JP2001261724A - Flame-retarded resin composition, flame-retarded adhesive composition and metallic joined product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retarded resin composition and a flame-retarded adhesive composition, hardly providing bad effects to a human body or the environment, and excellent in flame retardancy and adhesion. SOLUTION: This flame-retarded resin composition comprises (1) a polymerizable vinyl monomer, (2) a polymerization initiator, (3) a reducing agent, and (4) a condensed phosphoric acid. The composition can further contain (5) a metal hydroxide and (6) an elastormer component, and the flame-retarded resin composition can be the flame-retarded adhesive composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant resin composition having excellent moisture resistance, and more particularly to a room-temperature-curable flame-retardant adhesive composition suitable for joining metals.

[0002]

2. Description of the Related Art Metal sheets are used for interior materials of buildings, for example, partition boards, doors, elevators, and storages.

[0003] As an adhesive used for metal bonding, it is required to use a room-temperature fast-curing adhesive composition which cures in a short time at room temperature in terms of labor saving, resource saving and energy saving. Conventionally, room-temperature fast-curing adhesive compositions include two-pack type fast-curing epoxy adhesive compositions, anaerobic adhesive compositions, instantaneous adhesive compositions, and second-generation acrylic adhesive compositions (SGA )It has been known.

[0004] The two-pack type fast-curing epoxy-based adhesive measures and mixes a main agent and a curing agent, applies the mixture to an adherend, and cures by a reaction between the main agent and the curing agent. However, the two-pack type quick-curing epoxy adhesive has a drawback that the peel strength and the impact strength are low.

[0005] The anaerobic adhesive is cured by pressing the adhesive composition between adherends to block air. However, the anaerobic adhesive composition has a drawback that, when a part of the adhesive composition comes out of the adherend at the time of pressure bonding, the part that comes out comes into contact with air and thus does not cure. Further, there is a disadvantage that the composition does not cure even when the clearance between the adherends is large.

[0006] The instant adhesive usually contains cyanoacrylate as a main component and has excellent workability. However, there were drawbacks in that the peel strength and impact strength were low, and the moisture resistance and water resistance were poor.

Although SGA is two-packed, it does not require accurate measurement of two-package, and cures in a few minutes to tens of minutes at room temperature, even if measurement or mixing is incomplete, or even sometimes only two-pack contact. Therefore, excellent workability, high peel strength and impact strength,
It is widely used because of good curing of the exposed portion.

However, since the cured SGA is an organic polymer compound, when the bonded body bonded by the SGA is heated by a fire, the polymer chain depolymerizes or thermally decomposes, and the cured SGA is used as an adhesive. There was a possibility that the function could not be performed. As a result, there has been a restriction that the conventional SGA cannot be used for applications in which a fire is assumed.

As a result, a method using a double-sided tape having flame retardancy or a welding method has been adopted for applications in which the joint may be exposed to a flame.

As a method of using a double-sided tape provided with flame retardancy, Japanese Patent Application Laid-Open Nos. 9-194797 and 10-1
No. 40094 discloses a fast-curing flame-retardant double-sided tape to which a photopolymerization initiator and ammonium polyphosphate are added.

However, in this method, metal adherence cannot be performed because the adherend needs to be irradiated with ultraviolet rays, and in applications where a high load is applied for a long period of time due to low adhesiveness. There was a problem that durability was insufficient.

[0011] On the other hand, the welding method does not use an organic compound for joining metals, so that there is an advantage that the joining portion does not peel off even when exposed to high temperatures, but distortion occurs in the joined body due to heat generated during welding. As a result, there is a problem that a work of removing distortion is required. In addition, there is a problem that the appearance is impaired in a metal panel that requires design.

According to the present invention, in order to solve these problems, when a resin composition using a specific component is used, the adhesive composition is used for applications having flame retardancy and danger of being exposed to a flame. The present inventors have found that the present invention is used as such, and have completed the present invention.

[0013]

That is, the present invention provides (1)
A flame-retardant resin composition containing a polymerizable vinyl monomer, (2) a polymerization initiator, (3) a reducing agent, and (4) condensed phosphoric acid, and further contains (5) a metal hydroxide. And (6) the flame-retardant resin composition containing an elastomer component, and (1) the polymerizable vinyl monomer is polymerizable (meth) acrylic. The flame-retardant resin composition is an acid derivative, and the flame-retardant resin composition is further divided into a first agent and a second agent, wherein the first agent contains at least (2) a polymerization initiator. And a two-part flame-retardant resin composition wherein the second part contains at least (3) a reducing agent. Further, it is a flame-retardant adhesive composition comprising the flame-retardant resin composition. Further, it is a cured product of the flame-retardant resin composition. And it is a metal joined body joined by this flame-retardant adhesive composition.

[0014]

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

The flame-retardant resin composition used in the present invention comprises:
(1) a polymerizable vinyl monomer, (2) a polymerization initiator,
The resin composition contains (3) a resin composition containing a reducing agent and (6) an elastomer component used as required, and (4) condensed phosphoric acid and (5) a metal hydroxide as needed. Note that the resin composition may contain paraffins and antioxidants.

The (1) polymerizable vinyl monomer used in the present invention may be any one as long as it is capable of radical polymerization. Among the polymerizable vinyl monomers, the polymerizable vinyl monomer is preferably a polymerizable (meth) acrylic acid derivative from the viewpoint of curing speed and the like.
70 parts by mass of the polymerizable (meth) acrylic acid derivative
It is more preferable that the amount is at least part by mass, and it is most preferable that all the polymerizable vinyl monomers are polymerizable (meth) acrylic acid derivatives.

Here, the polymerizable (meth) acrylic acid derivative means a polymerizable acrylic acid derivative and / or a polymerizable methacrylic acid derivative. These are usually used in liquid or solid form. Examples of the polymerizable (meth) acrylic acid derivative include the following.

General formula ZOR₁ A monomer represented by Wherein Z is (meth) acryloyl
Group, CH_Two= CHCOOCH_Two-CH (OH) CH_Two-Group or CH _Two= C (CH_Three)
COOCH_Two-CH (OH) CH_Two-Represents a group, R₁Is hydrogen, carbon number 1
To 20 alkyl groups, cycloalkyl groups, benzyl groups,
Phenyl group, tetrahydrofurfuryl group, glycidyl
Group, dicyclopentyl group, dicyclopentenyl group or
It represents a (meth) acryloyl group.

Examples of such monomers include (meth) acrylic acid, methyl (meth) acrylate, (meth)
Cyclohexyl acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, glycerol (meth) acrylate and glycerol di (meth) acrylate Is mentioned.

The general formula Z—O— (R_TwoO)_p-R₁ A monomer represented by Where Z and R₁Is as described above.
You. R_TwoIs -C_TwoH_Four−, −C_ThreeH₆-, -CH_TwoCH (CH _Three) −, −C_FourH
₈-Or -C₆H₁₂And p represents an integer of 1 to 25.

Examples of such a monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, ethoxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, and phenoxyethyl (meth) acrylate. Acrylate,
Examples thereof include dicyclopentenyloxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, tripropylene glycol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate.

General formula

Embedded image A monomer represented by In the formula, Z and R ₂ are as described above. R ₃ represents hydrogen or an alkyl group having 1 to 4 carbon atoms;
q represents an integer of 0 to 8.

Examples of such a monomer include 2,2
-Bis (4- (meth) acryloxyphenyl) propane, 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane And 2,2-bis (4- (meth) acryloxypropoxyphenyl) propane and 2,2-bis (4- (meth) acryloxytetraethoxyphenyl) propane.

(Meth) acrylic acid esters of polyhydric alcohols not included in the above or the above-mentioned monomers.

Examples of such a monomer include trimethylolpropane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate. Can be

A urethane prepolymer having a (meth) acryloyloxy group. Such a monomer can be obtained, for example, by reacting a (meth) acrylate having a hydroxyl group, an organic polyisocyanate, and a polyhydric alcohol.

The (meth) acrylate having a hydroxyl group includes, for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate.

Examples of the organic polyisocyanate include:
Examples include toluene diisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.

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 (I).

Embedded image In the formula, R is a CH ₂ CRCR ₄ CO (OR ₅ ) _m — group (where R ₄ is a hydrogen or methyl group, R ₅ is —C ₂ H ₄ —, —C ₃ H ₆ —, —CH ₂ CH (C
H ₃ )-, -C ₄ H _8- , -C ₆ H ₁₂ -or

Embedded image And m represents an integer of 1 to 10. ), And n is 1
Or an integer of 2.

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) phospho. Fate and the like.

One, two or more of the above monomers can be used.

Examples of the polymerizable vinyl monomer other than the polymerizable (meth) acrylic acid derivative include styrene, α
-Alkylstyrene, divinylbenzene, vinyl ether, divinyl ether, N-vinylpyrrolidone, 2-vinylpyridine, and vinyl esters such as vinyl acetate and vinyl propionate.

As the polymerization initiator (2) used in the present invention, an organic peroxide is preferable. Examples of the organic peroxide include cumene hydroperoxide, paramenthane hydroperoxide, tertiary butyl hydroperoxide, diisopropylbenzene dihydroperoxide, methyl ethyl ketone peroxide, benzoyl peroxide and tertiary butyl peroxybenzoate. Can be Among them, cumene hydroperoxide is preferable in terms of reactivity.

The amount of the polymerization initiator to be used is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, per 100 parts by mass of the polymerizable vinyl monomer. If the amount is less than 0.1 part by mass, the curing rate may be low, and if it exceeds 20 parts by mass, the storage stability may be deteriorated.

The reducing agent (3) used in the present invention can be any known reducing agent which reacts with the polymerization initiator to generate radicals. Examples of the reducing agent include a tertiary amine, a thiourea derivative, and a transition metal salt.

The tertiary amine includes, for example, triethylamine, tripropylamine, tributylamine and N, N-dimethylparatoluidine. Examples of the thiourea derivative include 2-mercaptobenzimidazole, methylthiourea, cybutylthiourea, tetramethylthiourea, and ethylenethiourea.
Examples of the transition metal salt include cobalt naphthenate, copper naphthenate, and vanadyl acetylacetonate. Among these, a thiourea derivative is preferred in terms of reactivity, and ethylenethiourea is more preferred.

The amount of the reducing agent used is the amount of the polymerizable vinyl monomer 1
0.05 to 15 parts by mass is preferable with respect to 00 parts by mass,
0.5-5 mass parts is more preferred. If the amount is less than 0.05 part by mass, the curing rate may be low. If the amount exceeds 15 parts by mass, an unreacted reducing agent remains, and the adhesiveness may be reduced.

The condensed phosphoric acid (4) used in the present invention is
It refers to phosphate in which two or more PO ₄ tetrahedrons are produced by covalently polymerizing oxygen atom, polyphosphate general formula represented by _{H n + 2 P n O 3n} + 1 (n is an integer of 2 or more) , (HPO ₃ ) _n
(N is an integer of 3 or more) meta-phosphoric acid, xH ₂ O
· YP refers ultra phosphoric acid represented by _{2 O 5 (0 <x /} y <1). Among these, polyphosphoric acid is preferred in terms of good flame retardancy and curability.

The degree of condensation n of the condensed phosphoric acid (4) is preferably 10 or more, more preferably 100 or more. If the degree of condensation is less than 10, the protons released in the resin composition may inhibit the curability.

The amount of condensed phosphoric acid used is 100 parts by mass of a resin composition containing (1) a polymerizable vinyl monomer, (2) a polymerization initiator, (3) a reducing agent, and (6) an elastomer component used as required. 10 to 75 parts by mass, preferably 15 to 50 parts by mass, per part. If it is less than 10 parts by mass, sufficient flame retardancy may not be obtained, and if it exceeds 75 parts by mass, adhesiveness is reduced, accompanied by a significant increase in viscosity,
There is a possibility that the application operation of the adhesive composition becomes difficult.

Further, in the present invention, in terms of improving flame retardancy,
(5) It is preferable to use a metal hydroxide.

As the (5) metal hydroxide used in the present invention, those which release water of crystallization within a temperature range of 200 to 400 ° C. where thermal decomposition and depolymerization of each component in the resin composition can occur. Preferably, specifically, aluminum hydroxide and / or
Or, magnesium hydroxide is more preferred. Among these, aluminum hydroxide is preferred in terms of curability and flame retardancy.

The amount of the metal hydroxide used is as follows: (1) a polymerizable vinyl monomer, (2) a polymerization initiator, (3) a reducing agent, and (6) a resin composition containing an elastomer component used as required. The amount is preferably from 10 to 75 parts by mass, more preferably from 15 to 50 parts by mass, per part by mass. If the amount is less than 10 parts by mass, sufficient flame retardancy may not be obtained. If the amount is more than 75 parts by mass, the adhesiveness may be reduced, and the viscosity may be significantly increased, which may make it difficult to apply the adhesive composition. is there.

The total amount of the condensed phosphoric acid and the metal hydroxide used is (1) a polymerizable vinyl monomer, (2) a polymerization initiator, (3) a reducing agent, and (6) an elastomer used if necessary. The amount is preferably from 15 to 120 parts by mass, more preferably from 30 to 100 parts by mass, per 100 parts by mass of the resin composition containing the component.

The method for adding the condensed phosphoric acid and the metal hydroxide is not particularly limited, and a method in which different agents are added to the first agent and the second agent, a method in which only one of the agents is added, the same ratio, etc. There is a method of uniformly distributing the amounts, but the method is preferable in that the viscosity of the first agent and that of the second agent are equal.

Further, in the present invention, from the viewpoint of improving the adhesiveness,
(6) It is preferable to use an elastomer component. The elastomer component 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 (meth) acrylic acid derivative.

As the elastomer component (6), acrylonitrile-butadiene-methacrylic acid copolymer, acrylonitrile-butadiene-methyl methacrylate copolymer, methyl methacrylate-butadiene-
Acrylonitrile-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer (MBS), acrylonitrile-styrene-butadiene copolymer, and acrylonitrile-butadiene rubber, linear polyurethane, styrene-butadiene rubber, chloroprene rubber and butadiene rubber Styrene-based thermoplastic elastomers such as synthetic rubber, natural rubber, styrene-polybutadiene-styrene-based synthetic rubber, polyethylene-EPDM
Olefinic thermoplastic elastomers such as synthetic rubber,
And caprolactone type, adipate type and PTMG
Urethane-based thermoplastic elastomer such as mold, polyester-based thermoplastic elastomer such as polybutylene terephthalate-polytetramethylene glycol multi-block polymer, polyamide-based thermoplastic elastomer such as nylon-polyol block copolymer or nylon-polyester block copolymer, 1, Examples thereof include 2-polybutadiene-based thermoplastic elastomer, and PVC-based thermoplastic elastomer. One or more of these elastomer components can be used as long as they have good compatibility. Also, polybutadiene modified with a methacrylic terminal can be used.

Of these, methyl methacrylate-butadiene-acrylonitrile-styrene copolymer and / or acrylonitrile-butadiene rubber are preferable in terms of solubility and adhesion to the resin composition, and methyl methacrylate-butadiene-acrylonitrile-styrene is preferred. More preferably, the copolymer and the acrylonitrile-butadiene rubber are used in combination.

The amount of the elastomer component used is preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass, per 100 parts by mass of the polymerizable vinyl monomer. If the amount is less than 5 parts by mass, the viscosity and the adhesiveness may be reduced. If the amount is more than 50 parts by mass, the viscosity may be too high to cause inconvenience in work.

In the present invention, fine silica powder or the like can be used for adjusting the viscosity and adjusting the viscosity and fluidity.

In the flame-retardant resin composition of the present invention, various paraffins can be used in order to rapidly 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. Of these, paraffin is preferred. The melting point of paraffins is 40-100 ° C
Is preferred.

The amount of the paraffin used is preferably 0.1 to 5 parts by mass based on 100 parts by mass of the polymerizable vinyl monomer. 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, various antioxidants including a polymerization inhibitor can be used for the purpose of improving the storage stability. Examples of the antioxidant include hydroquinone, hydroquinone monomethyl ether, 2,6-ditert-butyl-p-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol),
Triphenyl phosphite, phenothiazine and N-isopropyl-N'-phenyl-p-phenylenediamine. Of these, p-methoxyphenol is preferred.

The amount of the antioxidant used is preferably 0.001 to 3 parts by mass based on 100 parts by mass of the polymerizable vinyl monomer. If the amount is less than 0.001 part by mass, there may be no effect, and if it exceeds 3 parts by mass, the curing strength may be reduced.

In addition, besides these, if desired, a plasticizer,
Known substances such as fillers, colorants or rust inhibitors can also be used.

An embodiment of the present invention is preferably used as an adhesive composition, more preferably as a two-part adhesive composition. For the two-part 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 part and a second part, and at least a polymerization initiator is contained in the first part, At least the reducing agent is stored separately in the second liquid. The two-pack type is preferred in that it has excellent storage stability. In this case, the two agents can be used as a two-part adhesive composition by simultaneously or separately applying and contacting and curing.

An adherend is joined with the adhesive composition of the present invention to produce a joined body. For various materials of the adherend,
There is no limitation on paper, wood, ceramic, glass, ceramics, rubber, plastic, mortar, concrete, metal, etc., but when the adherend is metal, it exhibits excellent adhesion.

[0059]

The present invention will be described in more detail with reference to the following experimental examples. Hereinafter, the unit of the amount of each substance used is shown in parts by mass. The following abbreviations were used for each substance. The melting point of paraffin is 56 ° C. NBR: acrylonitrile-butadiene rubber MBAS: methyl methacrylate-butadiene-acrylonitrile-styrene copolymer Acidic phosphoric acid compound: acid phosphoxyethyl methacrylate

Various physical properties were measured as follows.

[Viscosity] In accordance with JIS K-7117, 500 ml of each of the first liquid and the second liquid was taken and left in a thermostat at 25 ° C. for 24 hours to obtain a sample. Measurement of viscosity is 25
The temperature was continuously measured at 2 ° C. for 2 minutes using a single cylindrical viscometer (rotor rotation speed: 20 rpm).

[Tensile shear bond strength] JIS K-685
According to No. 6, a test piece (100 mm × 25 mm × 1.6 mm
t, SECC-D sandblast treatment), and a mixture of equal amounts of the first agent and the second agent was applied. Then, the other test piece was immediately superimposed and bonded, and then cured at room temperature for 24 hours to obtain a sample. The tensile shear bond strength (unit: MPa) of the sample was measured at a tensile speed of 10 mm / min in an environment at a temperature of 23 ° C. and a relative humidity of 50%.

[Flame Retardancy] A cured product having a thickness of 1/8 inch (0.3175 cm) was prepared according to the UL-94 vertical combustion test method, and the flammability was evaluated.

Experimental Example 1 A resin composition having the composition shown in Table 1 was prepared. Using this resin composition, a two-part flame-retardant adhesive composition having the composition shown in Table 2 was prepared, and the physical properties were evaluated. Table 2 shows the results.

[0065]

[Table 1]

[0066]

[Table 2]

Experimental Example 2 The same procedure as in Experimental Example 1 was carried out except that a two-part flame-retardant adhesive composition having the composition shown in Table 3 was prepared. Table 3 shows the results.

[0068]

[Table 3]

[0069]

Industrial Applicability The flame-retardant resin composition of the present invention can provide a metal joined body which is less harmful to the human body and the environment and has excellent flame retardancy and adhesiveness. large.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 3/32 C08K 3/32 C08L 33/04 C08L 33/04 101/00 101/00 C09J 4/00 C09J 4/00 F-term (reference) 4J002 AC07W BB15W BG04W BG07X BN14W CK02W CL08W DE079 DE149 DH029 EH076 EK007 EN028 EV128 FD139 FD206 FD207 FD208 GJ01 4J011 PA36 PA46 PA69 PA76 PA78 PB29 CAB12AC034 CA042 CA072 CA082 CA142 DA122 DB011 DB022 DB041 DB052 DB062 DD051 DE011 DE021 DF012 DF041 DF051 DF052 DF082 DH031 DH041 DJ021 EC012 EC321 ED002 EF002 EF351 FA041 FA061 FA081 FA091 HC11 HA141HA31FA01 FA141 FA151 FA161 FA01 FA141 FA151 KA11 KA14 KA36 LA08 MA02 MA04 MA05 MA06 MA08 MA09 MA10 MA12 NA12 4J100 AL0 8P AL63P BA02P BA03P BA04P BA08P BC04P BC43P BC53P BC54P CA01 JA03

Claims (8)

[Claims] A flame-retardant resin composition comprising (1) a polymerizable vinyl monomer, (2) a polymerization initiator, (3) a reducing agent, and (4) condensed phosphoric acid. 2. The flame-retardant resin composition according to claim 1, further comprising (5) a metal hydroxide. 3. The flame-retardant resin composition according to claim 1, further comprising (6) an elastomer component. 4. The flame-retardant resin composition according to claim 1, wherein (1) the polymerizable vinyl monomer is a polymerizable (meth) acrylic acid derivative. 5. The flame-retardant resin composition according to claim 1, which is divided into a first agent and a second agent, wherein the first agent contains at least (2) a polymerization initiator. And a two-part flame-retardant resin composition wherein the second part contains at least (3) a reducing agent. 6. A flame-retardant adhesive composition comprising the flame-retardant resin composition according to claim 1. 7. A cured product of the flame-retardant resin composition according to claim 1. 8. A metal joined body joined by the flame-retardant adhesive composition according to claim 6.