JP2002308944A - Curable resin composition, adhesive composition and bonding method - Google Patents

Abstract

(57) [Summary] [Problem] It has a low odor, can be applied without stringing from a nozzle of a coating device, can be applied to a vertical surface or an edge surface without dripping, and has an adhesive property. Provide curable resin composition because of its superiority. SOLUTION: The static viscosity at 20 rpm is 110,000 mPa.
A curable resin composition having a thixotropy coefficient of 1.7 or more obtained by dividing a static viscosity at 2 rpm by a static viscosity at 20 rpm, and (1) containing a polymerizable vinyl monomer. Further, (2) an elastomer component, (3)
It may contain a polymerization initiator, (4) a reducing agent, and (5) a filler. The curable resin composition is divided into a first agent and a second agent, and the first agent may contain (3) a polymerization initiator, and the second agent may contain (4) a reducing agent. It may be used for application.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a method for an unskilled worker to easily, in any place, accurately, sufficiently, firmly, and in an excellent working environment apply a bonding surface intended for an adhesive composition. The present invention relates to a curable resin composition that can be applied to a curable resin composition.
That is, when applied by a simple and portable hand-operated coating device such as a syringe or the like, the coating can be performed well without dripping from the nozzle of the coating device and without dripping even when applied on a vertical surface or an edge surface. The present invention also relates to a low-odor curable resin composition having excellent adhesive properties such as shear adhesive strength, peel adhesive strength and impact adhesive strength.

[0002]

2. Description of the Related Art The demand for a room-temperature fast-curing adhesive which cures in a short time at room temperature tends to increase year by year in order to save labor, resources and energy. Conventionally, as a room-temperature fast-curing adhesive, for example, a second-generation acrylic adhesive (SG
A) is known.

Although SGA is a two-part type, it does not require accurate metering of two parts, and can be cured in a few minutes or tens of minutes at room temperature by incomplete weighing or mixing, and sometimes even contact of two parts. Excellent workability. In addition, SGA is widely used because it has high peel adhesive strength and high impact adhesive strength, and has good curing of the exposed portion. Recently, SGAs with low odor, low volatility and low flammability have been demanded in terms of work environment.

[0004] Such an SGA is disclosed in Japanese Unexamined Patent Publication No. 55-7 / 55.
1770, JP-A-57-87484, JP-A-57-90073, JP-A-57-100168
JP-A-58-152076 and JP-A-58-152076
JP-A 1-34082 discloses an adhesive composition containing a high boiling polymerizable vinyl monomer.

[0005]

However, although these adhesive compositions have a low odor, they have the following problems. That is, although the low-odor adhesive composition has a large shear adhesive strength, there is a problem that the peel adhesive strength and the impact adhesive strength are small.

[0006] Further, as a device for applying the two-component adhesive composition, a device for automatically mixing and applying the two components by operating an actuator using a power source such as electricity, hydraulic pressure, or compressed air; An example is a manual device in which an operator manually performs mixing and coating. 2. Description of the Related Art As a manual device, a device for pressurizing two agents manually is known, for example, a manual discharge gun. The manual type device has an advantage that a complicated and difficult-to-manage device such as an actuator is not required, and since the device is small, it can be carried and used anywhere.

Further, when the conventional adhesive composition is used for parts having a vertical surface or an edge surface, dripping occurs after the application of the adhesive composition. However, there was a risk that the design was deteriorated, and that parts at adjacent locations could not be adhered to accurate positions. For this reason, there has been a problem that a worker needs some skill in order to apply the adhesive composition to the vertical surface and the edge surface satisfactorily.

In particular, there has recently been a demand for an adhesive composition which has a low odor, low flammability, can be applied to a vertical surface or an edge surface without dripping with a simple application device such as a syringe, and has an excellent balance of adhesive properties. It has come to be.

The present inventors have conducted intensive studies to solve these problems, and as a result, a specific curable resin composition having a low odor can be easily applied without stringing from a nozzle of a coating apparatus. Furthermore, it can be applied to the vertical surface and edge surface without dripping, and furthermore, it has excellent adhesive properties such as shear adhesive strength, peel adhesive strength and impact adhesive strength,
Even if the operator is unskilled, he obtained the knowledge that it can be accurately, sufficiently, firmly, and easily applied to the target adhesive surface using a manual application device such as a two-cylinder syringe. Thus, the present invention has been completed.

[0010]

That is, the present invention provides a 20r
at 110,000 mPa or less and 2 rpm
The thixotropy coefficient obtained by dividing the static viscosity at 20 rpm by the static viscosity at 20 rpm is 1.7 or more, (1) a curable resin composition containing a polymerizable vinyl monomer, and (2) an elastomer component And (3) the curable resin composition containing a polymerization initiator, and (4) the curable resin composition containing a reducing agent. A resin composition,
(5) The curable resin composition containing a filler, wherein (1) the polymerizable vinyl monomer is (A) a general formula (A)
A polymerizable vinyl monomer having the structure of the general formula (A) Z—O— (R ₂ O) p —R ₁ [wherein Z represents a (meth) acryloyl group, and R ₁ represents a phenyl group or a carbon atom of 1 R ₂ representing a phenyl group having an alkyl group of 3 to 3 is —C ₂ H ₄ —, —C ₃ H ₆ —, —CH ₂ CH (CH ₃ )
-, - C ₄ H ₈ - or -C ₆ H ₁₂ - it indicates, p is an integer of 1 to 10. (B) a polymerizable vinyl monomer having a structure of the general formula (B)

Embedded image And (C) a polymerizable vinyl monomer having a structure represented by the general formula (C): General formula (C) Z—O— (R ₂ O) p —H wherein Z and R ₂ are as described above. Wherein the curable resin composition is divided into a first agent and a second agent, wherein the first agent contains (3) a polymerization initiator, and the second agent Is a two-part curable resin composition containing (4) a reducing agent, and is a curable resin composition for syringe application comprising the curable resin composition. And it is an adhesive composition which consists of this curable resin composition.
Further, there is provided a method for bonding an adherend, characterized by using the curable resin composition.

[0011]

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

The curable resin composition used in the present invention can be applied with a manual discharge gun such as a syringe, and has a speed of 20 rpm.
m, the static viscosity at 25 ° C. is 110,000 mPa or less;
It is preferably 10,000 mPa or less. If it exceeds 110,000 mPa, there is a possibility that the coating cannot be performed with a manual discharge gun such as a syringe.

The lower limit of the static viscosity of the curable resin composition used at 20 rpm at 25 ° C. is 30,000 m.
Pa is preferable, and 50,000 mPa is more preferable. 30,000 mPa
If it is less than the above, the curable resin composition may drips during application to a vertical surface or an edge surface and may not be applied well.

The curable resin composition used in the present invention can be used without causing stringing from a nozzle of a coating device such as a syringe or the like, without causing dripping of the curable resin composition during application to a vertical surface or an edge surface. In that it can be applied accurately and sufficiently to the adhesive surface, the static viscosity at 2 rpm and 25 ° C. is 20 rpm,
The thixotropy factor divided by the static viscosity at 25 ° C is 1.
7 or more, preferably 2.0 or more. If it is less than 1.7, the curable resin composition is threaded from a nozzle of a coating device such as a syringe at the time of application, and the curable resin composition drips at the time of application to a vertical surface or an edge surface, and a desired adhesive surface May not be applied accurately and sufficiently.

The curable resin composition used in the present invention has a static viscosity at 25 rpm at 2 rpm of 20 rpm.
The upper limit of the thixotropic coefficient divided by the static viscosity at 5 ° C. is preferably 7.0, and more preferably 5.0. If it exceeds 7.0, it may not be possible to apply well with a syringe.

The polymerizable vinyl monomer (1) used in the present invention is (A) a polymerizable vinyl monomer having a structure of the general formula (A) because of its low odor and large adhesiveness.
It is preferable to contain (B) a polymerizable vinyl monomer having a structure of the general formula (B) and (C) a polymerizable vinyl monomer having a structure of the general formula (C).

The polymerizable vinyl monomer (A) having the structure of the formula (A) used in the present invention has the following structure. Formula (A) Z—O— (R ₂ O) p —R ₁ [wherein, Z represents a (meth) acryloyl group, and R ₁ represents a phenyl group or a phenyl group having an alkyl group having 1 to 3 carbon atoms. R ₂ showing a is _{-C 2 H 4 -, - C} 3 H 6 -, - CH 2 CH (CH 3)
-, - C ₄ H ₈ - or -C ₆ H ₁₂ - it indicates, p is an integer of 1 to 10. ]

(A) Examples of the polymerizable vinyl monomer having the structure of the general formula (A) include phenoxyethyl (meth) acrylate and phenoxydiethylene glycol (meth).
Examples include acrylate, phenoxy polyethylene glycol (meth) acrylate, phenoxypropyl (meth) acrylate, phenoxydipropylene glycol (meth) acrylate, and phenoxy polypropylene glycol (meth) acrylate.

(A) The amount of the polymerizable vinyl monomer having the structure of the general formula (A) is preferably 20 to 60 parts by mass, more preferably 35 to 35 parts by mass, per 100 parts by mass of the polymerizable vinyl monomer.
~ 40 mass is more preferred. If the amount is less than 20 parts by mass, the adhesiveness may decrease, and if it exceeds 60 parts by mass, the adhesiveness may decrease.

The polymerizable vinyl monomer (B) having the structure of the formula (B) used in the present invention has the following structure.

[0021]

Embedded image

(B) The polymerizable vinyl monomer having the structure of the general formula (B) includes 2,2-bis (4- (meth)
Acryloxyphenyl) propane, 2,2-bis (4-
(Meth) acryloxyethoxyphenyl) propane,
2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypropoxyphenyl) propane, 2,2-bis (4- (meth) acryloxy Tetraethoxyphenyl)
And propane and 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane.

(B) The amount of the polymerizable vinyl monomer having the structure of the formula (B) is preferably 3 to 25 parts by mass, more preferably 5 to 1 part by mass per 100 parts by mass of the polymerizable vinyl monomer.
5 mass is more preferred. If the amount is less than 3 parts by mass, the adhesiveness may decrease, and if it exceeds 25 parts by mass, the adhesiveness may decrease.

The polymerizable vinyl monomer (C) having the structure of the formula (C) used in the present invention has the following structure. General formula (C) Z—O— (R ₂ O) p —H wherein Z and R ₂ are as described above. ]

(C) Examples of the polymerizable vinyl monomer having the structure of the general formula (C) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, diethylene glycol mono (meth) acrylate and polypropylene glycol ( (Meth) acrylate and the like.

(C) The amount of the polymerizable vinyl monomer having the structure of the general formula (C) is preferably 25 to 75 parts by mass, more preferably 45 to 75 parts by mass, per 100 parts by mass of the polymerizable vinyl monomer.
55 mass is more preferred. If the amount is less than 25 parts by mass, the adhesiveness may decrease. If the amount exceeds 75 parts by mass, the adhesiveness may decrease.

The (2) elastomer component used in the present invention refers to a polymer substance having rubber-like elasticity at room temperature, and for example, those which can be dissolved or dispersed in a polymerizable vinyl monomer are preferable.

As such an elastomer component, acrylonitrile-butadiene-methacrylic acid copolymer,
Acrylonitrile-butadiene-methyl methacrylate copolymer, butadiene-styrene-methyl methacrylate copolymer (MBS), acrylonitrile-styrene-
Butadiene copolymer, methyl methacrylate-butadiene-acrylonitrile-styrene copolymer (MBA
S) and acrylonitrile-butadiene rubber (N
BR), linear polyurethane, various synthetic rubbers such as styrene-butadiene rubber, chloroprene rubber and butadiene rubber, natural rubber, styrene-based thermoplastic elastomers such as styrene-polybutadiene-styrene-based synthetic rubber,
Polyolefin-based thermoplastic elastomers such as polyethylene-EPDM synthetic rubber, urethane-based thermoplastic elastomers such as caprolactone type, adipate type and PTMG type, polyester-based thermoplastic elastomers such as polybutylene terephthalate-polytetramethylene glycol multi-block polymer, and nylon-polyol Polyamide-based thermoplastic elastomer such as block copolymer or nylon-polyester block copolymer, 1,2-polybutadiene-based thermoplastic elastomer,
In addition, a PVC-based thermoplastic elastomer can be used.
One or more of these elastomer components may be used as long as they have good compatibility.

[0029] Among these, acrylonitrile is preferred from the viewpoints of solubility and adhesion to the polymerizable vinyl monomer.
Butadiene rubber is preferred. Further, a butadiene-styrene-methyl methacrylate copolymer may be used in combination. If these elastomer components have good compatibility, 1
Species or two or more can be used.

(2) The amount of the elastomer component used is
(1) With respect to 100 parts by mass of the polymerizable vinyl monomer, 1
The amount is preferably from 0 to 25 parts by mass, more preferably from 13 to 20 parts by mass. If the amount is less than 10 parts by mass, the adhesiveness decreases, the viscosity decreases, and the curable resin composition drips when applied to a vertical surface or an edge surface.
If the amount is more than 5 parts by mass, the viscosity may be too high, and it may not be possible to discharge from the syringe.

The (3) polymerization initiator used in the present invention is preferably an organic peroxide. As organic peroxides,
Examples include cumene hydroperoxide, paramenthane hydroperoxide, tertiary butyl hydroperoxide, diisopropylbenzene dihydroperoxide, methyl ethyl ketone peroxide, benzoyl peroxide and tertiary butyl peroxybenzoate. Among them, cumene hydroperoxide is preferable in terms of reactivity.

(3) The amount of the polymerization initiator to be added is 0.5 to 10 with respect to (1) 100 parts by mass of the polymerizable vinyl monomer.
A mass part is preferable and 1-7 mass is more preferable. 0.5
If the amount is less than 10 parts by mass, the curing rate may be low. If the amount exceeds 10 parts by mass, the storage stability may be deteriorated.

As the reducing agent (4) used in the present invention, any known reducing agent which reacts with the polymerization initiator (3) to generate radicals can be used. Typical reducing agents include
Examples include tertiary amines, thiourea derivatives and metal salts.

As the tertiary amine, triethylamine, tripropylamine, tributylamine and N, N
-Dimethyl paratoluidine and the like. Examples of the thiourea derivative include 2-mercaptobenzimidazole, methylthiourea, cybutylthiourea, tetramethylthiourea, and ethylenethiourea. Examples of the metal salt include cobalt naphthenate, copper naphthenate, and vanadyl acetylacetonate. Among these,
A metal salt is preferable, and vanadyl acetylacetonate is more preferable, since the surface hardening property of the surface part protruding from the adherend is good.

(4) The amount of the reducing agent used is 0.1 to 100 parts by mass of the polymerizable vinyl monomer (100 parts by mass).
The amount is preferably from 05 to 10 parts by mass, more preferably from 0.1 to 8 parts by mass. If the amount is less than 0.05 parts by mass, the curing speed is slow.
If the amount exceeds the mass part, an unreacted reducing agent remains, and the adhesive strength may be reduced.

Further, in the present invention, it is preferable to use a filler (5) from the viewpoint of increasing the viscosity and the adhesiveness.

As the filler (5) used in the present invention,
Silica powder such as crystalline silica powder, fused silica powder and colloidal fine powder silica, silica sand, carbon black, titanium oxide,
Inorganic fillers such as magnesium oxide, calcium carbonate powder, mica, aluminum hydroxide, aluminum powder, stainless steel powder, titanium powder, silicon carbide powder, silicon nitride powder, boron nitride powder, talc powder, glass beads, and polyethylene powder, An organic filler such as a silicon resin powder can be used. Among these, silica powder is preferred in terms of dispersibility and adhesiveness to the polymerizable vinyl monomer. These fillers can be used alone or in combination of two or more as long as the dispersibility is good.

(5) The amount of the filler used is preferably 3 to 40 parts by mass, more preferably 5 to 35 parts by mass based on 100 parts by mass of the total of (1) the polymerizable vinyl monomer and (2) the elastomer component. preferable. If the amount is less than 3 parts by mass, the viscosity and the adhesiveness may decrease. If the amount exceeds 40 parts by mass, the viscosity may be too high and the syringe may not be able to be discharged.

In the present invention, an acidic phosphoric acid compound represented by the general formula (D) can be used from the viewpoint of increasing the adhesiveness.

[0040]

Embedded image

Examples of the acidic phosphoric acid compound represented by the general formula (D) include acid phosphooxyethyl (meth) acrylate, acid phosphooxypropyl (meth) acrylate, and bis (2- (meth) acryloyloxyethyl) phosphate. Is mentioned.

The amount of the acidic phosphoric acid compound represented by the general formula (D) is preferably 0.05 to 10 parts by mass with respect to (1) 100 parts by mass of the polymerizable vinyl monomer from the viewpoint of adhesiveness. 0.1 to 7 parts by mass is more preferred.

Further, in the curable resin composition used in the present invention, various paraffins can be used in order to quickly cure the portion in contact with air. Examples of paraffins include paraffin, microcrystalline wax, carnauba wax, beeswax, lanolin, whale wax, ceresin, candelilla wax and the like.

The amount of the paraffin used is preferably 0.1 to 5 parts by mass, more preferably 0.3 to 2.5 parts by mass, per 100 parts by mass of the polymerizable vinyl monomer (1).
If the amount is less than 0.1 part by mass, curing of the portion in contact with the air may be deteriorated. If the amount exceeds 5 parts by mass, the adhesive strength may be reduced.

Further, a polymerization inhibitor can be used for the purpose of improving the storage stability. As a polymerization inhibitor, hydroquinone, hydroquinone monomethyl ether,
2,6-di-tert-butyl-p-cresol, 2,
2'-methylenebis (4-methyl-6-tert-butylphenol), triphenylphosphite, phenothiazine and N-isopropyl-N'-phenyl-p-
Phenylenediamine and the like.

The amount of the polymerization inhibitor to be used is preferably from 0.001 to 3 parts by mass, more preferably from 0.01 to 1 part by mass, per 100 parts by mass of the polymerizable vinyl monomer.
If the amount is less than 0.001 part by mass, there is a possibility that there is no effect.
If the amount is more than 10 parts by mass, the curing strength may decrease.

Although the components used in the present invention have been described above, polymerizable vinyl monomers having low odor can be used in addition to the above components.

Further, for the purpose of adjusting viscosity and fluidity, chlorosulfonated polyethylene, polyurethane, styrene-
Thermoplastic polymers such as acrylonitrile copolymer and polymethyl methacrylate can also be used.

If desired, known substances such as plasticizers, colorants and rust preventives can be used.

As an embodiment of the present invention, an embodiment for use as an adhesive composition for syringe application, particularly for a two-cylinder syringe application is preferred. Since the syringe is a simple application device, it is convenient for transportation, and can be easily used even by a non-skilled person, thereby improving workability. further,
There is no need to artificially control the mixing ratio of the first agent and the second agent, and mixing and coating can always be performed at a constant optimum ratio, so that the management of the coating device and adhesion is easy.

In general, the term "syringe" used herein means a cartridge and a push rod inserted into the cartridge, and the term "two-cylinder syringe" stores a two-part curable resin composition separately. Refers to two cylindrical cartridges. When a two-cylinder syringe is used, it is preferable to apply it with a manual gun because the device is small and can be used anywhere. As a manual gun provided with a two-cylinder syringe, for example, two cylindrical cartridges for separately storing a two-part curable resin composition, and these two cartridges are mounted and a grip portion is provided. An extruder having a lever portion and two extruding rods each having a piston-like extruding portion at the tip, and a nozzle portion connected to the tip of the cartridge using the extruding device, and having a grip portion. When the lever portion is squeezed, an extruder is used to extrude the adhesive composition in each cartridge to the nozzle portion, to join and eject the composition.

In this case, all the essential components of the adhesive composition of the present invention are not mixed during storage, and the adhesive composition is filled into a two-cylinder syringe divided into a first agent and a second agent. . At this time, (3) a polymerization initiator and a (4) reducing agent are separately charged and stored in the first agent and the second agent, respectively. By simultaneously applying, contacting and curing both agents, it can be used as an adhesive composition for two-cylinder syringe application.

As another embodiment, one or both of the first agent and the second agent are preliminarily containing (1) a polymerizable vinyl monomer and other optional components, and the two components are mixed at the time of curing, and then the mixture is simply added. By filling in a single-cylinder syringe,
An embodiment in which the composition is used as a one-part adhesive composition is exemplified.

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

In the present invention, the adherend is joined with the cured body of the curable resin composition to produce a joined body. There are no particular restrictions on the material of the adherend, such as paper, wood, ceramic, glass, porcelain, rubber, plastic, mortar, concrete, and metal. However, when the adherend is a metal, it exhibits better adhesion.

[0056]

The present invention will be described below with reference to experimental examples.

Commercial products were used for each substance. However,
For 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, q in the general formula (B) was used, paraffin was used for paraffin, and polymerization inhibitor was hydroquinone monomethyl ether. . In addition, each physical property was measured as follows.

Further, as a manual discharge gun, two cylindrical cartridges (two-cylinder syringe) for separately storing the two-part adhesive composition, and these two cartridges are mounted. An extruding device including a grip portion, a lever portion, and two extruding rods each having a piston-like extruding portion at the end, and a static mixer using the extruding device and connected to the end of a cartridge, the end of which is a nozzle portion. When the lever part is squeezed with the grip part, the extruding part mixes the adhesive composition in each cartridge with a static mixer, extrudes it to the nozzle part, and uses a coating device that can discharge it. Was.

[Static Viscosity] A sample was adjusted to a liquid temperature of 25 ° C. in accordance with JIS K-6838. Using a BH-type viscometer, the static viscosity was calculated from the scale of the pointer after rotating the rotor at 2 rpm and 20 rpm for 2 minutes. The thixotropy coefficient (thixotropy value) was a value obtained by dividing the static viscosity at a rotation speed of 2 rpm by the static viscosity at 20 rpm.

[Liquid dripping] About 1 g of the mixture obtained by a static mixer was applied by a manual discharge gun to a stainless steel plate in the form of dots from a two-cylinder syringe and allowed to stand for 30 seconds. Thereafter, the board was set upright, and the length of the adhesive composition applied in the form of a dot was measured until the adhesive composition was cured.

[Threading property] Using a manual discharge gun, about 1 g mixed with a static mixer is applied to a stainless steel flat plate from the tip of a nozzle of a two-cylinder syringe, and the adhesive composition is threaded from the tip of the nozzle. Was observed.
Judgment: ○ No stringing, △ Slightly stringing, × Stringing

[Syringe applicability] Using a manual discharge gun, about 1 g mixed with a static mixer was applied to a stainless steel flat plate from a two-cylinder syringe, and the extrudability of the adhesive composition was evaluated. Judgment: ○ Extrusion coating is easy, Δ can be applied by applying a little force, ×
Extrusion has considerable resistance and cannot be applied

[Tensile shear bond strength] Temperature 23 ° C, humidity 5
According to JIS K-6850 in an environment of 0%, a single test piece (aluminum A-2024 sandblasted steel plate of 100 mm × 25 mm × 1.6 mm) was provided with an adhesive composition and a two-cylinder syringe on one surface of the test piece. Apply using a manual discharge gun and apply another test piece (100 mm × 25
mm × 1.6 mm aluminum A-2024 sandblasted steel sheet). Then, it was cured at room temperature for 24 hours and used as a sample for measuring tensile shear adhesive strength.
In order to make the thickness of the adhesive composition layer uniform, a particle size of 1
A trace amount of 25 μm glass beads was added. Tensile shear adhesive strength (unit: MPa) was measured at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 10 mm / min.

[Peel strength] Temperature 23 ° C., Humidity 50%
In accordance with JIS K-6854, one test piece (200 × 25 × 0.5 mm, aluminum A-202)
4 sandblasted steel sheet) with an adhesive composition on one side.
It was applied using a manual discharge gun equipped with a two-cylinder syringe, and bonded to another test piece (aluminum A-2024 sandblasted steel plate of 100 × 25 × 1.6 mm). Then, it was cured at room temperature for 24 hours and used as a sample for measuring peel adhesion strength. In order to make the thickness of the adhesive composition layer uniform, a very small amount of glass beads having a particle size of 400 μm was added. Peeling adhesive strength (unit: kN / m) was measured at a tensile speed of 50 mm / min in an environment of a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 50 mm / min.

[Impact bond strength] Temperature 23 ° C, humidity 50%
According to JIS K-6855 in an environment of RH, the adhesive composition was applied to one surface of one test piece (25 mm × 25 mm × 9 mm, iron sand blasting block) using a manual ejection gun equipped with a two-cylinder syringe. And bonded to another test piece (25 mm × 44 mm × 19 mm, iron sandblasted block). After this, at room temperature
After curing for 4 hours, this was used as a sample for measuring the impact adhesive strength.
The impact adhesive strength (unit: kJ / m ² ) was measured with an Izod impact tester at an environment of a temperature of 23 ° C. and a humidity of 50%.

[Odor] The odor intensity of the adhesive composition was as follows. Judgment: ○ Almost no odor, × Clear odor

Experimental Example 1 Each substance was mixed at the composition ratio shown in Table 1 to prepare an adhesive composition comprising the first agent and the second agent shown in Table 1, and used in equal amounts. The physical properties of the obtained two-part adhesive composition were measured. The results are shown in Table 1.

[0068]

[Table 1]

Experimental Example 2 An experiment was performed in the same manner as in Experimental Example 1, except that the substances were mixed in the amounts used in Table 2 to prepare an adhesive composition comprising the first and second agents shown in Table 2. . The results are shown in Table 3.

[0070]

[Table 2]

[0071]

[Table 3]

Experimental Example 3 An experiment was carried out in the same manner as in Experimental Example 1 except that the substances were mixed in the amounts used in Table 4 to prepare an adhesive composition comprising the first and second agents shown in Table 4. . The results are shown in Table 4.

[0073]

[Table 4]

Experimental Example 4 An experiment was carried out in the same manner as in Experimental Example 1, except that the respective substances were mixed in the amounts used in Table 5 to prepare an adhesive composition comprising the first and second agents shown in Table 5. . The results are shown in Table 5.

[0075]

[Table 5] Experimental Example 5 The same operation as in Experimental Example 1 was performed except that a commercially available acrylic low-odor adhesive composition was used. The results are shown in Table 6.

[0076]

[Table 6]

[0077]

EFFECT OF THE INVENTION The curable resin composition of the present invention has a low odor, a high shear adhesive strength, a high peel adhesive strength and a high impact adhesive strength. Is obtained. In particular, the working environment can be improved by reducing the odor. Furthermore, it can be easily applied using a hand-operated coating device such as a two-cylinder syringe that can be carried anywhere, and can be applied without stringing from the nozzle of the coating device. It can be applied without dripping. Therefore, unskilled workers
The industrial benefit is enormous because the adhesive composition can be applied precisely, sufficiently, firmly and easily in a good working environment to the adhesive surface intended at any location.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08F 291/02 C08F 291/02 4J040 299/02 299/02 4J100 C08K 3/00 C08K 3/00 C08L 71 / 02 C08L 71/02 101/00 101/00 C09J 4/00 C09J 4/00 4/02 4/02 4/06 4/06 5/00 5/00 F term (reference) 4J002 AC01X AC04X AC07X AC08X AC09X BB024 BB15X BD03X BN14X BN15X BN16X BP01X CF05X CH05W CH05Y CK02X CL08X CP034 DA038 DA098 DA118 DC008 DE078 DE138 DE148 DE238 DJ008 DJ017 DJ048 DJ058 DK007 DL008 EE047 EG067 EH079 EK016 EK046 EK027 FG01 014 PA14 PA15 PA64 PA65 PA66 PA69 PA76 PA78 PA79 PA88 PA95 PA96 PA99 PB06 PB22 PB38 PC08 4J015 CA04 CA05 CA07 CA08 4J026 AA12 AA13 AA17 AA24 AA45 AA49 AA68 AA71 AB02 AB10 AB28 AC02 AC10 AC11 AC12 AC15 AC16 AC32 BA28 BA30 BA50 BB04 DA05 DA16 DB25 4J027 AC02 AC03 AC04 AC06 AJ02 AJ08 AJ09 BA07 BA08 BA19 CA02 CA03 CA04 CA06 CA07 CA08 CA10 CA12 CA14 CA18 CA01 CA03 CA03 CA01 CA01 CA03 CA04 CA052 CA071 CA072 CA081 CA082 CA151 CA152 DA021 DA022 DA121 DA122 DL141 DL142 DM011 DM012 ED001 ED002 EF001 EF002 FA141 FA142 FA161 FA162 FA281 FA282 JA13 KA13 KA21 KA25 KA42 LA01 LA06 LA11 PB03 4J100 AL08P BA08 BA08 BA08 BA08 BA08 BA08 BA08 BA08 BA08 BA08 FA03 JA03

Claims (10)

[Claims] 1. The static viscosity at 20 rpm is 110,000 mPa
A curable resin composition having a thixotropy coefficient of 1.7 or more obtained by dividing a static viscosity at 2 rpm by a static viscosity at 20 rpm, and (1) containing a polymerizable vinyl monomer. 2. The curable resin composition according to claim 1, further comprising (2) an elastomer component. 3. The curable resin composition according to claim 1, further comprising (3) a polymerization initiator. 4. The curable resin composition according to claim 1, further comprising (4) a reducing agent. 5. The curable resin composition according to claim 1, further comprising (5) a filler. 6. The polymerizable vinyl monomer according to claim 1, wherein (A) the polymerizable vinyl monomer having the structure represented by the general formula (A): ZO— (R ₂ O) p —R ₁ in, Z is (meth) shows acryloyl group, R ₁ is R ₂ to a phenyl group having a phenyl group or an alkyl group having 1 to 3 carbon atoms _{-C 2 H 4 -, - C} 3 H 6 -, - CH ₂ CH (CH ₃ )
-, - C ₄ H ₈ - or -C ₆ H ₁₂ - it indicates, p is an integer of 1 to 10. (B) a polymerizable vinyl monomer having the structure of general formula (B): And (C) a polymerizable vinyl monomer having a structure represented by the general formula (C): General formula (C) Z—O— (R ₂ O) p —H wherein Z and R ₂ are as described above. The curable resin composition according to any one of claims 1 to 5, comprising: 7. The curable resin composition is divided into a first part and a second part, wherein the first part contains (3) a polymerization initiator and the second part contains (4) a reducing agent. The two-part curable resin composition according to any one of claims 4 to 6, wherein 8. A curable resin composition for syringe application, comprising the curable resin composition according to claim 1. 9. An adhesive composition comprising the curable resin composition according to claim 1. Description: 10. A method for bonding an adherend, comprising using the curable resin composition according to claim 1. Description: