the curing speed is slow and the adhesive strength is lowered, and if the amount exceeds 5 parts by weight, the storage stability is lowered.

(acidic phosphorus compound)
Examples of acidic phosphorus compounds contained in agent B include phosphoric acid, pyrophosphoric acid, polyphosphoric acid, acidic phosphoric acid esters, and phosphoric acid group-containing (meth)acrylates. Acidic phosphates include monomethyl phosphate, dimethyl phosphate, monoethyl phosphate, diethyl phosphate, monoisopropyl phosphate, diisopropyl phosphate, monobutyl phosphate, dibutyl phosphate, monoethoxyethyl phosphate, diethoxyethyl phosphate, monobutoxyethyl phosphate, di Butoxyethyl phosphate, phenyl phosphate, diphenyl phosphate and the like can be mentioned. Examples of phosphoric acid group-containing (meth)acrylates include acid phosphooxyethyl (meth)acrylate, acid phosphooxypropyl (meth)acrylate, acid phosphooxybutyl (meth)acrylate and the like. The acidic phosphorus compound is preferably an acidic phosphoric acid ester or a phosphoric acid group-containing (meth)acrylate, more preferably a phosphoric acid group-containing (meth)acrylate. The phosphoric acid group-containing (meth)acrylate is preferably acid phosphooxyethyl methacrylate (also referred to as 2-hydroxyethyl methacrylate acid phosphate). Acid phosphooxyethyl methacrylate is available, for example, from Johoku Kagaku Co., Ltd. under the trade name JPA-514.

Acidic phosphorus compounds have the effect of accelerating the curing of the modified silicone polymer. In addition, the acidic phosphorus compound acts on the redox catalyst system between the vanadium compound and the organic peroxide together with the α-hydroxyketones and/or α-hydroxyesters described above to accelerate the curing of the (meth)acrylic monomer. It also has the effect of

The content of the acidic phosphorus compound is 0.1 to 10 parts by weight, preferably 0.5 to 8 parts by weight, more preferably 1 to 7 parts by weight, per 100 parts by weight of the acrylic monomer of the B agent. This is because if the amount is less than 0.1 part by weight, the curing reaction does not proceed sufficiently, and if the amount exceeds 10 parts by weight, no improvement in curing speed is observed.

(elastomer)
The B agent may further contain an elastomer. Elastomers are polymeric substances that exhibit rubber elasticity near room temperature. By containing an elastomer, flexibility, impact strength, and peel strength can be further improved. Specific examples of elastomers include methyl methacrylate-butadiene-styrene copolymer (MBS resin), methyl methacrylate-butadiene-acrylonitrile-styrene copolymer (MBAS resin), styrene-butadiene copolymer (SBS resin), acrylonitrile- Thermoplastic elastomers such as butadiene-styrene copolymer (ABS resin), styrene-butadiene rubber (SBR), polybutadiene rubber (BR), polyisoprene rubber (IR), chloroprene rubber (CR), acrylonitrile-butadiene rubber (NBR) , ethylene-acrylic rubber, epichlorohydrin rubber, and other synthetic rubbers. Thermoplastic elastomers are preferred. Among thermoplastic elastomers, MBS resins are preferred. For example, MBS resin (trade name: Paraloid BTA-751) manufactured by Dow Chemical Japan Co., Ltd., MBS resin (trade name: Kaneace B-56) manufactured by Kaneka Corporation, etc. are commercially available. As synthetic rubbers, ethylene-acrylic rubber (trade name Baymac G) manufactured by DuPont, carboxyl group-containing acrylonitrile-butadiene rubber (trade name Nipol 1072) manufactured by Nippon Zeon Co., Ltd., and the like are commercially available.

The content of the elastomer is 10 to 60 parts by weight, preferably 30 to 50 parts by weight, more preferably 30 to 40 parts by weight, per 100 parts by weight of the (meth)acrylic monomer of the B component. This is because if the amount is less than 10 parts by weight, the effect of improving the adhesive strength is not sufficient, and if the amount exceeds 60 parts by weight, the viscosity increases and the workability decreases.

(Polymerization inhibitor)
The B agent may further contain a polymerization inhibitor. Storage stability can be further improved. Specific examples of polymerization inhibitors include hydroquinone, methylhydroquinone, t-butylhydroquinone, hydroquinone monomethyl ether, quinhydrone, p-benzoquinone, toluquinone, 6-t-butyl-2,4-xylenol, 2,6-di-t -Butyl-4-methylphenol, 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis[6-(1-methylcyclohexyl-p-cresol)], etc. can be done.

The content of the polymerization inhibitor is 0.01 to 2 parts by weight, preferably 0.02 to 1 part by weight, more preferably 0.05 to 1 part by weight with respect to the total 100 parts by weight of the (meth)acrylic monomer. Department.

Furthermore, agent A and agent B can also contain the following known compounds according to the purpose within a range that does not impair the effects of the composition of the present invention.

(Silane coupling agent)
The silane coupling agent can further improve adhesion to the adherend. Although the silane coupling agent is not particularly limited, examples thereof include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane and the like. The content of the silane coupling agent is 0.01 to 2 parts by weight, preferably 0.05 to 1 part by weight, per 100 parts by weight of the total (meth)acrylic monomer.

(thixotropic agent)
A thixotropic agent such as fumed silica, bentonite, sepiolite and polyethylene oxide may be added to the composition of the present invention to impart thixotropy.

In addition, paraffins, waxes, pigments, colorants, etc. may be added in order to accelerate the curing of the air contact portion.

EXAMPLES The present invention will be described in more detail below using examples and comparative examples, but the present invention is not limited to the following examples. All "parts" indicating the amount of each component used are "parts by weight".

<Preparation of curable composition>
Table 1 shows the component names used in the A agent and the B agent. The compositions of the prepared agents A and B are shown in Tables 2 and 3, respectively. In Tables 1 to 3, components 1, 2, 3, 4, 5 and 6 are modified silicone polymers, organic peroxides, α-hydroxycarbonyl compounds, and (meth)acrylic Monomers, vanadium compounds and acidic phosphorus compounds are meant.

<Storage stability test of agent A>
A 100 ml container made of polyethylene was filled with agent A and allowed to stand at 40° C. to examine whether gelation had occurred. In addition, all B agents were stable at 40° C. for 30 days or more.
The storage stability of agent A was determined according to the following criteria.
◯: No increase in viscosity or gelation occurred for 30 days or longer.
x: Gelation occurred within 10 days.

<Measurement of pot life>
0.5 g of each of A and B were weighed and mixed in a polyethylene container with a capacity of 2 ml at 23° C. When the reaction started, the viscosity started to rise and the time during which adhesion was possible was measured to determine the pot life. .

<Measurement of set time>
An SPCC-SD sandblasted steel plate with dimensions of 100×25×1.6 mm was used as an adherend. Adhesive is applied to one test piece at 23°C with a lap length of 12.5 mm, A and B are adhered at a weight ratio of 1:1, and a load of 3 kg is applied. Measured and set time

<Measurement of Shore hardness A of cured product>
2.5 g each of A and B were weighed and mixed in a polyethylene container having an inner diameter of 30 mm and a depth of 7 mm, and after 24 hours at 23° C., the Shore hardness A of the cured product was measured. A hardness tester GS-610 manufactured by Teclock was used for the measurement.

<Measurement of tensile shear strength>
An SPHC sandblasted steel plate with dimensions of 100×20×2.3 mm was used as the metal plate, and an acrylic plate and an ABS resin plate with dimensions of 100×25×3.0 mm were used as the hard plastic plate. Further, a calcium silicate board (abbreviated as a silica board) with dimensions of 100×25×3 mm was used as the inorganic board, a slate board and a lauan plywood with dimensions of 100×25×3 mm were used as the wooden board. Plates of the same type were adhered to each other at 23° C. with A and B in a ratio of 1:1, and the tensile shear strength (N/mm ² ) was measured after 24 hours at a test speed of 25 mm/min. Autograph AG-X50KNX manufactured by Shimadzu Corporation was used for the measurement. The measurement temperature is 23°C. The length of the wrap was 10 mm for the steel plate, and 12.5 mm for the hard plastic plate, inorganic plate and lauan plywood.

<Measurement of T-type peel strength>
As the metal plate, an SPHC sandblasted steel plate of 150×25×0.3 mm was used. Agents A and B were adhered at a weight ratio of 1:1, and the T-peel strength was measured after 24 hours at a tensile speed of 250 mm/min. The measurement temperature is 23°C.

<Water resistance test>
A sandblasted steel plate of SPHC having dimensions of 100×20×2.3 mm was used as an adherend. At 23°C, A and B were bonded at a weight ratio of 1:1 with a lap length of 10 mm, cured at 23°C for 24 hours, and immersed in hot water at 60°C for 250 hours, then cured at 23°C for 24 hours. and the tensile shear strength (N/mm ² ) was measured at a test speed of 25 mm/min.

Here, the strength retention rate was calculated by the following formula.
[(Tensile shear strength after water resistance test) / (Initial tensile shear strength)] × 100 (%)

<Thermal aging test>
A sandblasted steel plate of SPHC having dimensions of 100×20×2.3 mm was used as an adherend. At 23°C, A and B were bonded at a weight ratio of 1:1 with a wrap length of 10 mm, cured at 23°C for 24 hours, and exposed to a dryer at 100°C for 250 hours. After curing, the tensile shear strength (N/mm ² ) was measured at a test speed of 25 mm/min.

Here, the strength retention rate was calculated by the following formula.
[(Tensile shear strength after heat aging test) / (Initial tensile shear strength)] × 100 (%)

<Hot T-type peel strength>
As the metal plate, an SPHC sandblasted steel plate of 150×25×0.3 mm was used. A and B were mixed and bonded at a weight ratio of 1:1, and after 24 hours, the T-peel strength was measured at temperatures of -30°C, 0°C, 23°C, and 100°C at a tensile speed of 250 mm/min. It was measured.

(result)
Test results are shown in Tables 4-8.

As shown in Table 2, in the storage stability test of agent A, A-5 and A-6 using lactic acid or glycolic acid, which are α-hydroxycarboxylic acids, caused gelation within 10 days. Other A-1 to A-4 and A-7 to A-11 were stable for 30 days or longer. From this, it was confirmed that agent A containing α-hydroxyketones or α-hydroxyesters as component 3 has excellent storage stability. In addition, all agents B were stable at 40° C. for 30 days or longer, showing excellent storage stability.

Table 4 shows the results of Examples 1-5 and Comparative Examples 1-4. Examples 1 to 4 differ in the type of component 3 of agent A. In Examples 1 to 4, it was confirmed that the set time was shortened and the curing speed was improved as compared with Comparative Example 3, which does not contain Component 3. Moreover, in Examples 1 to 4, good properties were obtained in pot life, Shore hardness of the cured product, tensile shear strength and T-peel strength. In particular, in Example 1 using hydroxyacetone and Example 2 using benzoin, the set time could be greatly shortened. Although the set times of Comparative Examples 1 and 2 are shorter than that of Comparative Example 3, the storage stability is poor as described above, and it is difficult to put them to practical use. In addition, Example 5 is an example in which 5 parts by weight of hydroxyacetone was used as component 3 of agent A, and compared to Example 1 in which 1 part by weight was used, the pot life and set time were shortened, and the shore of the cured product was reduced. Similar properties were obtained for hardness, tensile shear strength and T-peel strength. On the other hand, Comparative Example 4 is an example in which 7 parts by weight of hydroxyacetone was used as Component 3 of Agent A, and the set time was slower than in Examples 1 and 5, and the Shore hardness, tensile shear strength, and T-type of the cured product were reduced. The peel strength was also low.

Table 5 shows the results of Examples 6-11 and Comparative Examples 5-7. Examples 6 to 11 differ in the type of component 4 of agent B. In Examples 6-11, it was confirmed that the set time was shortened and the curing speed was improved as compared with Comparative Examples 5-7. Comparative Example 5 is an example in which the carboxyl group-containing (meth)acrylic monomer is not included as Component 4 of the B agent, and the tensile shear strength and T-peel strength are greatly reduced. Comparative Examples 6 and 7 are examples in which a carboxyl group-containing (meth)acrylic monomer is included as component 4 of agent B, but component 3 of agent A is not included. From this, by containing a carboxyl group-containing (meth)acrylic monomer as component 4 of agent B and containing component 3 in agent A, the cured product has good properties in terms of Shore hardness, tensile shear strength and T-peel strength. It was confirmed that the curing speed can be improved while maintaining the

Table 6 shows the results of the water resistance test and heat aging test for Examples 1, 6, 10 and 11. In these examples, the strength retention rate of tensile shear strength was 90% or more even in the water resistance test and heat aging test, and they had excellent durability.

Table 7 shows the measurement results of tensile shear strength for various adherends for Examples 1, 6, 10 and 11. In any of the examples, no curing failure occurred, cohesive failure was exhibited, and excellent adhesive strength to various adherends was exhibited.

Table 8 shows the measurement results of the T-peel strength of Examples 1, 6, 10 and 11 at temperatures of -30°C, 0°C, 23°C and 100°C. In any of the examples, excellent adhesive strength was exhibited without peeling at a wide temperature range of -30°C to 100°C.

As described above, according to the two-part curable composition of the present invention, the curing speed can be increased, so that the composition can be cured in a shorter time. In addition, the two-component curable composition of the present invention has good storage stability, the cured product has rubber-like elasticity, the adhesiveness to each adherend is stable, and the water resistance and heat aging are excellent. It has also been confirmed that the material is excellent in durability as well as excellent in durability.

The two-component curable composition of the present invention has excellent reliability and can improve the curing speed. Therefore, it can be applied to various adherends such as metals, hard plastics, wood, ceramics, etc., where two-component acrylic adhesives are conventionally used, which are characterized by fast curing, and adhesion with excellent workability. It can provide agents, sealants, and coating materials.

Claims (7)

A two-component curable composition comprising an A agent and a B agent,
Agent A comprises 100 parts by weight of a polyalkylene oxide polymer containing a hydrolyzable silyl group, 0.1 to 10 parts by weight of an organic peroxide, and 0.1 parts by weight of α-hydroxyketones and/or α-hydroxyesters. 01 to 5 parts by weight,
Agent B comprises 100 parts by weight of a (meth)acrylic monomer containing 0.5 to 30 parts by weight of a carboxyl group-containing (meth)acrylic monomer, 0.01 to 5 parts by weight of a vanadium compound,
and 0.1 to 10 parts by weight of an acidic phosphorus compound. The α-hydroxyketones include hydroxyacetone, dihydroxyacetone, acetoin, benzoin, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropanone, and 1-[4-(2- Hydroxyethoxy)phenyl]-2-hydroxymethylpropanone. 3. The two-component curable composition according to claim 1, wherein the α-hydroxy ester is at least one selected from the group consisting of methyl lactate, ethyl lactate, propyl lactate, methyl glycolate, and ethyl tartrate. Composition. The two-part curable composition according to any one of claims 1 to 3, wherein the carboxyl group-containing (meth)acrylic monomer is (meth)acrylic acid. 5. The two-part curable composition according to any one of claims 1 to 4, wherein the organic peroxide is hydroperoxide. 6. The two-part curable composition according to any one of claims 1 to 5, wherein the acidic phosphorus compound is an acidic phosphoric acid ester or a phosphoric acid group-containing (meth)acrylate. 7. The two-component curable composition according to any one of claims 1 to 6, wherein the B agent contains 20 to 60 parts by weight of an elastomer with respect to 100 parts by weight of the (meth)acrylic monomer.