JP7119880B2 - Two-component curable composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a curable resin composition that can be cured at room temperature, and more particularly to a two-component curable resin composition.

Curable compositions containing a polymer having a room-temperature curing type reactive group include compositions containing various polymers such as modified silicone, urethane, polysulfide and acrylic. Widely used as adhesives, sealants, paints, etc. in electronics-related applications and automobile-related applications. For example, a modified silicone polymer is a curable composition based on an oxyalkylene polymer having a hydrolyzable silyl group. It is widely used as a base polymer for adhesives and sealants because it is a well-balanced material.
A modified silicone-based curable resin composition is usually provided as a one-component type or a two-component type. In the case of the one-component type, there is no need to perform a mixing operation before use, which is convenient. Therefore, it is necessary to fill a container such as a cartridge, and there is a limit to the amount that can be filled in one package, so there is a problem that packaging material costs increase. In addition, since the coating is applied in a state in which moisture is sufficiently controlled, there is a problem that deep curing is slowed down when curing proceeds due to humidity in the air after coating.
On the other hand, in the case of the two-component type, although work such as mixing is required before use, it is easy to balance the pot life and the curing time, and hardening of the deep part tends to proceed quickly.

Patent Document 1 describes a two-component modified silicone sealant that exhibits excellent curing properties such as storage stability, mechanical properties, and adhesiveness by using a non-phthalic acid plasticizer, an epoxy resin, and a divalent tin catalyst. It is described that it becomes a sexual composition.
However, since a polyoxyalkylene derivative such as polypropylene glycol is used as a plasticizer, it cannot be said to be sufficient from the viewpoint of weather resistance.
In addition, Patent Documents 2 and 3 are techniques for providing a curable composition having excellent deep-part curability by using an epoxy resin, water, etc. However, since it does not substantially contain a plasticizer, the composition There was a problem that the viscosity of the material was high and the workability at the time of construction was inferior.

Special republication WO00/056817 Japanese Patent Application Laid-Open No. 2004-225020 Special republication WO06/075482

An object of the present invention is to provide a two-component curable resin composition which has excellent workability due to its low viscosity and whose cured product has excellent mechanical properties and weather resistance.

As a result of intensive studies to solve the above problems, it was found that by using a (meth)acrylic acid ester copolymer with a specific molecular weight range as a plasticizer, it is possible to achieve both workability during construction and weather resistance of the cured product. I found
That is, the present invention has been completed based on this finding, and the present specification provides the following means.

[1] A two-component curable resin composition containing components (A) and (B), wherein the component (A) is an oxyalkylene polymer containing a hydrolyzable silyl group (A-1 ) and a (meth)acrylic acid ester polymer (A-2) containing no hydrolyzable silyl group, and as the component (B), a divalent tin compound (B-1) and an amine compound (B-2 ), a two-component curable resin composition.
[2] As the component (B), a divalent tin compound (B-1), an amine compound (B-2), and a (meth)acrylic acid ester polymer (B-3) containing no hydrolyzable silyl group The two-component curable resin composition according to [1], comprising:
[3] The two-component curing according to [1] or [2], wherein the (meth)acrylic acid ester polymer (A-2) containing no hydrolyzable silyl group has a weight average molecular weight of 1500 or more and 20000 or less. elastic resin composition.
[4] The (meth)acrylate polymer (A-2) containing no hydrolyzable silyl group is added to 100 parts by mass of the oxyalkylene polymer (A-1) containing the hydrolyzable silyl group. and the (meth)acrylic acid ester polymer (B-3) containing no hydrolyzable silyl group is 20 parts by mass or more and 150 parts by mass or less, any one of [1] to [3]. 2-component curable resin composition according to.

Since the two-component curable composition of the present invention has low viscosity and excellent workability, and has excellent mechanical properties and high weather resistance after curing, it is suitably used for two-component sealants and adhesives. be done.

The present invention will be described in detail below. In this specification, "(meth)acryl" means acryl and/or methacryl, and "(meth)acrylate" means acrylate and/or methacrylate. A "(meth)acryloyl group" means an acryloyl group and/or a methacryloyl group.

The two-component curable composition in the present invention comprises components (A) and (B), and as component (A) an oxyalkylene polymer having a hydrolyzable silyl group (A-1) and a hydrolyzable silyl A (meth)acrylic acid ester polymer (A-2) containing no group, and a divalent tin compound (B-1) and an amine compound (B-2) as components (B) as essential components. . Details of each component are described below.

<(A-1) Component: Oxyalkylene Polymer Having Hydrolyzable Silyl Group>
The oxyalkylene polymer having a hydrolyzable silyl group is not particularly limited as long as it contains a repeating unit represented by the following general formula (1).
- OR ² - (1)
(In the formula, R ² is a divalent hydrocarbon group.)
Examples of R ² in the general formula (1) are as follows.
(CH ₂ ) _n (n is an integer of 1 to 10)
CH( _CH3 ) _CH2
CH _{( C2H5} ) _CH2
C ( _CH3 ) _2CH2
The oxyalkylene-based polymer may contain one or a combination of two or more of the above repeating units, and among these, CH(CH ₃ )CH ₂ is preferable from the viewpoint of excellent workability.

The hydrolyzable silyl group contained in the oxyalkylene polymer containing a hydrolyzable silyl group is not particularly limited, and examples thereof include an alkoxysilyl group, a halogenosilyl group, a silanol group, etc., but the reactivity is easily controlled. An alkoxysilyl group is preferred. Specific examples of the alkoxysilyl group include trimethoxysilyl group, methyldimethoxysilyl group, dimethylmethoxysilyl group, triethoxysilyl group, methyldiethoxysilyl group and dimethylethoxysilyl group.

The method for producing the oxyalkylene polymer is not particularly limited, but for example, a polymerization method using a corresponding epoxy compound, diol or triol as a raw material using an alkali catalyst such as KOH, or a transition metal compound-porphyrin complex catalyst. A polymerization method, a polymerization method using a double metal cyanide complex catalyst, a polymerization method using phosphazene, and the like can be mentioned.
Moreover, the oxyalkylene polymer may be either a linear polymer or a branched polymer. Moreover, you may use these in combination.

The average number of hydrolyzable silyl groups contained in one molecule of the oxyalkylene polymer is preferably in the range of 1 to 4, more preferably in terms of performance such as adhesiveness and tensile properties of the cured product. It ranges from 1.5 to 3.
The position of the reactive silyl group contained in the oxyalkylene-based polymer is not particularly limited, and can be the side chain and/or terminal of the polymer.
Further, the oxyalkylene-based polymer may be either a linear polymer or a branched polymer. Moreover, you may use these in combination.

The number average molecular weight (Mn) of the oxyalkylene polymer having a hydrolyzable silyl group is preferably 5,000 or more, more preferably 10,000 or more, still more preferably 15, from the viewpoint of mechanical properties. 000 or more. Mn may be 18,000 or more, 22,000 or more, or 25,000 or more. The upper limit of Mn is preferably 60,000 or less, more preferably 50,000 or less, and still more preferably 40,000 or less from the viewpoint of workability (viscosity) during coating of the curable composition. . The range of Mn can be set by combining the above upper limit and lower limit. ,000 or more and 50,000 or less, or 22,000 or more and 50,000 or less.

A commercially available oxyalkylene polymer having a hydrolyzable silyl group may be used. Specific examples include Kaneka's "MS Polymer S203", "MS Polymer S303", "MS Polymer S810", "Syryl SAT200", "Syryl SAT350", "Syryl EST280" and "Syryl SAT30" (all trade names ), and “Exester ES-S2410”, “Exester ES-S2420” and “Exester ES-S3430” (all trade names) manufactured by AGC.

<(A-2) component: (meth)acrylate polymer containing no hydrolyzable silyl group>
The (meth)acrylic acid ester polymer is a polymer having a structural unit derived from a (meth)acrylic acid ester monomer. For example, a monomer mixture containing a (meth)acrylic acid ester monomer is polymerized. can be obtained by The (meth)acrylic acid ester monomer is a monomer having a (meth)acryloyl group in the molecule, and examples thereof include (meth)acrylic acid alkyl esters and (meth)acrylic acid alkoxyalkyl esters. The amount of the (meth)acrylic acid ester monomer used is preferably in the range of 10 to 100% by mass, more preferably 30 to 100% by mass, based on the total constituent monomers of the (meth)acrylic acid ester polymer. %, more preferably 50 to 100 mass %.

Specific examples of the (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and (meth)acrylic acid. n-butyl, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylic acid Methylcyclohexyl, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, (meth)acrylic Decyl acid, undecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, (meth)acrylic acid Heptadecyl, stearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, henicosyl (meth)acrylate, behenyl (meth)acrylate, tetracosyl (meth)acrylate, hexacosyl (meth)acrylate , octacosyl (meth) acrylate, triacontyl (meth) acrylate, dotriacontyl (meth) acrylate, tetratriacontyl (meth) acrylate, hexatriacontyl (meth) acrylate, octatriacon (meth) acrylate Chill, tetracontyl (meth)acrylate, isodecyl (meth)acrylate, isoundecyl (meth)acrylate, isolauryl (meth)acrylate, isotridecyl (meth)acrylate, isotetradecyl (meth)acrylate, (meth)acrylic isopentadecyl acid, isohexadecyl (meth)acrylate, isoheptadecyl (meth)acrylate, isostearyl (meth)acrylate, isononadecyl (meth)acrylate, isoeicosyl (meth)acrylate, isoheneicosyl (meth)acrylate, isobehenyl (meth) acrylate, isotetracosyl (meth) acrylate, isohexacosyl (meth) acrylate, isooctacosyl (meth) acrylate, isotriacontyl (meth) acrylate, isodotriacontyl (meth) acrylate, (meth) ) isotetratriacontyl acrylate, isohexatriacontyl (meth)acrylate, Examples include (meth)acrylic acid alkyl esters having linear or branched aliphatic alkyl groups or alicyclic alkyl groups such as isooctatotriacontyl (meth)acrylate and isotetracontyl (meth)acrylate. , one or more of these can be used.
Among these, (meth)acrylic acid alkyl esters having an alkyl group of 1 to 8 carbon atoms are preferred from the viewpoint of mechanical properties of the cured product. The amount of the (meth)acrylic acid alkyl ester having an alkyl group of 1 to 8 carbon atoms used is preferably 10% by mass or more, more preferably It is 30% by mass or more, more preferably 50% by mass or more. The upper limit is 100% by mass or less, may be 90% by mass or less, may be 80% by mass or less, or may be 50% by mass or less.

Among the above, when a (meth)acrylic acid alkyl ester having an alkyl group having 10 or more carbon atoms is used, good compatibility with the oxyalkylene polymer is ensured, and mechanical properties and weather resistance are improved. point is preferable. The number of carbon atoms in the alkyl group is preferably 10-20, more preferably 12-20. The amount of the (meth)acrylic acid alkyl ester having an alkyl group of 10 or more carbon atoms to be used is preferably 5% by mass or more, more preferably It is 10% by mass or more, more preferably 20% by mass or more. The upper limit is 100% by mass or less, may be 90% by mass or less, may be 80% by mass or less, or may be 50% by mass or less.

Specific examples of the (meth)acrylic acid alkoxyalkyl esters include methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, methoxybutyl (meth)acrylate, methoxyhexyl (meth)acrylate, (meth) ) ethoxymethyl acrylate, ethoxyethyl (meth)acrylate, ethoxybutyl (meth)acrylate, ethoxyhexyl (meth)acrylate, butoxymethyl (meth)acrylate, butoxyethyl (meth)acrylate, (meth)acrylic Butoxybutyl acid, butoxyhexyl (meth)acrylate and the like can be mentioned, and one or more of these can be used. Among these, from the viewpoint of the mechanical properties of the cured product, (meth)acrylic acid alkoxyalkyl esters having an alkoxyalkyl group having 2 to 8 carbon atoms are preferable, and (meth)acryl having an alkoxyalkyl group having 2 to 4 carbon atoms. Acid alkoxyalkyl esters are more preferred. The amount of the (meth)acrylic acid alkoxyalkyl ester used is preferably 10% by mass or more, more preferably 30% by mass or more, and still more preferably, based on the total constituent monomers of the (meth)acrylic polymer. is 50% by mass or more. The upper limit is 100% by mass or less, may be 90% by mass or less, may be 80% by mass or less, or may be 50% by mass or less.

The (meth)acrylic acid ester polymer may be copolymerized with other monomers copolymerizable with them in addition to the above monomers, but the monomer containing a hydrolyzable silyl group is except.
Other monomers include (meth)acrylic acid, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and glycidyl (meth)acrylate. , 2-aminoethyl (meth)acrylate, functional group-containing monomers such as ethylene oxide adducts of (meth)acrylic acid;
(meth)acrylic acid aromatic esters such as phenyl (meth)acrylate, toluyl (meth)acrylate, and benzyl (meth)acrylate;
(Meth)trifluoromethylmethyl acrylate, 2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutyl (meth)acrylate Ethyl, 2-perfluoroethyl (meth)acrylate, perfluoromethyl (meth)acrylate, diperfluoromethylmethyl (meth)acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth)acrylate , Fluorine-containing (meth)acrylic acid esters such as 2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, and 2-perfluorohexadecylethyl (meth)acrylate;
fluorine-containing olefins such as perfluoroethylene, perfluoropropylene and vinylidene fluoride; aromatic monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof;
maleic anhydride; unsaturated dicarboxylic acids such as maleic acid and fumaric acid, and their mono- and dialkyl esters;
Maleimide compounds such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, phenylmaleimide, cyclohexylmaleimide;
Nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile;
amide group-containing vinyl monomers such as acrylamide and methacrylamide;
vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate;
alkenes such as ethylene and propylene;
Conjugated dienes such as butadiene and isoprene;
Examples include, but are not limited to, vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol, and the like. Also, one or more of these can be used.

The weight average molecular weight (Mw) of the (meth)acrylic acid ester polymer containing no hydrolyzable silyl group is a polystyrene equivalent molecular weight obtained by gel permeation chromatography (hereinafter also referred to as “GPC”), and the composition From the viewpoint of workability, it should be 20000 or less. It is more preferably 10,000 or less, and still more preferably 5,000 or less. From the viewpoint of weather resistance of the cured product, it is preferably 1,500 or more, more preferably 2,000 or more, and even more preferably 2,500 or more.

The viscosity of the (meth)acrylate polymer is preferably 500 mPa·s or more, more preferably 800 mPa·s or more at 25°C. The viscosity may be 1,000 mPa·s or more, 3,000 mPa·s or more, or 5,000 mPa·s or more. The upper limit of the viscosity is preferably 100,000 mPa s or less, more preferably 50,000 mPa s or less, still more preferably 20,000 mPa s or less, and still more preferably 10,000 mPa s or less. be.
A viscosity of 500 mPa·s or more is preferable because dripping when applied to a vertical surface is suppressed, and a viscosity of 100,000 mPa·s or less improves the workability of the curable composition.
The range of viscosity can be set by combining the above upper limit and lower limit. It may be 1,000 mPa·s or more and 10,000 mPa·s or less.

The (meth)acrylic acid ester polymer can be produced by ordinary radical polymerization. Any method of solution polymerization, bulk polymerization and dispersion polymerization may be employed, and a living radical polymerization method may also be used. The reaction process may be batch, semi-batch or continuous polymerization. Among these, a high-temperature continuous polymerization method at 100 to 350° C. is preferred.

In general, when the crosslinkable functional groups are uniformly introduced into the polymer, the curability of the curable composition containing the polymer and physical properties such as weather resistance of the resulting cured product are improved. In this respect, it is preferable to use a stirred tank type reactor because a (meth)acrylic acid ester polymer having a relatively narrow composition distribution (distribution of crosslinkable functional groups) and molecular weight distribution can be obtained. Further, a process using a continuous stirred tank reactor is more preferable in terms of narrowing the composition distribution and molecular weight distribution.

As the high-temperature continuous polymerization method, known methods disclosed in JP-A-57-502171, JP-A-59-6207 and JP-A-60-215007 may be followed.
For example, after filling a pressurizable reactor with a solvent and setting it to a predetermined temperature under pressure, a monomer mixture consisting of each monomer and, if necessary, a polymerization solvent is fed into the reactor at a constant rate. and withdrawing an amount of the polymerization liquid corresponding to the amount of the monomer mixture supplied.
Moreover, a polymerization initiator can be added to the monomer mixture, if necessary. When blended, the blending amount is preferably 0.001 to 2 parts by mass with respect to 100 parts by mass of the monomer mixture. The pressure depends on the reaction temperature and the boiling points of the monomer mixture and solvent used, and does not affect the reaction, but may be any pressure that can maintain the reaction temperature. The residence time of the monomer mixture is preferably 1 to 60 minutes. If the residence time is less than 1 minute, the monomer may not react sufficiently, and if the unreacted monomer exceeds 60 minutes, the productivity may deteriorate. A preferred residence time is 2 to 40 minutes.

The polymerization initiator used for obtaining the (meth)acrylic acid ester polymer is not particularly limited as long as it is an initiator that generates radicals at a predetermined reaction temperature. Specifically, di-t-butyl peroxide, di-t-hexyl peroxide, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, cumene hydroperoxide oxides and organic peroxides such as t-butyl hydroperoxide, 2,2′-azobis(isobutyronitrile), 2,2′-azobis(2-methylbutyronitrile), azobiscyclohexacarbonitrile, Azo compounds such as azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-amidinopropane) dihydrochloride and 4,4'-azobis(4-cyanovaleric acid).
One of these polymerization initiators may be used alone, or two or more thereof may be used in combination. When a polymerization initiator having a high hydrogen abstraction ability is used, the resulting polymer tends to have a high double bond concentration. For example, using an organic peroxide tends to yield a polymer with a higher double bond concentration than using an azo compound.
The amount of the polymerization initiator to be used can be appropriately adjusted depending on the type of the polymerization initiator and monomer, the desired molecular weight, polymerization conditions, etc., but in general, it is It is 0.001 to 10 parts by mass. When obtaining a polymer having the same molecular weight, the less the amount of the polymerization initiator used, the higher the double bond concentration in the resulting polymer.

When an organic solvent is used for the production of the (meth)acrylic acid ester polymer, organic hydrocarbon compounds are suitable, and cyclic ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbon compounds such as benzene, toluene and xylene, Examples include esters such as ethyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone and cyclohexanone, and alcohols such as methanol, ethanol, and isopropanol, and one or more of these can be used. Solvents that do not dissolve the (meth)acrylic acid ester copolymer well tend to cause scale to grow on the wall of the reactor, which tends to cause production problems in the washing process and the like. Further, when an organic solvent having high chain transfer ability such as isopropanol is used, the concentration of double bonds in the resulting polymer tends to be low.
The amount of solvent used is preferably 80 parts by mass or less with respect to 100 parts by mass of all vinyl monomers. By setting the amount to 80 parts by mass or less, a high conversion rate can be obtained in a short time. More preferably, it is 1 to 50 parts by mass. Dehydrating agents such as trimethyl orthoacetate and trimethyl orthoformate can also be added.

A known chain transfer agent may be used for the production of the (meth)acrylate polymer.

<(B-1) Divalent tin compound>
Divalent tin compounds act as curing catalysts for cross-linking of hydrolyzable silyl groups. Generally, divalent and tetravalent tin compounds are present, but in the case of tetravalent tin compounds, since they are stable, they continue to exist while maintaining their catalytic activity even after application and curing. As a result, excessive cross-linking reaction progresses with time, and the cured product becomes hard, resulting in a problem that the flexibility of the cured product is impaired.
On the other hand, a divalent tin compound is oxidized over time and its catalytic activity is lowered, so that excessive cross-linking reaction does not occur and initial flexibility can be maintained for a long period of time.
Specific examples of divalent tin compounds include tin (II) acetate, tin (II) propionate, tin (II) butanoate, tin (II) 2-ethylhexanoate, tin (II) stearate and versatic acid. Examples include, but are not limited to, tin(II). Among these, tin (II) 2-ethylhexanoate is preferred from the viewpoint of catalytic activity and solubility in resins.

<(B-2) Amine compound>
The amine compound is added together with the divalent tin compound to promote the cross-linking reaction of hydrolyzable silyl groups.
Specific examples of amine compounds include propylamine, butylamine, 2-ethylhexylamine, laurylamine, stearylamine, dipropylamine, dibutylamine, ethanolamine, diethanolamine, triethanolamine, ethylenediamine, hexylenediamine, triethylenediamine, and diethylenetriamine. , triethylenetetramine, benzylamine, morpholine, N-methylmorpholine and 1,8-diazabicyclo(5,4,0)undecene-7, etc., and these may be used alone or in combination of two or more. .
Among these, laurylamine and stearylamine are preferable from the viewpoints of little odor and solubility in resins.

<(B-3) (Meth)acrylic acid ester polymer containing no hydrolyzable silyl group>
The (meth)acrylic acid ester polymer containing no hydrolyzable silyl group (B-3) is the same as (A-2) above. In the present invention, (B-3) may be the same as or different from (A-2).

<Mass ratio of each component>
When the oxyalkylene polymer (A-1) having a hydrolyzable silyl group is 100 parts by mass, a (meth) acrylic acid ester copolymer (A-2) containing no hydrolyzable silyl group and hydrolyzed The total amount of the (meth)acrylic acid ester copolymer (B-3) containing no silyl group is preferably 20 parts by mass or more and 150 parts by mass or less. When the amount is 20 parts by mass or more, the workability during construction is improved, and when the amount is 150 parts by weight or less, the weather resistance of the cured product is improved. It is preferably 25 parts by mass or more and 100 parts by mass, more preferably 30 parts by mass or more and 70 parts by mass or less.
The amount of the divalent tin compound (B-1) to be added is 0.3 to 10 parts by mass when the oxyalkylene polymer (A-1) having a hydrolyzable silyl group is 100 parts by mass. is preferred. When the amount is 0.3 parts by mass or more, the resin is cured quickly, and when the amount is 10 parts by mass or less, the tensile physical properties are improved.
The amount of the amine compound (B-2) added is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the oxyalkylene polymer (A-1) having a hydrolyzable silyl group. When the amount is 0.1 parts by mass or more, the resin is cured quickly, and when the amount is 10 parts by mass or less, the tensile physical properties are improved.

<Other components in component A>
In addition to the above, the A component in the present invention may contain a filler, a plasticizer other than (A-2), an epoxy resin, an anti-aging agent, an anti-tack agent, water for accelerating curing, and the like.

Fillers include light calcium carbonate with an average particle size of about 0.02 to 2.0 μm, heavy calcium carbonate with an average particle size of about 1.0 to 5.0 μm, titanium oxide, carbon black, synthetic silicic acid, talc, Examples include zeolite, mica, silica, calcined clay, kaolin, bentonite, aluminum hydroxide, barium sulfate, glass balloons, silica balloons and polymethyl methacrylate balloons. These fillers can improve the mechanical properties of the cured product and improve the strength and elongation.
Among these, light calcium carbonate, heavy calcium carbonate and titanium oxide, which are highly effective in improving physical properties, are preferred, and a mixture of light calcium carbonate and heavy calcium carbonate is more preferred. The amount of filler added is preferably 20 to 300 parts by mass, more preferably 50 to 200 parts by mass, when the total amount of components (A) and (B) is 100 parts by mass. When a mixture of light calcium carbonate and heavy calcium carbonate is used as described above, the mass ratio of light calcium carbonate/heavy calcium carbonate is preferably in the range of 90/10 to 50/50.

Examples of plasticizers include liquid polyurethane resins, polyester plasticizers obtained from dicarboxylic acid and diol; etherified products or esterified products of polyalkylene glycols such as polyethylene glycol and polypropylene glycol; sugar polyhydric alcohols such as sucrose; Polyether-based plasticizers such as saccharide-based polyethers obtained by addition polymerization of alkylene oxides such as oxide and propylene oxide followed by etherification or esterification; polystyrene-based plasticizers such as poly-α-methylstyrene; Examples thereof include poly(meth)acrylates having no functional groups.

Antiaging agents include UV absorbers such as benzophenone compounds, benzotriazole compounds and anilide oxalate compounds, light stabilizers such as hindered amine compounds, antioxidants such as hindered phenols, heat stabilizers, or An anti-aging agent which is a mixture of these can be used.
Examples of ultraviolet absorbers include BASF's trade names "TINUVIN 571", "TINUVIN 1130" and "TINUVIN 327". Examples of light stabilizers include "TINUVIN 292", "TINUVIN 144" and "TINUVIN 123" manufactured by the same company, and "SANOL 770" manufactured by Sankyo.
Examples of heat stabilizers include trade names "Irganox 1135", "Irganox 1520" and "Irganox 1330" manufactured by BASF.
A mixture of UV absorbers/light stabilizers/heat stabilizers under the trade name "TINUVIN B75" manufactured by BASF may also be used.

Examples of anti-tack agents include acrylic oligomers "Aronix M8030", "M8100" and "M309" manufactured by Toagosei Co., Ltd., or mixtures with photopolymerization initiators, saturated fatty acid oils such as tung oil and linseed oil, Examples include the product name "R15HT" manufactured by Idemitsu Oil Co., Ltd., the product name "PBB3000" manufactured by Nippon Soda Co., Ltd., and the product name "Gocerac 500B" manufactured by Nippon Synthetic Chemical Industry Co., Ltd.

Examples of epoxy resins include glycidyl ether of bisphenol A type resin, glycidyl ether of bisphenol F type resin, glycidyl group-containing acrylic resin, novolac type epoxy resin, and glycidyl ether of hydrogenated bisphenol A type resin.

<Regarding other components in the B component>
In addition to the above, a filler, a plasticizer other than (B-3), and the like may be added to the B component of the present invention. Moreover, when an epoxy resin is added to the A component, a curing agent for the epoxy resin can also be added.
The plasticizer other than (B-3) is the same as the plasticizer other than (A-2).
Curing agents for epoxy resins include, in addition to the amine compounds exemplified in (B-2), polyamine compounds and ketimine compounds.

The two-component curable composition of the present invention has the following advantages over the one-component curable composition.
The one-component type needs to be stored in a dehydrated state because the curing progresses during storage. Immediately after coating, the material is dehydrated and hardening progresses gradually from the surface, so it takes time to harden deep parts, and temperature changes during that time can cause changes in the width of the joints, which may cause problems in hardening. On the other hand, since the two-component type does not need to be stored in a dehydrated state, it has the advantage of fast hardening in the deep part.
In addition, since the two-component type does not allow the curable resin and the curing agent (catalyst) to coexist during storage, there is very little risk of curing during storage.
In the two-component curable resin composition of the present invention, the A component and the B component are mixed and stored separately. Immediately before coating, the A component and the B component are mixed in a predetermined ratio, sufficiently mixed with a stirrer such as a disper, and then the mixture can be coated.

EXAMPLES The present invention will be specifically described below based on examples. It should be noted that the present invention is not limited by these examples. In the following, "parts" and "%" mean parts by weight and % by weight unless otherwise specified.
Methods for analyzing the polymers obtained in Production Examples, Examples and Comparative Examples, and evaluation methods for the cured products obtained from the curable compositions are described below.

<Molecular weight measurement>
Using a gel permeation chromatograph (model name “HLC-8320”, manufactured by Tosoh Corporation), the number average molecular weight (Mn) and weight average molecular weight (Mw) in terms of polystyrene were obtained under the following conditions. Also, the molecular weight distribution (Mw/Mn) was calculated from the obtained values.
○ Measurement conditions Column: Tosoh TSKgel Super Multipore HZ-M × 4 columns Column temperature: 40 ° C.
Eluent: Tetrahydrofuran Detector: RI

<Viscosity measurement of (meth)acrylic acid ester polymer>
E-type viscosity was measured under the following conditions using a TVE-20H type viscometer (cone/plate type, manufactured by Toki Sangyo Co., Ltd.).
○ Measurement conditions Cone shape: angle 1°34′, radius 24 mm (less than 10000 mPa s)
Angle 3°, Radius 7.7mm (10000mPa s or more)
Temperature: 25°C ± 0.5°C

<Average number of hydrolyzable silyl groups contained in the (meth)acrylate polymer>
The number (average number) f (Si) of alkoxysilyl groups that are hydrolyzable silyl groups is obtained by the following formula from the parts by mass of the monomer having a reactive silyl group when the total number of constituent monomers is 100 parts by mass. was calculated using
f(Si) = {mass parts of silyl group monomer/(molecular weight of silyl group monomer x 100/Mn)}

<Production of (meth)acrylate polymer (A-2) containing no hydrolyzable silyl group>
(Production example 1)
The temperature of a 1000 mL pressurized stirred tank reactor equipped with an oil jacket was maintained at 263°C. Then, while keeping the pressure of the reactor constant, 100 parts of butyl acrylate (hereinafter referred to as "BA"), 20 parts of isopropyl alcohol (hereinafter referred to as "IPA"), methyl ethyl ketone (hereinafter referred to as "MEK") 20 parts of a monomer mixture consisting of 2 parts of di-t-butyl peroxide (manufactured by NOF Corporation, trade name "Perbutyl D", hereinafter referred to as "DTBP") as a polymerization initiator, at a constant supply rate. (48 g/min, residence time: 12 min), continuous supply from the raw material tank to the reactor was started, and the reaction liquid corresponding to the supply amount of the monomer mixture was continuously withdrawn from the outlet. Immediately after the start of the reaction, the reaction temperature dropped once and then increased due to the heat of polymerization.
The point at which the temperature stabilized from the start of the supply of the monomer mixture was the starting point for collecting the reaction solution, and the reaction was continued for 25 minutes. Liquid was collected. Thereafter, the reaction solution was introduced into a thin film evaporator to separate volatile components such as unreacted monomers to obtain a (meth)acrylic acid ester polymer A-2-1. Table 1 shows the properties of the obtained polymer.

(Production Examples 2 to 8 and Comparative Production Example 1)
(Meth)acrylic polymers A-2-2 to A-2-9 were obtained in the same manner as in Production Example 1, except that the raw material supply composition and the internal temperature of the reactor were changed as shown in Table 1. .

In Table 1, abbreviations have the following meanings.
BA: butyl acrylate HA: 2-ethylhexyl acrylate TDA: tetradecyl acrylate MMA: methyl methacrylate TMS: 3-methacryloxypropyltrimethoxysilane DMS: 3-methacryloxypropylmethyldimethoxysilane IPA: isopropyl alcohol MEK: methyl ethyl ketone MOA : Trimethyl orthoacetate DTBP: Di-t-butyl peroxide (manufactured by NOF Corporation, trade name “Perbutyl D”)
DTHP: Di-t-hexyl peroxide (manufactured by NOF Corporation, trade name "Perhexyl D")
Mw: mass average molecular weight Mn: number average molecular weight

<Preparation of curable resin composition, creation of evaluation sample and evaluation>
Examples 1 to 11, Comparative Examples 1 to 2
As component A, a commercially available ESS2420 (manufactured by AGC, trade name "Exester S2420" or ESS3430 (manufactured by AGC, trade name "Excester S3430") is added in a planetary mixer at an amount ratio shown in Table 2 below. A component was obtained by mixing for 1 hour at a temperature of 60° C. and 10 Torr.
On the other hand, in another container, component B was obtained by stirring and mixing in the ratio shown in Table 2 until it became transparent.
Next, the A component and the B component obtained above were mixed for 1 minute and defoamed for 30 seconds using a rotation/revolution mixer at a rotation speed of 2000 rpm to obtain the curable resin composition of the present invention.
This composition was applied on a Teflon (registered trademark) sheet to a thickness of 2 mm and cured at 23° C. and 50% RH for 2 weeks to obtain a cured product.

<Viscosity measurement of formulation>
From Table 2, the same mixing operation as above was performed without B-1 or the curing catalyst, and immediately after that, the viscosity was measured. The viscosity measurement conditions were the same as those for the (meth)acrylic acid ester polymer viscosity measurement, and the rotation speed was fixed at 1 rpm.

<Tensile test>
A dumbbell for tensile test (JIS K 6251 No. 3 type) was prepared from the obtained cured product with a thickness of 2 mm, and a tensile tester (Autograph AGS-J, manufactured by Shimadzu Corporation) was used at a tensile speed of 200 mm / min. The breaking elongation and breaking strength under the conditions were measured.

<Weather resistance test>
The cured product having a thickness of 2 mm was placed in a metal weather meter ("DAIPLA METAL WEATHER KU-R5NCI-A" manufactured by Daipla-Wintes Co.) to conduct an accelerated weather resistance test. The test was conducted under the conditions of irradiation at 63° C., 70% RH, and illuminance of 80 mW/cm 2 and showering for 2 minutes once every 2 hours. The time at which abnormalities such as cracks began to appear in the appearance was recorded.

<Heat resistance test>
The resulting 2 mm thick sheet was heated in an atmosphere of 100° C. for 1 week, removed, and conditioned at 23° C. and 50% RH for 1 day. Thereafter, a tensile test was performed under the same conditions as the above tensile test to evaluate changes in physical properties.

In Tables 2 and 3, abbreviations have the following meanings.
ESS2420: manufactured by AGC, trade name “Exester-S2420” (linear modified silicone)
ESS3430: manufactured by AGC, trade name “Excester S3430” (branched modified silicone)
PPG: propylene glycol (molecular weight 3000)
CCR: Light calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., trade name “Shiraenka CCR”)
Super SS: Heavy calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., trade name “Super SS”)
R820: Titanium oxide (manufactured by Ishihara Sangyo Co., Ltd.)
Tinuvin B75: anti-aging agent (manufactured by BASF)
M-8100: Multifunctional acrylate (manufactured by Toagosei Co., Ltd., trade name “Aronix M-8100”)

As can be seen from the results in Tables 2 and 3, when Examples 1 to 11 and Comparative Example 1 are compared, the Example shows higher breaking strength than Comparative Example 1. This indicates that having a silyl group in the plasticizer causes a decrease in tensile properties.
When Examples 1 to 11 and Comparative Example 2 are compared, the example shows excellent weather resistance while maintaining substantially the same tensile properties as Comparative Example 2.
Regarding Example 3 and Comparative Example 3, the example using divalent tin showed less change in tensile properties after the heat resistance test than the initial value compared to Comparative Example 3 using tetravalent tin. Therefore, the use of divalent tin shows excellent results in heat resistance.
In comparison among Examples 1 to 11, the higher the molecular weight, the better the weather resistance, but the viscosity of the formulation tends to increase. On the other hand, the tensile properties showed no significant change.

Since the two-component curable composition of the present invention has low viscosity and excellent workability, and has excellent mechanical properties and high weather resistance after curing, it is suitably used for two-component sealants and adhesives. be done.

Claims (4)

A two-component curable resin composition containing components (A) and (B), wherein the component (A) is an oxyalkylene polymer (A-1) containing a hydrolyzable silyl group and hydrolyzed Containing a (meth)acrylic acid ester polymer (A-2) containing no decomposable silyl group, and containing a divalent tin compound (B-1) and an amine compound (B-2) as the component (B) , a two-component curable resin composition. As the component (B), a divalent tin compound (B-1), an amine compound (B-2), and a (meth)acrylic acid ester polymer (B-3) containing no hydrolyzable silyl group, The two-component curable resin composition according to claim 1. 3. The two-component curable resin composition according to claim 1, wherein the (meth)acrylic acid ester polymer (A-2) containing no hydrolyzable silyl group has a weight average molecular weight of 1500 or more and 20000 or less. With respect to 100 parts by mass of the oxyalkylene polymer (A-1) containing the hydrolyzable silyl group, the (meth)acrylic acid ester polymer (A-2) containing no hydrolyzable silyl group and the hydrolyzable The two components according to any one of claims 1 to 3, wherein the total amount of the (meth)acrylate polymer (B-3) containing no degradable silyl group is 20 parts by mass or more and 200 parts by mass or less. A mold-curable resin composition.