JP3305613B2 - Curable resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a curable resin composition containing a polymerizable vinyl monomer having a low odor and excellent durability and moisture resistance, and more particularly to an adhesive composition.

[0002]

2. Description of the Related Art The demand for a room-temperature fast-curing adhesive that cures at room temperature in a short time tends to increase year by year in order to save labor, resources and energy. Conventionally, as a room-temperature fast-curing adhesive, a two-component fast-curing epoxy adhesive, an anaerobic adhesive, an instant adhesive, and a second-generation acrylic adhesive (S
GA) is known.

The two-component type rapid curing epoxy adhesive is one in which a main agent and a curing agent are weighed and mixed, applied to an adherend, and cured by a reaction between the main agent and the curing agent. However, the two-component fast-curing epoxy adhesive may cause a significant decrease in strength when the main component and the curing agent are not sufficiently measured and mixed, and
There is a drawback that the peeling strength and the impact strength are low even when the weighing and mixing are sufficiently performed. The anaerobic adhesive is cured by pressing the adhesive composition between the adherends to block air. However, when a part of the adhesive composition is exfoliated from the adherend during pressure bonding, there is a drawback that the extruded part comes into contact with air and is not cured. or,
It has a drawback that it does not cure even when the clearance between adherends is large.

Instant adhesives usually contain cyanoacrylate as a main component and are excellent in workability. However, it has the drawback of low peel strength and impact strength. Further, there is a drawback that the range of use is remarkably limited due to poor moisture resistance and water resistance. Although SGA is a two-part type, it does not require accurate metering of the two parts, and it cures in a few minutes or tens of minutes at room temperature even with incomplete metering or mixing, and sometimes contact between the two parts, so workability is improved. In addition, SGA is widely used because it has high peeling strength and impact strength and also has a good hardening at the portion where the blemishes are exposed. However, since such SGA uses a highly volatile and odorous (meth)acrylic acid alkyl ester such as methyl methacrylate as a polymerizable vinyl monomer, it has a strong odor and flammability, and therefore has a high work environment. It was a big problem.

[0005]

SUMMARY OF THE INVENTION In order to solve these drawbacks, JP-A-55-71770 and JP-A-57 are used.
-87484, JP-A-57-90073,
JP-A-57-100168, JP-A-58-152
076 and JP-A-61-34082,
An adhesive composition containing a high boiling polymerizable vinyl monomer is disclosed. These adhesive compositions have solved the problems of volatility and flammability, but have a problem that they have poor odor, durability and moisture resistance and are difficult to use for bonding products and parts. In particular, recently, there has been a demand for an adhesive composition that has a low odor in the working environment, low flammability, and excellent durability and moisture resistance. The present invention, in order to solve these problems, by combining a specific polymerizable vinyl monomer, a finding that a curable resin composition having a low odor and good durability achieves this object. Thus, the present invention has been completed.

[0006]

[In the formula, Z represents a (meth)acryloyl group, and R₁Represents a phenyl group or a phenyl group having an alkyl group having 1 to 3 carbon atoms. R₂Is -C₂H_Four−, −C₃H₆−, −CH₂CH(CH ₃)−, −C_FourH₈-Or-C₆H₁₂Represents -, and p represents an integer of 1 to 10. ]

(2) Polymerizable vinyl monomer having the structure of general formula (B)

[Chemical 2] (3) General formula polymerizable vinyl monomer general formula (C) in _{Z-O- (R 2 O)} p -H [wherein having the structure of (C), Z and R ₂ are as defined above. (4) Organic peroxide (5) Reducing agent is contained, and the curable resin composition is characterized by further containing (6) Elastomer component. (5) The curable resin composition, wherein the reducing agent is a metal salt. The curable resin composition is a two-part curable resin composition comprising a first liquid and a second liquid, the first liquid containing an organic peroxide, and the second liquid being a reducing agent. It is a two-component type curable resin composition comprising: A bonded body characterized by being a cured body of the curable resin composition, wherein an adherend is joined by the cured body, wherein the adherend is a metal A method for adhering an adherend, which is a body and uses the curable resin composition.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The polymerizable vinyl monomer having the structure of (1) general formula (A) used in the present invention has the following structure. Formula (A) Z-O- (R 2 O) p -R 1 where Shikichu, Z is shown a (meth) acryloyl group, R ₁ is a phenyl group having a phenyl group or an alkyl group having 1 to 3 carbon atoms Indicates. R ₂ 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. (1) As the polymerizable vinyl monomer having the structure of the general formula (A), phenoxyethyl (meth)acrylate,
Examples thereof include phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, phenoxypropyl (meth)acrylate, phenoxydipropylene glycol (meth)acrylate and phenoxypolypropylene glycol (meth)acrylate.

The addition amount of the polymerizable vinyl monomer having the structure of the general formula (A) is preferably 20 to 85 parts by weight in 100 parts by weight in total of (1), (2) and (3), and 35 to 35 parts by weight.
70 weight is more preferable. If it is less than 20 parts by weight, the adhesiveness may decrease, and if it exceeds 85 parts by weight, the adhesiveness may decrease.

The (2) polymerizable vinyl monomer having the structure of the general formula (B) used in the present invention has the following structure.

[Chemical 3] (2) The polymerizable vinyl monomer having the structure of the general formula (B) includes 2,2-bis(4-(meth)acryloxyphenyl)propane and 2,2-bis(4-(meth)acryloxyethoxy. Phenyl)propane, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypropoxyphenyl)propane, 2,2-bis(4-( Meta)
Examples thereof include acryloxytetraethoxyphenyl)propane and 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane.

The addition amount of the polymerizable vinyl monomer having the structure of the general formula (B) is 1 in total of (1), (2) and (3).
5 to 30 parts by weight is preferable in 10 parts by weight, and 10 to 25 parts by weight.
Weight is more preferred. If it is less than 5 parts by weight, the adhesiveness may decrease, and if it exceeds 30 parts by weight, the adhesiveness may decrease.

In the present invention, (3) a polymerizable vinyl monomer having the structure of general formula (C) is added. (3) The polymerizable vinyl monomer having the structure of general formula (C) has the following structure. Formula (C) Z-O- (R 2 O) p -H In the formula, Z and R ₂ are the same as in (1). (3) As the polymerizable vinyl monomer having the structure of the general formula (C), 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, diethylene glycol mono(meth)acrylate and polypropylene glycol (meth)acrylate. Etc.

The addition amount of the polymerizable vinyl monomer having the structure of the general formula (C) is 1 in total of (1), (2) and (3).
In 50 parts by weight, 10 to 50 parts by weight are preferable, and 20 to 4
0 weight is more preferred. If it is less than 10 parts by weight, the adhesiveness may decrease, and if it exceeds 50 parts by weight, the moisture resistance may decrease.

(4) Organic peroxides used in the present invention include cumene hydroperoxide, paramenthane hydroperoxide, tertiary butyl hydroperoxide, diisopropylbenzene dihydroperoxide, methyl ethyl ketone peroxide, benzoyl peroxide. And tertiary butyl peroxybenzoate. Among these, cumene hydroperoxide is preferable from the viewpoint of reactivity.

The amount of organic peroxide added is (1), (2)
And 0.5 to 10 with respect to 100 parts by weight in total of (3).
Parts by weight are preferable, and 1 to 7 parts by weight is more preferable. 0.5
If it is less than 10 parts by weight, the curing speed is slow, and if it exceeds 10 parts by weight, the storage stability may deteriorate.

The reducing agent (5) used in the present invention may be any known reducing agent that reacts with the organic peroxide to generate radicals. Typical reducing agents include tertiary amines, thiourea derivatives and metal salts. Examples of the tertiary amine include triethylamine, tripropylamine, tributylamine, N,N-dimethylparatoluidine and the like. 2 as thiourea derivatives
-Mercaptobenzimidazole, methylthiourea, cibutylthiourea, tetramethylthiourea, ethylenethiourea and the like. Examples of the metal salt include cobalt naphthenate, copper naphthenate and vanadyl acetylacetonate. Among these, metal salts are preferable, and vanadyl acetylacetonate is more preferable, from the viewpoint of good surface curability of the surface portion protruding from the adherend.
When a thiourea derivative is used, the surface of the protruding portion is not cured and stickiness is observed, which may result in poor surface curability.

The amount of the reducing agent added is preferably 0.05 to 10 parts by weight, and more preferably 0.1 to 8 parts by weight, based on 100 parts by weight of the total of (1), (2) and (3). 0.
If it is less than 05 parts by weight, the curing speed is slow, and if it exceeds 10 parts by weight, unreacted reducing agent remains and the adhesive strength may be lowered.

The components used in the present invention have been described above, but the curable resin composition of the present invention may further contain the following polymerizable vinyl monomers having less odor. (Meth)acrylic acid ester of higher alcohol. Examples of such a polymerizable vinyl monomer include (meth)acrylic acid esters of higher aliphatic alcohols such as 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate and stearyl (meth)acrylate, dicyclopentanyloxyalkyl( (Meth)acrylate,
Examples thereof include dicyclopentenyloxyalkyl (meth)acrylate, and (meth)acrylic acid ester of monoether alcohol such as ethylene glycol.

(Meth)acrylic acid esters of polyhydric alcohols. Examples of such a polymerizable vinyl monomer include trimethylolpropane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tetra(meth)acrylate and dipentaerythritol hexa(meth)acrylate.

A urethane prepolymer having a (meth)acryloyloxy group. Such a polymerizable vinyl monomer can be obtained, for example, by reacting a (meth)acrylic acid ester having a hydroxyl group, an organic polyisocyanate and a polyhydric alcohol. Examples of the (meth)acrylic acid ester having a hydroxyl group include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate. As the organic polyisocyanate, toluene diisocyanate, 4,
4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and the like can be mentioned. Examples of the polyhydric alcohol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol and polyester polyol.

An acidic phosphoric acid compound represented by the following general formula (D).

[Chemical 4] Examples of the acidic phosphoric acid compound represented by the general formula (I) include acid phosphooxyethyl (meth)acrylate, acid phosphooxypropyl (meth)acrylate and bis(2-(meth)acryloyloxyethyl).
Examples include phosphate. Among these, the acidic phosphoric acid compound represented by the general formula (D) is preferable in terms of adhesiveness. The amount of the acidic phosphoric acid compound represented by the general formula (D) is 0.05 to 10 parts by weight based on 100 parts by weight of the total of (1), (2) and (3) in terms of adhesiveness. Preferably, 0.1 to 7 parts by weight is more preferable.

In the present invention, the (6) elastomer component is preferably used in the curable resin composition in order to improve the peel strength and impact strength. The elastomer component refers to a polymer substance having rubber-like elasticity at room temperature, and for example, one that can be dissolved or dispersed in a polymerizable vinyl monomer is preferable. Examples of such an elastomer component include methyl methacrylate-butadiene-styrene copolymer (MBS), acrylonitrile-styrene-butadiene copolymer, linear polyurethane, acrylonitrile-butadiene rubber, styrene-butadiene rubber, chloroprene rubber and butadiene rubber. And various synthetic rubbers, and natural rubber. Of these, acrylonitrile-butadiene rubber is preferable from the viewpoint of solubility and adhesiveness to the polymerizable vinyl monomer. These elastomer components may be used alone or in combination of two or more as long as they have good compatibility.

The addition amount of the elastomer component of the present invention is
The total amount of (1), (2) and (3) is 100 parts by weight, preferably 5 to 35 parts by weight, more preferably 10 to 30 parts by weight. If the amount is less than 5 parts by weight, the viscosity and adhesiveness may be lowered, and if the amount is more than 35 parts by weight, the viscosity may be too high and work may be inconvenient.

In addition to the above, thermoplastic polymers such as chlorosulfonated polyethylene, polyurethane, styrene-acrylonitrile copolymer and polymethylmethacrylate, and fine powder silica may be used for the purpose of adjusting viscosity and fluidity. it can. In addition, the curable resin composition of the present invention may 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, spermaceti, ceresin and candelilla wax. The amount of paraffins added is preferably 0.1 to 5 parts by weight, and more preferably 0.3 to 2.5 parts by weight, based on 100 parts by weight of the total of (1), (2) and (3). If it is less than 0.1 part by weight, the curing of the part in contact with air may be deteriorated, and if it exceeds 5 parts by weight, the adhesive strength may be lowered.

Further, various antioxidants including a polymerization inhibitor may be used for the purpose of improving storage stability. Antioxidants include hydroquinone, hydroquinone monomethyl ether, 2,6-ditertiarybutyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), triphenylphosphite, phenothiazine and N. -Isopropyl-N'-phenyl-p-phenylenediamine and the like can be mentioned. The addition amount of the polymerization inhibitor is preferably 0.001 to 3 parts by weight, more preferably 0.01 to 1 part by weight, based on 100 parts by weight of the total of (1), (2) and (3).
If it is less than 0.001 part by weight, no effect is obtained, and if it exceeds 3 parts by weight, the curing strength may decrease. In addition to these, known substances such as a plasticizer, a filler, a colorant, and a rust preventive can be used if desired.

In an embodiment of the present invention, it is preferably used as an adhesive composition. In this case, for example,
It may be used as a two-component adhesive composition. Regarding the two-pack type, all the essential components of the adhesive composition of the present invention are not mixed during storage, the adhesive composition is divided into a first liquid and a second liquid, and an organic peroxide is added to the first liquid. The reducing agent is stored separately in the second liquid. In this case, the two liquids can be used as a two-component type adhesive composition by applying the both liquids simultaneously or separately and contacting and curing them. In another embodiment, one or both of the first liquid and the second liquid contain a polymerizable vinyl monomer and other optional components in advance, and the two components are mixed at the time of curing to form a one-pack type adhesive. It can be used as an agent composition. Among these embodiments, it is preferable to use it as a two-pack type adhesive composition because of its excellent storage stability.

In the present invention, the adherends are joined with the cured body of the curable resin composition to form a joined body. Various materials for adherends include paper, wood, ceramics, glass,
Ceramics, rubber, plastics, mortars, concretes, metals, etc. are not limited, but when the adherend is a metal, it exhibits superior adhesiveness.

[0027]

The present invention will be described in more detail with reference to the following examples. In addition, hereinafter, the unit of the amount of each substance used is shown in parts by weight. For each substance, 2,2-bis(4-methacryloxypolyethoxyphenyl)propane having a q of 5 in the general formula (B) is used, and acrylonitrile-
Medium-high nitrile was used as the butadiene rubber, and BTAIIIN2 manufactured by Kureha Chemical Co., Ltd. was used as the butadiene-styrene-methylmethacrylate copolymer. Various physical properties were measured as follows.

[Tensile shear strength] Temperature 23° C., humidity 50%
In accordance with JIS K-6850, one test piece (100×25×1.6 mm, SPCC-D untreated steel plate or 100×25×2.0 mm aluminum A-5)
(052 sandblasted steel plate) was coated with the curable resin composition on one surface and was bonded to another test piece. In the case of the two-pack type curable resin composition, the first liquid was applied to one surface of one test piece, and the second liquid was applied to the other test piece. Immediately thereafter, the coated surfaces were overlaid and bonded. After that, it was aged at room temperature for 24 hours, and this was used as a sample for tensile shear strength measurement. Tensile shear strength of sample (unit: M
Pa) 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] A test piece (2 pieces) according to JIS K-6854 in an environment of a temperature of 23° C. and a humidity of 50%.
00x25x1.6mm, SPCC-D untreated steel plate)
The curable resin composition was applied to one side of the above, and the other test piece was attached. In the case of a two-pack type curable resin composition,
The first liquid was applied to one surface of one test piece, and the second liquid was applied to the other test piece (200×25×0.4 mm, untreated steel plate of SPCC-D). Immediately thereafter, the coated surfaces were overlaid and bonded. After that, it was aged at room temperature for 24 hours and used as a sample for peel strength measurement. In order to make the thickness of the curable resin composition layer uniform, the particle size is 100 μm.
Of glass beads were added in a trace amount. For the peel strength (unit: kN/m) of the sample, the T peel strength was measured at a tensile speed of 100 mm/min in an environment of a temperature of 23° C. and a humidity of 50%.

[Humidity Resistance Tensile Shear Strength Retention] Moisture resistance tensile shear strength retention was measured as an adhesive durability evaluation item. A sample for measuring the tensile shear strength of aluminum is heated to a temperature of 50.
After being left for 1 week in an environment of °C and a humidity of 98%, it was taken out and the tensile shear strength was measured in an environment of a temperature of 23°C and a humidity of 50%. Moisture resistance tensile shear strength retention rate (unit:%) is the ratio of tensile shear strength exposed to an environment of temperature 50°C and humidity of 98% to tensile shear strength exposed to an environment of temperature 23°C and humidity 50%. ).

[Odor] The odor intensity of each curable resin composition was set as follows. ○: Almost no odor. X: There is a clear odor.

(Examples 1 to 3 and Comparative Example 1) Liquids of compositions were prepared by mixing the substances except for cumene hydroperoxide in the amounts shown in Table 1. Then, cumene hydroperoxide was mixed and then immediately bonded. The measurement results are also shown in Table 1. Comparative Example 1 is a conventional adhesive, which has sufficient adhesive performance, but has a strong odor of methyl methacrylate.

[0033]

[Table 1]

(Examples 4 to 14 and Comparative Example 2) Tables 2 to 3
Each substance was mixed in the addition amount of 1 to prepare a curable resin composition composed of the first liquid and the second liquid. The measurement results are also shown in Tables 2 and 3. Comparative Example 2 was a conventional adhesive, which had an extremely weak odor but poor moisture resistance and did not show practical durability.

[0035]

[Table 2]

[0036]

[Table 3]

[0037]

[Table 4]

(Example 15) With respect to the curable resin composition of Example 11, one test piece (100 x 25 x 1.6 mm, untreated SPCC-D) under the environment of 23°C and 50% humidity. The first liquid and the second liquid were mixed and applied in an equal amount on one surface of a steel plate), and another test piece (the same as the above-mentioned one) was laminated and laminated. After that, it was aged at room temperature for 24 hours, and the surface curability of the portion protruding from the adherend was observed. The surface of the protruding portion was sufficiently cured and was good.

[0039]

EFFECTS OF THE INVENTION The curable resin composition of the present invention can provide a joined body having low odor and excellent durability and moisture resistance. Especially by reducing odor, the working environment can be improved and its industrial benefit is extremely large.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C09J 5/00 C09J 5/00 (56) References JP 62-1772 (JP, A) JP 59-207977 (JP , A) JP 59-174671 (JP, A) JP 60-120774 (JP, A) JP 55-71770 (JP, A) JP 57-87484 (JP, A) JP 57-90073 (JP, A) JP-A-57-100168 (JP, A) JP-A-58-152076 (JP, A) JP-A-61-34082 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 299/00-299/08 C08F 290/00-290/14 C08F 20/00-20/70 C08F 220/00-220/70 C09J 1/00-201/10

Claims (8)

(57) [Claims] 1. A total of (1), (2) and (3) in which (1) a polymerizable vinyl monomer having a structure of general formula (A ) is added.
20 to 85 parts by weight in 100 parts by weight, general formula (A) ZO-(R2O)p-R1 [In the formula, Z represents a (meth)acryloyl group, and R1 is a phenyl group or a carbon number of 1 to 1; 3 shows a phenyl group having an alkyl group of 3. R2 is -C2H4-, -C3H6-, -CH2CH(CH3)-,
-C4H8- or -C6H12- is shown, and p represents an integer of 1-10. (2) 100 parts by weight of the total of (1), (2) and (3) of the polymerizable vinyl monomer having the structure of the general formula (B).
Medium, 5 to 30 parts by weight, (3) A total of 100 parts by weight of the polymerizable vinyl monomer having the structure of the general formula (C) , (1), (2) and (3).
In the above, 10 to 50 parts by weight, general formula (C) ZO-(R2O)p-H [In the formula, Z and R2 are as described above. ] (4) Organic peroxide is combined with (1), (2) and (3)
0.5 to 10 parts by weight based on 100 parts by weight in total, (5) reducing agent , 10 in total of (1), (2) and (3)
A curable resin composition comprising 0.05 to 10 parts by weight with respect to 0 parts by weight . 2. Further, (6) an elastomer component ,
For 100 parts by weight of the total of (1), (2) and (3)
The curable resin composition according to claim 1, wherein the curable resin composition comprises 5 to 35 parts by weight . 3. The curable resin composition according to claim 1, wherein the reducing agent (5) is a metal salt. 4. The curable resin composition according to claim 1, claim 2 or claim 3 is divided into a first liquid and a second liquid, and the first liquid and
Polymerizable vinyl monomer in either or both of
A two-component type curable resin composition comprising a first liquid and a second liquid, wherein the first liquid contains an organic peroxide. A two-pack type curable resin composition, wherein the two-pack contains a reducing agent. 5. An adhesive comprising the curable resin composition according to claim 1, claim 2, claim 3 or claim 4 . 6. The curable resin composition according to claim 5.
Hardened body of adhesive . 7. The curable resin composition according to claim 5.
Depending on the hardened adhesive , the paper, wood, ceramic,
Lath, ceramics, rubber, plastic, mortar, concrete
Conjugate, such as products and components adherend such as REITs and metal products and parts are characterized by being joined. 8. A method for adhering an adherend, which comprises using the curable resin composition according to claim 1, claim 2, claim 3 or claim 4.