JP3332438B2 - Room temperature curable two-part composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a two-part composition curable at room temperature which can be widely used in various fields as an adhesive, a coating agent, a gap filler, and a casting agent.

[0002]

2. Description of the Related Art Conventionally, as a two-part type curable composition, for example, a radical polymerizable (meth) acrylate monomer is used as a main component, and one liquid contains an organic peroxide as a polymerization initiator. The other liquid is known as a polymerization accelerator, for example, a two-liquid radical polymerizable composition containing a metal chelate compound, an organic amine, a carboxylic acid, a polyamide, an organic phosphorus compound, a thiourea compound, and metal salts. I have. Such a two-part type radical polymerizable composition is excellent in quick-curing property, low-temperature curability, workability, etc., so that it can be used for bonding various parts of an automatic system, bonding each part of a speaker, and assembling electric equipment. If it is used in the fields of adhesion and protection coating of various parts of a small motor, production efficiency can be improved.

However, in most cases, a radical polymerizable monomer as a main component used in such an adhesive is a volatile monomer such as methyl methacrylate in order to impart surface drying properties. However, such (meth) acrylate monomers have the drawback that they are very hard and have a large curing shrinkage.

In order to improve such disadvantages, a method of dissolving and adding various high-molecular substances (for example, various synthetic rubbers and various synthetic resins) has been adopted, but an essential solution has not been reached. In the field of filling and bonding, where curing shrinkage is large, and in the field of repeated exposure to low and high temperatures, it is not possible to absorb the strain generated in the adherend and the adhesive layer, resulting in fatigue failure of the adherend. There is a problem that it easily occurs.

On the other hand, in the field of epoxy-based curable compositions, in order to make the cured product soft and flexible,
It is known that various rubbers are added or the epoxy compound is modified with a urethane group or various rubbers in the main chain and side chains.

Recently, a curable composition comprising a combination of a modified silicone and a known curing agent of epoxy and epoxy has been proposed as a composition exhibiting rubber-like elasticity. This kind of composition is used for an adhesive part which is repeatedly subjected to distortion or stress due to its properties, and greatly contributes to improvement in adhesion reliability and adhesion durability.

However, while the modified silicone-epoxy-epoxy curing agent composition has such excellent properties, it hardly cures at room temperature and low temperature, and is not suitable for bonding and assembling on a production line which requires fast curing. There are, coating,
In the field of painting, there has been a problem that use is restricted.

[0008]

SUMMARY OF THE INVENTION The present invention relates to a room-temperature-curable two-pack type composition having both the quick-curing property of a (meth) acrylate-based polymerizable composition and the rubber-like elasticity of a modified silicone-epoxy-based cured product. It is an object of the present invention to improve the disadvantages that the (meth) acrylate-based polymerizable composition has too hard cured properties and that the modified silicone-based curable composition has a low curing rate in order to obtain a functional material. . That is, it is intended to obtain a fast-curing, room-temperature curable composition having rubber-like elasticity.

The present inventors have made various studies to solve the above-mentioned problems in the two-pack type radical polymerizable (meth) acrylate composition and the modified silicone-based curable composition, and as a result, have found that (meth) By combining the acrylate monomer and the modified silicone, a room-temperature-curable two-part reactive composition that is fast-curing and rubber-elastic and has improved defects while leaving its respective excellent parts can be obtained. And have reached the present invention.

[0010]

That is, in the room-temperature-curable two-pack composition of the present invention, the liquid A comprises a polymer compound having a reactive silicon group and a polymerization accelerator of a radical polymerizable monomer as essential components. The liquid B contains a radical polymerizable monomer, a polymerization initiator of the radical polymerizable monomer, and a curing accelerator of a polymer compound having a reactive silicon group as essential components.

The polymerization accelerator and the polymerization initiator of the radical polymerizable monomer may be contained in one of the liquid A and the liquid B. Contrary to the above constitution, the polymerization initiator is added to the liquid A. Liquid B may also contain a polymerization accelerator.

Further, the radical polymerizable monomer may be contained in the solution A while being contained in the solution B.
In this case, the kind and combination of the radical polymerizable monomers used in the liquid A and the liquid B may be the same or different from each other.

Further, the solution A contains a polymer compound having a reactive silicon group, a radical polymerizable monomer, and a polymerization initiator of the radical polymerizable monomer as essential components.
The liquid may contain a curing accelerator for a polymer compound having a reactive silicon group and a polymerization accelerator for a radical polymerizable monomer as essential components.

Also in this case, the polymerization accelerator of the radical polymerizable monomer and the polymerization initiator may be contained in either one of the solution A and the solution B. A liquid B may contain a polymerization accelerator.

It is also possible that only the polymerization accelerator of the radical polymerizable monomer is an essential component of the solution B, and the remaining components are all contained in the solution A. Liquid B can be used as a honeymoon-type adhesive by using it as a curing-promoting primer.

There is no particular limitation on the mixing ratio of the liquid A and the liquid B, and any mixing ratio can be used as long as the effects of the present invention can be achieved.

The functional radically polymerizable monomer in the present invention is a radically polymerizable monomer containing acrylate and / or methacrylate as a main component. Examples of the acrylate and / or methacrylate, ie, (meth) acrylate, include Methyl (meth) acrylate, ethyl (meth) acrylate, stearyl (meth)
Alkyl or substituted alkyl-type monofunctional (meth) acrylates such as acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate; methoxyethyl ( Ether-type monofunctional (meth) such as meth) acrylate, methoxydiethylene glycol (meth) acrylate, and methoxypolyethylene glycol (meth) acrylate
Acrylates; alkylene-type bifunctional (meth) acrylates such as ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, and neopentyl glycol di (meth) acrylate; diethylene glycol di (meth) acrylate, polyethylene glycol Ether-type bifunctional (meth) acrylates such as di (meth) acrylate, polypropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol di (meth) acrylate; trimethylolpropane tri (meth) acrylate , Trimethylolethanetri (meta)
Trifunctional (meth) acrylates such as acrylates; polyfunctional (meth) acrylates such as pentaerythritol tetra (meth) acrylate, dipentaerythritol poly (meth) acrylate, tetramethylolmethanetetra (meth) acrylate; 2-hydroxyethyl (meth) acrylate )
Acrylate, tetramethylolmethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, 2,3-dibromopropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate,
Polar group or substituted atom-containing (meth) acrylate such as 2-chloroethyl (meth) acrylate or dimethylaminoethyl (meth) acrylate; 2,2-bis (4-acryloxy-diethoxyphenyl) propanedi (meth) acrylate, bis Oxypolyethylene bisphenol A
Epoxy (meth) acrylates such as di (meth) acrylate, bisoxypropyleneated bisphenol A-di (meth) acrylate, bisoxy-2-hydroxyethylated bisphenol A-di (meth) acrylate;
Polyester-type di (meth) acrylates such as adipic acid-1,6-hexanediol-di (meth) acrylate; and urethane (meth) acrylate.

These (meth) acrylates may be used alone or in combination of two or more. Further, depending on the case, a monomer other than the (meth) acrylate may be used together with these (meth) acrylates in a small amount. When using solid monomers,
It is desirable to use a liquid monomer such as 2-hydroxyethyl methacrylate in combination.

A specific example of a polymer compound having one or more reactive silicon groups in the molecule is disclosed in JP-A-50-1565.
No. 99, JP-A-52-73998, JP-A-5-73998
Compounds proposed in JP-A-8-10418, JP-A-62-230822, etc.
7, an organic silicone compound having at least two silicon atoms to which a hydrolyzable group is bonded in a molecule, JP-A-60-228516, JP-A-63-112642, There is a composition such as a composition comprising an oxyalkylene polymer having a silicon group and a (meth) acrylate (co) polymer having a silicon group proposed in JP-A-1-131271.

Further, a polyester polyol urethane prepolymer and a polyether polyol urethane prepolymer in which terminal isocyanate groups are blocked with an active hydrogen group-containing silane coupling agent such as mercaptosilane, aminosilane, or hydroxysilane, etc. Those obtained by directly reacting isocyanate silane with hydroxyl groups of polyether polyol and polyester polyol can be used.

These polymer compounds having reactive silicon may be used alone or in combination of two or more. Further, in some cases, a polymerizable monomer such as (meth) acrylate may be used in combination.

As a method for curing the (meth) acrylate component of the present invention, a method already used for a two-component radically polymerizable composition can be used.

That is, examples of the radical polymerization initiator include diacyl peroxides such as benzoyl peroxide and acetyl peroxide; hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide; methyl ethyl ketone peroxide; Ketone peroxides such as cyclohexanone peroxide; dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide; peroxyesters such as t-butylperoxyacetate; thioglycerol and pyrazoles and / or A combination of pyrazolones; and various other known radical polymerization initiators. Two or more radical polymerization initiators can be used in combination.

The polymerization accelerator used in combination with the radical polymerization initiator for curing the (meth) acrylate component of the composition of the present invention includes, for example, N, N-dimethylaniline, N, N-dimethyl-P- Tertiary amines such as toluidine, diisopropanol-P-toluidine and triethylamine; polyamines such as diethylenetriamine, triethylenetetramine and pentaethylenehexamine; thioureas such as thiourea, ethylenethiourea, benzoylthiourea, acetylthiourea and tetramethylthiourea Ureas;
Known organic compounds such as organic acid or inorganic acid salts of metals such as copper, cobalt, manganese and vanadium and organic chelates with acetylacetone; reducing organic compounds such as ascorbic acid and gallic acid; mercaptans; Accelerators. Two or more of these curing accelerators can be used in combination.

The amounts of the radical polymerization initiator and the polymerization accelerator used in the two-part composition curable at room temperature of the present invention are the same as those in the prior art. ~ 20% by weight, preferably 0.1 ~
It is about 10% by weight. If the amount used is too small, the polymerization curing speed becomes slow, and the curing takes a long time. If the amount is too large, heat generation becomes large, and the cured product layer contains air bubbles and the physical properties of the cured product are reduced.

In the room temperature-curable two-part composition of the present invention, a wax or a wax such as a paraffin wax or a rice wax may be used as a surface drying property improving material, if necessary, in a portion containing a radical polymerizable monomer as a main component. P-benzoquinone, quinone-type stabilizers such as hydroquinone, hindered phenolic antioxidants such as butylhydroxytoluene, inorganic and organic fillers, dyes, pigments, thixotroping agents, aminosilane, epoxysilane, and acidic phosphoric acid group-containing An adhesion-imparting agent such as a (meth) acrylate monomer can be contained.

As a method for curing a polymer compound having a reactive silicon group, which is the other main component of the present invention, a curing accelerator which has already been put to practical use and which is already known can be used. Examples of the curing accelerator include organic tin compounds such as dibutyltin dilaurate, dioctyltin dimaleate, dibutyltin phthalate, stannous octylate, dibutyltin methoxide, dibutyltin diacetylacetate, and dibutyltin diversate; tetrabutyl titanate, tetraisopropyl titanate Organic titanate compounds such as triethanolamine titanate; metal salts of carboxylic acids such as lead octylate and cobalt naphthenate; aminosilanes such as γ-aminopropyltriethoxysilane and γ-aminopropyltrimethoxysilane; tetramethylammonium chloride And quaternary ammonium salts such as benzalkonium chloride; and organic phosphoric compounds such as monomethyl phosphoric acid, di-n-butyl phosphoric acid, and triphenyl phosphate. I can do it.

These may be used alone or in combination of two or more. These compounds can be added to the component having a reactive silicon group. However, it is preferable to add the compound to a portion composed of only a radical polymerizable monomer in terms of storage stability and the like. There is an advantage that it becomes easier. The amount of the curing accelerator used is sufficient if it is about the amount conventionally used.

In the two-part composition curable at room temperature according to the present invention, waxes such as paraffin wax and rice wax may be further added as necessary to the surface-drying property-improving material, in the portion mainly containing reactive silicon groups. Various (meth) acrylate monomers; quinone-type stabilizers such as P-benzoquinone and hydroquinone, hindered phenolic antioxidants such as butylhydroxytoluene, inorganic and organic fillers, dyes, pigments, thixotropic agents, and defoamers An agent, a leveling agent, a thickener, a thickener such as a high-boiling solvent, and other various additives can be blended.

Further, when an acidic phosphoric acid compound such as di-n-butylphosphoric acid or 2- (meth) acryloxyethyl phosphate which gives a very fast curing property is used as a curing accelerator for the reactive silicon group, the reactivity is low. If such an acid remains even after the silicon group is cured, it acts as a catalyst for depolymerization of the polymer and may extremely reduce the heat aging property. It is recommended to add an inorganic filler such as calcium oxide, calcium carbonate, and magnesium oxide which has a function of soaking, and an epoxy compound such as bisphenol A type epoxy and bisphenol F type epoxy. Further, an adhesive agent such as epoxysilane and aminosilane may be contained.

[0031]

Embodiments of the present invention will be described below. In the following, all parts and percentages are expressed on a weight basis unless otherwise specified. The present invention relates to a room-temperature-curable two-part composition, which requires two kinds of liquid compositions, and is named for convenience of explanation. The liquid composition containing the polymer compound having reactive silicon is referred to as [liquid A], and the liquid composition containing a functional radical polymerizable monomer as a main component is referred to as [liquid B].

Example 1 [Preparation of Solution A] Modified silicone S-303 (trade name of a polymer compound having reactive silicon, manufactured by Kanegabuchi Chemical Industry Co., Ltd.)
100 parts of dicyclopentenyl methacrylate 2
Solution A was prepared by stirring and mixing 0 parts and 2 parts of cumene hydroperoxide with a lab stirrer.

[Preparation of solution B] Dicyclopentenyl methacrylate 50 parts, 2-hydroxypropyl methacrylate 50 parts, vanadium acetylacetonate 0.05
, 0.5 part of hydroquinone and 2 parts of 2-methacryloxyethyl phosphate were stirred using a lab stirrer and dissolved and mixed to prepare a solution B. A mixing ratio of the liquid A and the liquid B was set to 1: 1 (weight ratio) to prepare a room temperature-curable two-part composition.

A curing test was performed on the obtained two-part curable composition at room temperature, and the following set time measurement, flexibility measurement and cured state observation were performed. The results are shown in Table 1. The set time was as good as 6 minutes, and the flexibility was also good. What is the cure situation? The whole was uniformly cured at the same time and was good.

Measurement of Set Time Two mild steel plates having a length of 100 mm, a width of 25 mm, and a thickness of 1.5 mm were used, bonded together in a half-inch wrap with the composition of Example 1, and a tensile load was applied in the vertical direction. The time required to withstand 3 kg was measured and defined as a set time.

Measurement of flexibility The composition of Example 1 was mixed at a predetermined ratio, and the length was 100 m.
A test piece was prepared by applying a coating having a thickness of 1.0 mm on a mild steel plate having a thickness of 25 mm and a width of 25 mm and a thickness of 0.5 mm and curing at room temperature for 24 hours. This is wound around a 1-inch mandrel at room temperature, and the condition of the surface of the cured product is observed.

Observation of Curing Condition The composition of Example 1 was mixed at a predetermined ratio to 50 g, and the condition of curing was observed.

Examples 2 to 5 [Preparation of Solution A] Instead of the modified silicone S-303,
Modified silicone SAT-010 [trade name of polymer compound having reactive silicon, manufactured by Kaneka Chemical Industry Co., Ltd., Example 2], modified silicone M-217 [trade name of polymer compound having reactive silicon, Liquid A was prepared in exactly the same manner as in Example 1 except that the following synthetic product (Example 4) and the following synthetic product (Example 5) manufactured by Kanegafuchi Chemical Industry Co., Ltd. were used.

Each of the above solutions A and B of Example 1 were mixed in the same manner as in Example 1, and the performance was measured by the same curing test as in Example 1. The results are shown in Table 1, and all the test results were good.

Preparation of Synthetic Product In a four-necked flask equipped with a stirrer, a thermometer, a nitrogen gas inlet, and a reflux condenser, 300 parts of polytetramethylene ether glycol having a molecular weight of 3000 were charged, and
While stirring the mixture while heating to ° C., dry nitrogen gas is blown thereinto to dry the contents until the content becomes 0.003% or less as measured by a Karl Fischer moisture meter. next,
The content was cooled to 30 ° C., and 44 parts of Y-9030 (trade name of isocyanate silane manufactured by Nippon Unicar Co., Ltd.) and 0.1 part of di-n-butyltin dilaurate were charged.
The mixture was stirred at ５０50 ° C., and the disappearance of the NCO group was confirmed by IR measurement, and the reaction was terminated. By this reaction, an isocyanate silane adduct of the polyol was obtained.

Preparation of Synthetic Product In the same four-necked flask as in Example 4, 2,000 parts of polypropylene glycol having a molecular weight of 2,000 was charged.
Dehydration is performed in the same manner as in Example 4. Next, the contents are
While maintaining the temperature at ~ 90 ° C, 68 parts of MDI are charged and the reaction is carried out at the same temperature until the NCO content becomes 1.45%. Next, 230 parts of γ-aminopropyltrimethoxysilane and 0.1 part of di-n-butyltin dilaurate were charged,
In the same manner as in Example 4, the disappearance of the NCO group was confirmed by IR measurement, and the reaction was terminated. By this reaction, a product obtained by adding aminosilane to the NCO group of the urethane prepolymer of the polyol was obtained.

[0042]

[Table 1]

Comparative Example 1 60 parts of methyl methacrylate, 40 parts of 2-hydroxyethyl methacrylate, 10 parts of Hiker 1072 (trade name of NBR rubber manufactured by Nippon Synthetic Rubber Co., Ltd.), 0.5 part of paraffin wax, 0.1 part of hydroquinone Is stirred with a lab stirrer to form a uniform solution. Next, this is bisected, and 4 parts of cumene hydroperoxide is added to one of the two to obtain a uniform solution (Solution A). To the other, 2 parts of ethylenethiourea and 1 part of 2-methacryloxyethyl phosphate are added to form a uniform solution (solution B). The mixing ratio of the liquid A and the liquid B is 1: 1 by weight. Thus, a conventional (meth) acrylate-based polymerizable composition (room temperature curable two-part composition) was obtained.

Liquid A and liquid B were mixed in the same manner as in Example 1, and the performance was measured by the same curing test as in Example 1. The set time was as good as 8 minutes, but cracking, peeling and foaming occurred, and the flexibility was poor. The curing status is
It was cured in a foamed state by the heat of reaction and was non-uniform.

Comparative Example 2 Kanebuchi Chemical Co., Ltd.
Obtained by adding 5 parts of tris, dimethylaminomethylphenol to 100 parts of Cyril 5B-30 (product A)
A composition (solution B) was prepared by adding 100 parts of Epicoat # 828 manufactured by Shell Chemical Co., Ltd. as an epoxy compound and 3 parts of dibutyltin dilaurate. The mixing ratio of the liquid A and the liquid B is 2: 1 by weight. Thus, a conventional room temperature-curable two-part composition was obtained.

Liquid A and Liquid B were mixed at a weight ratio of 2: 1 and the performance was measured by the same curing test as in Example 1. The set time was extremely long at 65 minutes.
The flexibility was good, but the curing condition was uneven after 60 minutes, with the surface being peeled off from the surface.

Examples 6 to 12 In the following examples, (a) is a polymerization initiator of a radically polymerizable monomer, (b) is a polymerization accelerator of a radically polymerizable monomer, and (c) is a polymerization initiator having reactive silicon. It is a curing accelerator for molecular compounds.

[Preparation of Solution A] Modified silicone S-303
[Kanabuchi Chemical Industry Co., Ltd., trade name of polymer compound having reactive silicon group] 100 parts, dicyclopentenyl methacrylate 20 parts, (a) 4 parts of cumene hydroperoxide (Example 6), ( b) 2 parts of ethylene thiourea (Example 7), (a) 4 parts of cumene hydroperoxide,
(B) 2,5-dimethylpyrazole 2 parts and 1-phenyl-3-methyl-5-pyrazolone 0.5 part (Example 8), (a) methyl ethyl ketone peroxide 4 parts (Example 9), (a) 1 part of benzoyl peroxide (Example 10), (a) 3,5-dimethylpyrazole 2
Parts and 0.5 part of thioglycerol (Example 11),
(A) 2 parts of cumene hydroperoxide and (b) 1 part of saccharin (Example 12) were added and prepared.

[Preparation of Solution B] For 50 parts of dicyclopentenyl methacrylate and 50 parts of 2-hydroxypropyl methacrylate, 2 parts of (b) ethylenethiourea and 1 part of (c) di-n-butyl phosphoric acid (Example 6) ), (A) 4 parts of cumene hydroperoxide and (c) 1 part of di-n-butyl phosphoric acid (Example 7), (b) 0.1 part of copper 2-ethylhexanoate, and (c) Phosmer M (oil and fat) Products Co., Ltd.
1 part (Example 8), (b) cobalt naphthenate 0.1 g (trade name of acid phosphoxyethyl methacrylate).
1 part and (c) 0.5 part of di-n-butyltin dilaurate (Example 9), (b) 1 part of N, N-dimethylparatoluidine and (c) 0.5 part of dibutyltin diacetylacetate
Part (Example 10), (b) 0.1 part of vanadium acetylacetonate and (c) Phosmer M (Oil and Fat Products Co., Ltd.)
1 part (Example 11), (b) 0.1 part of N, N-dimethylparatoluidine, copper 2-ethylhexanoate 0.01
And 1 part of tri-n-butylamine, 0.5 part of (c) dibutyltin diacetyl acetate and 1 part of γ-aminopropyltriethoxysilane (Example 12), respectively.

The performance of the obtained two-part curable composition at room temperature was evaluated in the same manner as in Example 1. The results are shown in Table 2, and all the test results were good.

From the results of Examples 6 to 12 described above, the room temperature-curable two-part composition of the present invention was prepared by using various types of radically polymerizable monomer polymerization initiators and polymerization accelerators. It was also found that good results were obtained. It was also found that various compounds can be used as a curing accelerator for a polymer compound having a reactive silicon group.

Further, as can be seen from Examples 6 and 7 in which the combination of the polymerization initiator and / or the polymerization accelerator of the radical polymerizable monomer was reversed between the solution A and the solution B, the radical polymerizable monomer was It was found that the monomer polymerization initiator and the curing accelerator can be exchanged between the liquid A and the liquid B.

[0053]

[Table 2]

Examples 13 to 21 In the following examples, (M) is a radical polymerizable monomer and (d) is a stabilizer.

[Preparation of Solution A] Modified silicone SAT-0
10 (manufactured by Kanegafuchi Chemical Co., Ltd., trade name of a polymer compound having a reactive silicon group): 100 parts, (M) 20 parts of methyl methacrylate, (a) 1 part of cumene hydroperoxide, (b) 3 , 5-dimethylpyrazole 2 parts, thioglycerol 0.5 part (Example 13), without (M),
(A) (b) Same as Example 13 (Example 14), (M)
20 parts of isobornyl acrylate, (a) (b) same as Example 13 (Example 15), (M) 20 parts of dicyclopentenyl acrylate, (a) (b) same as Example 13 (Example 16) , (M) diallyl phthalate monomer 1
0 parts, (a) (b) same as Example 13 (Example 17),
(M) None, (a) (b) Same as Example 13 (Example 1)
8), 20 parts of (M) NK ester BE400 [trade name of 2,2'-bis (4-methacryloxydiethoxyphenyl) propane, manufactured by Shin-Nakamura Kogyo Co., Ltd.], (a)
(B) Same as Example 13 (Example 19), (M) 10 parts of styrene monomer, (a) (b) Same as Example 13 (Example 20), (M) 20 parts of dicyclopentenyl methacrylate, ( a) 4 parts of cumene hydroperoxide,
(B) The same as in Example 13 (Example 21) was added, and the mixture was stirred and dissolved with a lab stirrer to prepare a liquid A.

[Preparation of Solution B] (M) 40 parts of methyl methacrylate and 60 parts of 2-hydroxyethyl methacrylate 60
3 parts of (b) and (c) accelerator VN ₂ (trade name of vanadium acidic phosphoric acid solution manufactured by Nippon Kayaku Co., Ltd.)
(D) 0.5 part of butylhydroxytoluene (Example 1)
3), (M) 2-hydroxypropyl methacrylate 6
0 parts and light ester 3002M (Kyoeisha Yushi Co., Ltd.)
, 40 parts of a product name of epoxy dimethacrylate)
(B) (c) (d) Same as Example 13 (Example 14),
(M) 60 parts of isobornyl acrylate and 40 parts of Art Resin UN-6060PTM (trade name of urethane dimethacrylate manufactured by Negami Industry Co., Ltd.), (b) and (c)
(D) Same as Example 13 (Example 15), (M) 50 parts of dicyclopentenyl acrylate and 50 parts of 2-hydroxypropyl acrylate, (b) (c) (d) Same as Example 13 (Example 16) ), (M) 10 parts of diallyl phthalate monomer and 90 parts of 2-hydroxypropyl methacrylate, (b) (c) (d) Same as Example 13 (Example 17), (M) 10 parts of trimethylolpropane trimethacrylate and 90 parts of dicyclopentenyl methacrylate, (b) (c) (d) Same as in Example 13 (Example 18), (M) NK ester BE400 [manufactured by Shin-Nakamura Kogyo Co., Ltd., 2,2′-bis (4 -Methacryloxydiethoxyphenyl) propane trade name], 20 parts, (b)
(C) (d) Same as Example 13 (Example 19), (M)
40 parts of styrene monomer and New Track 420S
(Kao Soap Co., Ltd., bisphenol A unsaturated polyester resin) 60 parts, (b) (c) (d) Same as Example 13 (Example 20), (M) Art resin UNA-6
(Trade name of urethane dimethacrylate, manufactured by Negami Industry Co., Ltd.) 60 parts and dicyclopentenyl methacrylate 40
Parts, (b) 2 parts of ethylene thiourea and 0.1 part of copper naphthenate.
02 parts, (c) 2 parts of dibutyltin diacetylacetate and 1 part of dibutyltin sulfide, and (d) the same as in Example 13 (Example 21) were each dissolved by stirring with a lab stirrer to prepare solution B.

The performance of the obtained room temperature-curable two-part composition was evaluated in the same manner as in Example 1. The results are shown in Table 3, and all the test results were good.

From the results of Examples 13 to 21, it can be seen that various polymerizable monomers can be used for the room temperature-curable two-part composition of the present invention.

[0059]

[Table 3]

Examples 22 to 26 [Preparation of solution A] 80 parts of modified silicone S-303 (trade name of polymer compound having a reactive silicon group, manufactured by Kaneka Chemical Industry Co., Ltd.) and modified silicone SAT-010 Cumene hydroperoxide 1 was added to 20 parts (trade name of a polymer compound having a reactive silicon group, manufactured by Kanebuchi Chemical Industry Co., Ltd.)
Part and thioglycerol 0.5 part were stirred and dissolved with a lab stirrer to prepare a solution A.

[Preparation of Solution B] 3,5-Dicyclopentenyl methacrylate 40 parts, 2-hydroxybutyl methacrylate 40 parts, NK ester BE-40020 parts were mixed with 3,5-
Dimethyl pyrazole 3 parts, accelerator VN ₂ 4 parts,
2 parts of γ-methacryloxypropyltrimethoxysilane,
Solution B was prepared by dissolving 0.3 part of butylhydroxytoluene by stirring with a laboratory stirrer.

The thus obtained solution A and solution B were used in a polymerization ratio of 10:90 (Example 22), 25:75 (Example 23), 50:50 (Example 24), and 75:25. The mixture was mixed at a ratio of (Example 25) and 90:10 (Example 26), and the curability and physical properties of the cured product were evaluated in the same manner as in Example 1. The results are shown in Table 4, and all the test results were good.

From the results of Examples 22 to 26, it was found that the room temperature-curable two-part composition of the present invention exhibited good performance in a wide range of the mixing ratio of the A liquid and the B liquid.

[0064]

[Table 4]

Example 27 [Preparation of Solution A] 100 parts of modified silicone S-303 (trade name of a polymer having a reactive silicon group, manufactured by Kaneka Chemical Industry Co., Ltd.), dicyclopentenyl methacrylate 10
In 0 parts, 4 parts of cumene hydroperoxide as a polymerization initiator of a radical polymerizable monomer was stirred and dissolved by a lab stirrer to prepare a liquid A.

[Preparation of Solution B] Vanadium acetylacetonate was used as a polymerization accelerator for radically polymerizable monomers.
2 parts and 1 part of di-n-butyl phosphoric acid as a curing accelerator for a polymer compound having a reactive silicon group were stirred and dissolved by a lab stirrer to prepare a liquid B.

The performance of the obtained room temperature-curable two-part composition was evaluated in the same manner as in Example 1. Set time is 8
Minute and good, and flexibility was also good. The curing status is
The whole was uniformly cured at the same time and was good.

From the results of Example 27, it can be seen that the room-temperature-curable two-part composition of the present invention comprises a polymer having a reactive silicon group, a radically polymerizable monomer, and a radically polymerizable monomer polymerization initiator in Solution A. In addition, it was found that the liquid B exhibited good performance even in the case of a composition containing only a curing accelerator of a polymer compound having a reactive silicon group and a polymerization accelerator of a radical polymerizable monomer.

The polymerization initiator of the radical polymerizable monomer and the polymerization accelerator can of course be interchanged with each other as long as no adverse reaction occurs with the curing accelerator of the polymer compound having a reactive silicon group. It is. Examples 28 to 33

[Preparation of Solution A] Modified silicone S-302
100 parts of a polymer compound having a reactive silicon group (manufactured by Kanegabuchi Chemical Industry Co., Ltd.), 100 parts of dicyclopentenyl methacrylate, 4 parts of cumene hydroperoxide as a polymerization initiator of a radical polymerizable monomer, 2 parts of dibutyltin diacetyl acetate as a curing accelerator for a polymer compound having a reactive silicon group, and 1 part of saccharin as a curing accelerator for radically polymerizable monomers in Examples 31 to 33, were stirred and dissolved by a lab stirrer. Then, solution A was prepared.

[Preparation of Solution B] An accelerator VN ₂ (trade name of an acidic phosphoric acid solution of vanadium, manufactured by Nippon Kayaku Co., Ltd.) 100 as a polymerization accelerator for a radical polymerizable monomer
Parts (Example 28), 100 parts of copper 8% solution of naphthenate (Example 29), 100 parts of 6% solution of cobalt naphthenate (Example 30), Banax # 808 [manufactured by DuPont,
100 parts of trade name of reaction product of aldehyde and amine] (Example 31), 100 parts of 8% copper naphthenate solution (Example 3)
2), 100 parts of a 6% solution of cobalt naphthenate (Example 3)
3) was used as B liquid.

The performance of the obtained two-part curable composition at room temperature was evaluated in the same manner as in Example 1. The results are shown in Table 5. As can be seen from Table 5, all the test results were good.

From the results of Examples 28 to 33, it can be seen that the room temperature-curable two-part composition of the present invention shows good performance even in the case of the composition in which the polymerization accelerator of the radically polymerizable monomer is blended with the solution B. Do you get it.

[0074]

[Table 5]

Examples 34 to 39 Using the same liquids A and B as in Examples 28 to 33, liquid B was applied thinly on one side with a waste cloth and liquid A was overlaid without intentional mixing. As for the method of applying the paint, tests for set time and flexibility were performed. Table 6 shows the results. As can be seen from Table 6, all the test results were good.

As can be seen from the results of Examples 34 to 39, the room temperature-curable two-part composition of the present invention showed good performance even when the liquid B was used as a curing acceleration primer. Further, the room temperature curing type two-part composition of the present invention,
Solution A was applied to one side, and solution B was applied to the other, and it was confirmed that honeymoon bonding was also possible.

[0077]

[Table 6]

[0078]

As described above, since the room-temperature-curable two-part composition of the present invention is quick-curing and has rubber-like flexibility, it can be used as a flexible protective coating material, a potting material, and a sealant. When used for materials and adhesives, work speeds up,
It is effective for high reliability.

Even when a low-odor (low-volatility) radical polymerizable monomer other than the methyl methacrylate monomer is used, since the curing system of a polymer compound having a reactive silicon group is used in combination, Can be performed promptly, so that the deterioration of the working environment due to the volatile polymerizable monomer can be prevented.

Further, without using a material such as NBR rubber which takes a long time to dissolve, only by mixing a liquid material,
Since the composition of the present invention can be produced, the production cost can be significantly reduced.

The room-temperature-curable two-part composition of the present invention is used for filling a large amount, which could not be used because the conventional (meth) acrylic curable composition had a large curing shrinkage and could not be used at low temperatures. It can be used effectively for bonding ferrite magnets that could not be used because of their high hardness, or for bonding large-area panels where curing shrinkage is large and distortion is likely to occur.

Further, the room temperature-curable two-part composition of the present invention is an on-site work at a low temperature where the conventional modified silicone-epoxy curable composition cannot be used at a low temperature because of its slow curing. It can be effectively used for gap filling which could not be used because the whole did not cure at a uniform speed, or for assembly work on a production line which could not be used because it did not cure quickly.

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Claims (7)

(57) [Claims] 1. A liquid contains a polymer compound having a reactive silicon group and a polymerization accelerator of a radical polymerizable monomer as essential components, and B liquid contains a radical polymerizable monomer and a polymerization initiator of a radical polymerizable monomer. And a curing accelerator for a polymer compound having a reactive silicon group as an essential component. 2. Liquid A contains a polymer compound having a reactive silicon group and a polymerization initiator of a radical polymerizable monomer as essential components, and Liquid B contains a polymerization initiator of a radical polymerizable monomer and a radical polymerizable monomer. And a curing accelerator for a polymer compound having a reactive silicon group as an essential component. 3. A liquid contains a polymer compound having a reactive silicon group, a radical polymerizable monomer and a polymerization accelerator of a radical polymerizable monomer as essential components, and B liquid contains a radical polymerizable monomer and a radical polymerizable monomer. A room temperature-curable two-part composition comprising, as essential components, a polymerization initiator of a monomer and a curing accelerator of a polymer compound having a reactive silicon group. 4. A liquid contains a polymer compound having a reactive silicon group, a radical polymerizable monomer and a polymerization initiator of a radical polymerizable monomer as essential components, and B liquid contains a radical polymerizable monomer and a radical polymerizable monomer. A room temperature-curable two-part composition comprising, as essential components, a polymerization accelerator of a monomer and a curing accelerator of a polymer compound having a reactive silicon group. 5. A liquid contains a polymer compound having a reactive silicon group, a radical polymerizable monomer, and a polymerization initiator of the radical polymerizable monomer as essential components, and B liquid has a reactive silicon group. A room-temperature-curable two-part composition comprising, as essential components, a curing accelerator of a polymer compound and a polymerization accelerator of a radical polymerizable monomer. 6. Solution A contains a polymer compound having a reactive silicon group, a radical polymerizable monomer, and a polymerization accelerator of the radical polymerizable monomer as essential components, and Solution B has a reactive silicon group. A room temperature-curable two-part composition comprising, as essential components, a curing accelerator of a polymer compound and a polymerization initiator of a radical polymerizable monomer. 7. A liquid comprises a polymer compound having a reactive silicon group, a radical polymerizable monomer, a polymerization accelerator for a radical polymerizable monomer, and a curing accelerator for a polymer compound having a reactive silicon group. A room-temperature-curable two-pack composition, which is contained as an essential component, and wherein the liquid B contains a polymerization initiator of a radical polymerizable monomer as an essential component.