JPH05331447A - Room temperature curing type two-pack composition - Google Patents

Abstract

PURPOSE:To obtain a quick-curing composition, having rubber-like flexibility and capable of achieving the speedup of operation and higher reliability as flexible protective coating, potting, sealing materials and an adhesive and preventing the working environment from deteriorating. CONSTITUTION:The composition comprises (A) asolution containing a polymer compound having reactive silicon group and a polymerization accelerator for a radical-polymerizable monomer as essential components and (B) a solution containing the radical-polymerizable monomer, a polymerization initiator for the radical-polymerizable monomer and a curing accelerator for the polymer compound having the reactive silicon group as essential components.

Description

Detailed Description of the Invention

[0001]

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

[0002]

Conventionally, as a two-pack type curable composition, for example, a radical-polymerizable (meth) acrylate monomer is used as a main component, and one solution is made to contain an organic peroxide as a polymerization initiator, As the polymerization accelerator in the other liquid, for example, a two-liquid radically polymerizable composition containing a metal chelate compound, an organic amine, a carboxylic acid, a polyamide, an organic phosphorus compound, a thiourea compound and a metal salt is known. There is. Since such a two-component type radically polymerizable composition is excellent in quick-curing property, low-temperature curing property, workability, etc., it is adhered to each part of an automatic system, each part of a speaker, and an assembly bond of an electric device. If it is used in the fields such as adhesion of various parts of a small motor and protective coating, the production efficiency can be improved.

However, the radical-polymerizable monomer used as the main component in such an adhesive is mostly a volatile monomer such as methyl methacrylate in order to impart surface dryness. However, such (meth) acrylate monomers have the drawbacks of being extremely hard and having a large curing shrinkage.

In order to improve such drawbacks, a method of dissolving and adding various polymer substances (for example, various synthetic rubbers and various synthetic resins) has been taken, but the essential solution has not been reached yet. However, in the field of filling adhesion where curing shrinkage is large, or in the field of repeated exposure to low temperature and high temperature, strain generated in the adherend and the adhesive layer cannot be absorbed and fatigue failure of the adherend occurs. There is a problem that it is easy to generate.

On the other hand, also in the field of epoxy type curable compositions, in order to impart softness and flexibility to the cured product,
It is known that various rubbers are added, or that main chains and side chains of epoxy compounds are modified with urethane groups and various rubbers.

Recently, a curable composition comprising a combination of a modified silicone, an epoxy, and a known curing agent for epoxy has been proposed as a composition exhibiting rubber-like elasticity. This type of composition is used for an adhesive portion that is repeatedly strained or stressed due to its characteristics, and greatly contributes to improvement of adhesion reliability and adhesion durability.

However, the composition of the modified silicone-epoxy-epoxy curing agent has such excellent properties, but on the other hand, it is slow to cure at room temperature and low temperature, and it can be used for bonding and assembling in a production line where rapid curing is required. There is a coating,
In the field of coating, there is a problem that its use is limited.

[0008]

DISCLOSURE OF THE INVENTION The present invention provides a room temperature curable two-component composition which has both fast curing properties of a (meth) acrylate type polymerizable composition and rubber-like elasticity of a modified silicone-epoxy type cured product. The present invention aims to improve the drawbacks of the (meth) acrylate-based polymerizable composition being too hard and the slow curing rate of the modified silicone-based curable composition for obtaining a polymer. .. That is, it is intended to obtain a fast-curing, room-temperature-curing composition having rubber-like elasticity.

The present inventors have conducted various studies to solve the above problems in the two-pack type radically polymerizable (meth) acrylate composition and the modified silicone-based curable composition, and as a result, (meth) By combining an acrylate monomer and a modified silicone, it is possible to obtain a room-temperature curable two-component reactive composition which is fast-curing and which has rubber-like elasticity and leaves respective excellent parts, and has improved defects. The present invention has been accomplished by finding the above.

[0010]

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

The above-mentioned polymerization accelerator and polymerization initiator of the radical-polymerizable monomer may be contained in either solution A or solution B. Contrary to the above construction, solution A contains a polymerization initiator. The solution B may contain a polymerization accelerator.

Further, the radical-polymerizable monomer may be contained in the liquid A while being contained in the liquid B.
In this case, the radical polymerizable monomers used in the liquids A and B may be of the same type or combination, or may be 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, and B
The liquid may contain a curing accelerator for a polymer compound having a reactive silicon group and a polymerization accelerator for a radically polymerizable monomer as essential components.

Also in the case of this constitution, the polymerization accelerator of the radical-polymerizable monomer and the polymerization initiator may be contained in either the liquid A or the liquid B. It is also possible to add a polymerization initiator to the solution B and a polymerization accelerator.

It is also possible that only the polymerization accelerator of the radically polymerizable monomer is an essential component of the liquid B, and the remaining components are all contained in the liquid A. It is also possible to use the liquid B as a curing-accelerating primer and use it as a honeymoon type adhesive.

The mixing ratio of the liquid A and the liquid B is not particularly limited, and any mixing ratio can be used as long as the action and effect of the present invention can be achieved.

The functional radical-polymerizable monomer in the present invention is a radical-polymerizable monomer containing acrylate and / or methacrylate as a main component, and the acrylate and / or methacrylate, that is, (meth) acrylate is, for example, 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, methoxypolyethylene glycol (meth) acrylate
Acrylate; alkylene type bifunctional (meth) acrylates such as ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 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, tetraethylene glycol di (meth) acrylate; trimethylolpropane tri (meth) acrylate , Trimethylolethane (meta)
Trifunctional (meth) acrylates such as acrylates; pentaerythritol tetra (meth) acrylates, dipentaerythritol poly (meth) acrylates, tetramethylolmethane tetra (meth) acrylates and other polyfunctional (meth) acrylates; 2-hydroxyethyl (meth )
Acrylate, tetramethylolmethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, 2,3-dibromopropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate,
A polar group or a substituent atom-containing (meth) acrylate such as 2-chloroethyl (meth) acrylate or dimethylaminoethyl (meth) acrylate; 2,2-bis (4-acryloxy-diethoxyphenyl) propane di (meth) acrylate, bis Oxypolyethylene bisphenol A
An epoxy (meth) acrylate such as di (meth) acrylate, bisoxypropyleneated bisphenol A-di (meth) acrylate, bisoxy-2-hydroxyethylated bisphenol A-di (meth) acrylate;
Examples include polyester type di (meth) acrylates such as adipic acid-1,6-hexanediol-di (meth) acrylate; and urethane (meth) acrylates.

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

Specific examples of the polymer compound having one or more reactive silicon groups in the molecule are described in JP-A-50-1565.
99, JP-A-52-73998, JP-A-5
Compounds proposed in JP-A-8-10418, JP-A-62-230822 and the like, JP-A-63-1267
Japanese Patent Application Laid-Open No. 60-228516, Japanese Patent Application Laid-Open No. 63-112642, There is a composition such as the one composed of an oxyalkylene polymer having a silicon group and a (meth) acrylate (co) polymer having a silicon group proposed in JP-A-1-131127.

Further, a polyester polyol-based urethane prepolymer whose end isocyanate group is blocked with a silane coupling agent containing an active hydrogen group such as mercaptosilane, aminosilane and hydroxysilane, and a polyether polyol-based urethane prepolymer, Those obtained by directly reacting the hydroxyl groups of polyether polyol and polyester polyol with isocyanate silane can be used.

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

As the method for curing the (meth) acrylate component of the present invention, the method already used for the 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, and the like. 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 Combinations of pyrazolones; and various other known radical polymerization initiators. Two or more radical polymerization initiators can be used in combination.

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

The amount of the radical polymerization initiator and the polymerization accelerator used in the room-temperature-curable two-component composition of the present invention is the same as the conventional one, and the total amount of the two is usually 0.05. ~ 20 wt%, preferably 0.1
It is about 10% by weight. If the amount of these used is too small, the polymerization and curing rate becomes slow and it takes a long time to cure, and if it is too large, heat generation becomes large and air bubbles are contained in the cured product layer to deteriorate the physical properties of the cured product.

In the portion of the room temperature-curable two-component composition of the present invention containing a radical-polymerizable monomer as a main component, waxes such as paraffin wax and rice wax may be used as a surface dryness improving agent, if necessary. Quinone-type stabilizers such as P-benzoquinone and hydroquinone, hindered phenolic antioxidants such as butylhydroxytoluene, inorganic and organic fillers, dyes, pigments, thixotropic agents, aminosilanes, epoxysilanes, acidic phosphate group-containing An adhesion imparting agent such as a (meth) acrylate monomer may be contained.

As a method for curing the polymer compound having a reactive silicon group which is the other main component of the present invention, a curing accelerator which has been already put into practical use and is 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, dibutyltin diversate; tetrabutyl titanate, tetraisopropyl titanate. , Organic titanate compounds such as triethanolamine titanate; metal carboxylic acid salts such as lead octylate and cobalt naphthenate; aminosilanes such as γ-aminopropyltriethoxysilane and γ-aminopropyltrimethoxysilane; tetramethylammonium chloride , Quaternary ammonium salts such as benzalkonium chloride; organic phosphoric acid compounds such as monomethyl phosphoric acid, di-n-butyl phosphoric acid and triphenyl phosphate. You can

These may be used alone or in admixture of two or more. These compounds can be added to the component having a reactive silicon group, but it is preferable to add them to a portion consisting only of radically polymerizable monomers in terms of storage stability. It has the advantage that it is easy to remove. The curing accelerator may be used in an amount that is conventionally used.

In the part mainly containing the reactive silicon group of the room temperature curable two-part composition of the present invention, waxes such as paraffin wax and rice wax may be further added as a surface drying property improver, if necessary. 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, defoaming agents An agent, a leveling agent, a thickener, a thinning agent such as a high boiling point solvent, and various other additives can be added.

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

[0031]

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

Example 1 [Preparation of solution A] Modified silicone S-303 (trade name of polymer compound having reactive silicon, Kanegafuchi Chemical Industry Co., Ltd.)
100 parts, dicyclopentenyl methacrylate 2
A solution was prepared by stirring and mixing 0 part 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
Solution, 0.5 parts of hydroquinone, and 2 parts of 2-methacryloxyethyl phosphate were stirred using a lab stirrer, dissolved and mixed to prepare a solution B. A room temperature curable two-part composition was prepared with the mixing ratio of the liquid A and the liquid B being 1: 1 (weight ratio).

A curing test was carried out on the obtained room-temperature-curable two-component composition, and the set time, flexibility, and cured state were measured as described below. 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 curing status? The whole was cured uniformly at the same time and was good.

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

Measurement of Flexibility The composition of Example 1 was mixed in a predetermined ratio to give a length of 100 m.
m, width 25 mm, thickness 0.5 mm, applied on a mild steel plate with a thickness of 1.0 mm, and aged at room temperature for 24 hours to obtain a test piece. This is wound around a 1-inch mandrel at room temperature and the surface condition of the cured product is observed.

Observation of Curing Condition The composition of Example 1 is mixed at a predetermined ratio to give 50 g, and the curing condition is 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 Kanegafuchi Chemical Industry Co., Ltd., Example 2], modified silicone M-217 [trade name of polymer compound having reactive silicon, Example 3] manufactured by Kanegafuchi Chemical Industry Co., Ltd., and a solution 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) were used.

The 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 300 parts of polytetramethylene ether glycol having a molecular weight of 3000 was charged in a four-necked flask equipped with a stirrer, a thermometer, a nitrogen gas inlet, and a reflux condenser.
While stirring while heating at 0 ° C., dry nitrogen gas is blown in to dry the content until the water content is 0.003% or less as measured by a Karl Fischer water content meter. next,
The content was cooled to 30 ° C. and charged with 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, and 30
Stirring was carried out at ˜50 ° C., the disappearance of NCO groups was confirmed by IR measurement, and the reaction was terminated. By this reaction, an isocyanate silane adduct of polyol was obtained.

Preparation of Synthetic Product Into a four-necked flask similar to that used in Example 4, 2000 parts of polypropylene glycol having a molecular weight of 2000 was charged.
Dehydration is performed in the same manner as in Example 4. Next, 80 contents
While maintaining at ~ 90 ° C, 68 parts of MDI is charged, and the reaction is carried out at the same temperature until the NCO content becomes 1.45%. Then, 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 reaction was terminated by confirming the disappearance of the NCO group by IR measurement. By this reaction, a product obtained by adding aminosilane to the NCO group of the urethane prepolymer of 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 divided into two equal parts, and 4 parts of cumene hydroperoxide is added to one of them to obtain a uniform solution (solution A). To the other part, 2 parts of ethylenethiourea and 1 part of 2-metaacryloxyethyl 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-component composition) was obtained.

Liquids A and 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 good at 8 minutes, but cracks, peeling and foaming were observed, 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 As a reactive silicon group-containing polymer compound, Kanegafuchi Chemical Co., Ltd.
Made by adding 5 parts of tris, dimethylaminomethylphenol to 100 parts of Cyril 5B-30 manufactured by Manufacture (solution A)
Then, as an epoxy compound, a composition (liquid B) was prepared in which 100 parts of Epicoat # 828 manufactured by Shell Chemical Co., Ltd. and 3 parts of dibutyltin dilaurate were added. The mixing ratio of liquid A and liquid B is 2: 1 by weight. Thus, a conventional room temperature curable two-part composition was obtained.

Liquids A and 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 65 minutes, which was extremely long.
Although the flexibility was good, the curing situation was non-uniform, with the skin peeling from the surface after 60 minutes.

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

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

[Preparation of Solution B] 50 parts of dicyclopentenyl methacrylate and 50 parts of 2-hydroxypropyl methacrylate, 2 parts of (b) ethylenethiourea and (c) 1 part of di-n-butylphosphoric acid (Example 6) ), (A) 4 parts of cumene hydroperoxide and (c) 1 part of di-n-butylphosphoric acid (Example 7), (b) 0.1 part of copper 2-ethylhexanoate and (c) Phosmer M (oil and fat). Products Co., Ltd.
Manufactured by Acid Phosoxyethyl Methacrylate) 1 part (Example 8), (b) Cobalt naphthenate 0.
1 part and (c) di-n-butyltin dilaurate 0.5 part (Example 9), (b) N, N-dimethylparatoluidine 1 part and (c) dibutyltin diacetylacetate 0.5.
Parts (Example 10), (b) 0.1 part of vanadium acetylacetonate and (c) Phosmer M (Oil and Fat Products Co., Ltd.)
Manufactured by Acid Phosphoroxyethyl Methacrylate) 1 part (Example 11), (b) N, N-dimethylparatoluidine 0.1 part, copper 2-ethylhexanoate 0.01
And 1 part of tri-n-butylamine, 0.5 part of (c) dibutyltin diacetylacetate and 1 part of γ-aminopropyltriethoxysilane (Example 12), respectively.

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 2, and all the test results were good.

From the results of Examples 6 to 12 described above, for the room temperature curable two-part composition of the present invention, various radical polymerizable monomer polymerization initiators and polymerization accelerators were used. It was 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 radically polymerizable monomer was reversed in the A liquid and the B liquid, the radical polymerizable monomer was mixed. It was found that the polymerization initiator and the curing accelerator of the monomer 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 Industry Co., Ltd., trade name of a polymer compound having a reactive silicon group), 20 parts (M) methyl methacrylate, (a) 1 part 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), (M) NK ester BE400 [trade name of 2,2′-bis (4-methacryloxydiethoxyphenyl) propane manufactured by Shin-Nakamura Industry Co., Ltd.] 20 parts, (a)
(B) Same as Example 13 (Example 19), (M) Styrene monomer 10 parts, (a) (b) Same as Example 13 (Example 20), (M) Dicyclopentenyl methacrylate 20 parts, ( a) 4 parts of cumene hydroperoxide,
(B) The same as Example 13 (Example 21) was added, and dissolved by stirring with a lab stirrer to prepare solution A.

[Preparation of Solution B] (M) 40 parts of methyl methacrylate and 60 parts of 2-hydroxyethyl methacrylate
Parts, (b) (c) accelerator VN ₂ (trade name of acidic phosphoric acid solution of vanadium manufactured by Nippon Kayaku Co., Ltd.) 3 parts,
(D) Butylhydroxytoluene 0.5 part (Example 1
3), (M) 2-hydroxypropyl methacrylate 6
0 parts and light ester 3002M (Kyoeisha Yushi Co., Ltd.)
Product name of epoxy dimethacrylate) 40 parts,
(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 Kogyo Co., Ltd.), (b) (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) diallyl phthalate monomer 10 parts and 2-hydroxypropyl methacrylate 90 parts, (b) (c) (d) same as Example 13 (Example 17), (M) trimethylolpropane trimethacrylate 10 parts and 90 parts of dicyclopentenyl methacrylate, (b) (c) (d) same as in Example 13 (Example 18), (M) NK ester BE400 [Shin-Nakamura Industry Co., Ltd., 2,2'-bis (4 Trade name of methacryloxydiethoxyphenyl) propane] 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
(Negami Kogyo Co., Ltd., trade name of urethane dimethacrylate) 60 parts and dicyclopentenyl methacrylate 40
Parts, (b) 2 parts of ethylenethiourea and copper naphthenate 0.
02 parts, (c) dibutyltin diacetylacetate 2 parts and dibutyltin sulfide 1 part, and (d) the same as Example 13 (Example 21) were dissolved by stirring with a lab stirrer to prepare a 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 is understood that various polymerizable monomers can be used in 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 reactive silicon group, manufactured by Kaneka Corporation) and modified silicone SAT-010 (Kanefuchi Chemical Industry Co., Ltd., trade name of a polymer compound having a reactive silicon group) 20 parts, cumene hydroperoxide 1
Parts and 0.5 parts of thioglycerol were dissolved by stirring with a lab stirrer to prepare solution A.

[Preparation of solution B] Dicyclopentenyl methacrylate 40 parts, 2-hydroxybutyl methacrylate 40 parts, NK ester BE-40020 parts, 3,5-
Dimethylpyrazole 3 parts, accelerator VN ₂ 4 parts,
2 parts of γ-methacryloxypropyltrimethoxysilane,
0.3 part of butylhydroxytoluene was dissolved by stirring with a lab stirrer to prepare solution B.

Liquid A and liquid B thus obtained were used in a polymerization ratio of 10:90 (Example 22), 25:75 (Example 23), 50:50 (Example 24) and 75:25. (Example 25) and 90:10 (Example 26) were mixed, and the curability and the 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-component composition of the present invention exhibited good performance in a wide range of the mixing ratio of liquid A and liquid B.

[0064]

[Table 4]

Example 27 [Preparation of solution A] 100 parts of modified silicone S-303 (trade name of polymer compound having reactive silicon group, manufactured by Kaneka Corporation), dicyclopentenyl methacrylate 10
4 parts of cumene hydroperoxide as a polymerization initiator of a radically polymerizable monomer was dissolved in 0 part with stirring with a lab stirrer to prepare a solution A.

[Preparation of Solution B] Vanadium acetylacetonate as a polymerization accelerator for radically polymerizable monomers.
2 parts and 1 part of di-n-butyl phosphoric acid, which is a curing accelerator for a polymer compound having a reactive silicon group, were 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. Set time is 8
And the flexibility was also good. The curing status is
The whole was cured uniformly at the same time and was good.

From the results of Example 27, the room temperature curable two-part composition of the present invention was prepared by adding the polymer compound having a reactive silicon group, the radical polymerizable monomer, and the polymerization initiator of the radical polymerizable monomer to solution A. It has been found that even in the case of the composition in which the solution B contains only the curing accelerator of the polymer compound having a reactive silicon group and the polymerization accelerator of the radically polymerizable monomer, good performance is exhibited.

The radical polymerization monomer polymerization initiator and the polymerization accelerator can be replaced with each other as long as no adverse reaction occurs with the curing accelerator of the polymer compound having a reactive silicon group. Is. Examples 28-33

[Preparation of Solution A] Modified Silicone S-302
(Kanefuchi Chemical Industry Co., Ltd., trade name of polymer compound having reactive silicon group) 100 parts, dicyclopentenyl methacrylate 100 parts, cumene hydroperoxide 4 parts as a polymerization initiator of radically polymerizable monomer, Dibutyltin diacetylacetate 2 parts as a curing accelerator for the polymer compound having a reactive silicon group, and in Examples 31 to 33, 1 part saccharin as a curing accelerator for the radically polymerizable monomer is further dissolved by stirring with a lab stirrer. Then, solution A was prepared.

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

The performance of the obtained room temperature-curable two-component composition 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, 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 radical-polymerizable monomer is added to the solution B. Do you get it.

[0074]

[Table 5]

Examples 34 to 39 Using the same solutions A and B as those in Examples 28 to 33, the solution B was thinly applied to one surface with a waste cloth, and the solution A was overlaid without intentionally mixing. As for the coating method, the set time and the flexibility were also tested. The results are shown in Table 6. 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 was found to exhibit good performance even when the solution B was used as a curing-accelerating primer. Furthermore, the room temperature curable two-part composition of the present invention,
It was confirmed that it is also possible to apply honeymoon bonding by applying the solution A to one side and the solution B to the other side and overlapping them.

[0077]

[Table 6]

[0078]

INDUSTRIAL APPLICABILITY As described above, the room-temperature-curable two-component composition of the present invention is fast-curing and has rubber-like flexibility, so that it is a flexible protective coating material, a potting material, and a seal. When used for materials and adhesives, speeds up work,
It is effective for high reliability.

Even when a low-odor (low-volatility) radical-polymerizable monomer other than the methylmethacrylate monomer is used, since the curing system of the polymer compound having a reactive silicon group is also used, the surface curing Since it can be rapidly performed, it is possible to prevent deterioration of the working environment due to the volatile polymerizable monomer.

Furthermore, even if a material such as NBR rubber that takes a long time to dissolve is not used, simply by mixing the liquid material,
Since the composition of the present invention can be produced, the production cost can be significantly reduced.

The room-temperature-curable two-component composition of the present invention is used for filling a large amount, which cannot be used in the conventional (meth) acrylic curable composition because of its large curing shrinkage, and that it can be used at a low temperature. It can be effectively used for bonding ferrite magnets, which cannot be used due to its high hardness, or for bonding large-area panels, which are susceptible to distortion due to large curing shrinkage.

Further, the room temperature-curable two-component composition of the present invention is a field work at a low temperature which cannot be used in the conventional modified silicone-epoxy curable composition because the curing at a low temperature is slow. However, it can be effectively used for the gap filling that could not be used because the whole did not cure at a uniform speed, or for the assembly work in the manufacturing line that could not be used because it did not cure rapidly.

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Claims (7)

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