JP2020063316A - Two-component curable composition - Google Patents

Abstract

To provide a two-component curable resin composition which has excellent workability with low viscosity and whose cured product is excellent in mechanical properties and weather resistance.SOLUTION: The two-component curable resin composition contains a component (A) and a component (B). As the component (A), an oxyalkylene-based polymer (A-1) containing a hydrolyzable silyl group and a (meth)acrylate polymer (A-2) containing no hydrolyzable silyl group are contained. As the component (B), a divalent tin compound (B-1) and an amine compound (B-2) are contained.SELECTED DRAWING: None

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.

Examples of the curable composition containing a polymer having a room temperature curable reactive group include modified silicone-based, urethane-based, polysulfide-based, acrylic-based, and other polymers containing various polymers, and are used for construction, electricity and Widely used as adhesives, sealing materials, paints, etc. in electronic field related applications, automobile related applications, etc. For example, a modified silicone polymer is a curable composition based on an oxyalkylene polymer having a hydrolyzable silyl group, but it has good workability and has excellent mechanical properties such as elongation at break and breaking strength. Since it is a well-balanced material, it is widely used as a base polymer for adhesives and sealing materials.
The 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 or the like before use, and it is simple, but in order to maintain stability during storage, it is necessary to perform sufficient water management. Therefore, it is necessary to fill a container such as a cartridge, and there is a limit to the amount that can be filled per package, which causes a problem of increasing the packaging material cost. Further, since the work is carried out in a state in which the water content is sufficiently controlled, there is a problem that the deep hardening is delayed when the hardening is promoted by the humidity in the air after the working.
On the other hand, in the case of the two-component type, although a work such as mixing is required before use, it has a feature that the pot life and the curing time are easily balanced, and the curing of the deep portion is easily promoted.

In Patent Document 1, in a two-component modified silicone sealant, by using a non-phthalic acid-based plasticizer, an epoxy resin and a divalent tin catalyst, curing excellent in storage stability, mechanical properties, adhesiveness, etc. It is described that it becomes a sexual composition.
However, since a polyoxyalkylene derivative such as polypropylene glycol is used as the 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 excellent in deep-part curability by using an epoxy resin, water, etc., but since the composition does not substantially contain a plasticizer, the composition is There was a problem that the viscosity of the product was high and the workability during construction was poor.

Special re-publication WO00 / 056817 JP, 2004-225020, A Special Republished WO 06/075482

  The present invention is to provide a two-component curable resin composition having a low viscosity and excellent workability, and a cured product having excellent mechanical properties and weather resistance.

As a result of extensive studies to solve the above problems, by using a (meth) acrylic acid ester copolymer in a specific molecular weight range as a plasticizer, workability during construction and weather resistance of the cured product can be compatible. Found.
That is, the present invention has been completed based on this finding, and according to the present specification, the following means are provided.

[1] A two-component curable resin composition containing a component (A) and a component (B), wherein an oxyalkylene polymer (A-1) containing a hydrolyzable silyl group as the component (A). ) And a hydrolyzable silyl group-free (meth) acrylic acid ester polymer (A-2), and as the component (B), a divalent tin compound (B-1) and an amine compound (B-2). Two-component curable resin composition containing
[2] As the component (B), a divalent tin compound (B-1), an amine compound (B-2) and a hydrolyzable silyl group-free (meth) acrylic acid ester polymer (B-3). The two-component curable resin composition according to [1], which comprises:
[3] The two-component type 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. Resin composition.
[4] (Meth) acrylic acid ester polymer (A-2) not containing the hydrolyzable silyl group per 100 parts by mass of the oxyalkylene polymer (A-1) containing the hydrolyzable silyl group. And the total amount of the (meth) acrylic acid ester polymer (B-3) not containing the hydrolyzable silyl group is 20 parts by mass or more and 150 parts by mass or less, [1] to [3]. The two-component curable resin composition described in 1.

  Since the two-component curable composition of the present invention has a low viscosity and excellent workability, and has excellent mechanical properties and high weather resistance after curing, it is suitable for use as a two-component sealing material or adhesive. To be

  Hereinafter, the present invention will be described in detail. In addition, in this specification, "(meth) acryl" means acryl and / or methacryl, and "(meth) acrylate" means acrylate and / or methacrylate. Further, the “(meth) acryloyl group” means an acryloyl group and / or a methacryloyl group.

  The two-component curable composition in the present invention contains the component (A) and the component (B), and the oxyalkylene polymer (A-1) having a hydrolyzable silyl group as the component (A) and the hydrolyzable silyl. A (meth) acrylic acid ester polymer (A-2) containing no group is used as a component (B) having a divalent tin compound (B-1) and an amine compound (B-2) as essential components. . The details of each component will be 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).
-O-R ² - (1)
(In the formula, R ² is a divalent hydrocarbon group.)
Examples of R ² in the above general formula (1) include the following.
(CH ₂ ) _n (n is an integer of 1 to 10)
CH (CH ₃ ) CH ₂
CH (C ₂ H ₅ ) CH ₂
C (CH ₃ ) ₂ CH ₂
The oxyalkylene polymer may contain one kind or a combination of two or more kinds 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, and a silanol group, but it is easy to control the reactivity. To alkoxysilyl groups are preferred. Specific examples of the alkoxysilyl group include a trimethoxysilyl group, a methyldimethoxysilyl group, a dimethylmethoxysilyl group, a triethoxysilyl group, a methyldiethoxysilyl group and a dimethylethoxysilyl group.

The method for producing the oxyalkylene polymer is not particularly limited. For example, a corresponding epoxy compound, diol or triol as a raw material is polymerized by an alkali catalyst such as KOH, or a transition metal compound-porphyrin complex catalyst is used. Examples thereof include a polymerization method, a polymerization method using a double metal cyanide complex catalyst, and a polymerization method using phosphazene.
The oxyalkylene polymer may be either a linear polymer or a branched polymer. Also, these may be used in combination.

The average value of the number of hydrolyzable silyl groups contained in one molecule of the oxyalkylene polymer is preferably in the range of 1 to 4 and more preferably from the viewpoint of performance such as adhesiveness and tensile properties of the cured product. It is in the range of 1.5 to 3.
The position of the reactive silyl group contained in the oxyalkylene polymer is not particularly limited and may be the side chain and / or the terminal of the polymer.
The oxyalkylene polymer may be either a linear polymer or a branched polymer. Also, these may be used 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, and further preferably 15, from the viewpoint of mechanical properties. It is more than 000. 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 further 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 upper limit value and the lower limit value described above, but is, for example, 5,000 or more and 60,000 or less, or may be 15,000 or more and 60,000 or less, 18 It may be 2,000 or more and 50,000 or less, or 22,000 or more and 50,000 or less.

  A commercially available product may be used as the oxyalkylene polymer having a hydrolyzable silyl group. As specific examples, "MS Polymer S203", "MS Polymer S303", "MS Polymer S810", "Cyril SAT200", "Cyril SAT350", "Cyril EST280" and "Cyril SAT30" manufactured by Kaneka (trade names are all available. ), And "Excester ES-S2410", "Excester ES-S2420" and "Excester ES-S3430" (all are trade names) manufactured by AGC.

<(A-2) component: (meth) acrylic acid ester 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, and for example, a monomer mixture containing a (meth) acrylic acid ester monomer is polymerized. It 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 ester and (meth) acrylic acid alkoxyalkyl ester. 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 all the constituent monomers of the (meth) acrylic acid ester polymer. %, And more preferably 50 to 100% by mass.

Specific examples of the (meth) acrylic acid alkyl ester 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, (meth) ac Tridecyl acidate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, stearyl (meth) acrylate, nonadecyl (meth) acrylate, (meth) acrylic Eicosyl acid, Henicosyl (meth) acrylate, Behenyl (meth) acrylate, Tetracosyl (meth) acrylate, Hexacosyl (meth) acrylate, Octacosyl (meth) acrylate, Triacontyl (meth) acrylate, (Meth) acrylic acid Dotriacontyl, tetramethacontyl (meth) acrylate, hexatriacontyl (meth) acrylate, octatriacontyl (meth) acrylate, tetracontyl (meth) acrylate, isodecyl (meth) acrylate, (meth) acrylic Acid a Undecyl, isolauryl (meth) acrylate, isotridecyl (meth) acrylate, isotetradecyl (meth) acrylate, isopentadecyl (meth) acrylate, isohexadecyl (meth) acrylate, isoheptadecyl (meth) acrylate, Isostearyl (meth) acrylate, Isononadecyl (meth) acrylate, Isoeicosyl (meth) acrylate, Isohenicosyl (meth) acrylate, Isobehenyl (meth) acrylate, Isotetracosyl (meth) acrylate, Isohexacosyl (meth) acrylate, Isomethacryl (meth) acrylate, Isotriacontyl (meth) acrylate, Isodotriacontyl (meth) acrylate, Isotetratriacontyl (meth) acrylate, Isohexatriacontyl (meth) acrylate, Illustrative examples include (meth) acrylic acid alkyl esters having a linear or branched aliphatic alkyl group or alicyclic alkyl group, such as isooctatriacontyl (meth) acrylate and isotetracontyl (meth) acrylate. Of these, one kind or two or more kinds can be used.
Among these, from the viewpoint of mechanical properties of the cured product, (meth) acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms is preferable. The amount of the (meth) acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms is preferably 10% by mass or more, more preferably 100% by mass, based on all the constituent monomers of the (meth) acrylic polymer. It is 30 mass% or more, and more preferably 50 mass% or more. The upper limit value is 100% by mass or less, 90% by mass or less, 80% by mass or less, or 50% by mass or less.

  Further, 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 an oxyalkylene polymer is secured, and mechanical properties and weather resistance are improved. It is preferable in terms. The carbon number of the alkyl group is preferably 10-20, more preferably 12-20. The amount of the (meth) acrylic acid alkyl ester having an alkyl group having 10 or more carbon atoms is preferably 5% by mass or more, and more preferably based on all the constituent monomers of the (meth) acrylic acid ester polymer. It is 10% by mass or more, and more preferably 20% by mass or more. The upper limit is 100% by mass or less, 90% by mass or less, 80% by mass or less, or 50% by mass or less.

  Specific examples of the (meth) acrylic acid alkoxyalkyl ester include methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, methoxybutyl (meth) acrylate, methoxyhexyl (meth) acrylate, and (meth) acrylic acid. ) Ethoxymethyl acrylate, ethoxyethyl (meth) acrylate, ethoxybutyl (meth) acrylate, ethoxyhexyl (meth) acrylate, butoxymethyl (meth) acrylate, butoxyethyl (meth) acrylate, (meth) acrylic Butoxybutyl acid and butoxyhexyl (meth) acrylate are listed, and one or more of them can be used. Among these, from the viewpoint of mechanical properties of the cured product, (meth) acrylic acid alkoxyalkyl ester having an alkoxyalkyl group having 2 to 8 carbon atoms is preferable, and (meth) acrylic 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 further preferably, based on all the constituent monomers of the (meth) acrylic polymer. Is 50% by mass or more. The upper limit is 100% by mass or less, 90% by mass or less, 80% by mass or less, or 50% by mass or less.

The (meth) acrylic acid ester polymer may be copolymerized with other monomers copolymerizable therewith 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, glycidyl (meth) acrylate. , A functional group-containing monomer such as 2-aminoethyl (meth) acrylic acid and an ethylene oxide adduct of (meth) acrylic acid;
Aromatic esters of (meth) acrylic acid such as phenyl (meth) acrylate, toluyl (meth) acrylate, and benzyl (meth) acrylate;
Trifluoromethylmethyl (meth) 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;
Aromatic monomers such as fluorine-containing olefins such as perfluoroethylene, perfluoropropylene and vinylidene fluoride styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrene sulfonic acid and salts thereof;
Maleic anhydride; unsaturated dicarboxylic acids such as maleic acid and fumaric acid, and their monoalkyl and dialkyl esters;
Maleimide compounds such as maleimide, methyl maleimide, ethyl maleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, phenyl maleimide, cyclohexyl maleimide;
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 thereof include, but are not limited to, vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol, and the like. Moreover, 1 type (s) or 2 or more types of these can be used.

  The weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer not containing the hydrolyzable silyl group is a polystyrene-equivalent molecular weight measured by gel permeation chromatography (hereinafter, also referred to as “GPC”). From the viewpoint of workability, it should be 20,000 or less. It is more preferably 10,000 or less, and even more preferably 5,000 or less. Further, from the viewpoint of weather resistance of the cured product, it is preferably 1500 or more, more preferably 2000 or more, and further preferably 2500 or more.

The viscosity of the (meth) acrylic acid ester polymer at 25 ° C. is preferably 500 mPa · s or more, more preferably 800 mPa · s or more. The viscosity may be 1,000 mPa · s or more, 3,000 mPa · s or more, and 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, further preferably 20,000 mPa · s or less, and further preferably 10,000 mPa · s or less. is there.
When the viscosity is 500 mPa · s or more, the sagging when applied on a vertical surface is suppressed, which is preferable, and when the viscosity is 100,000 mPa · s or less, the workability of the curable composition becomes good.
The range of viscosity can be set by combining the upper limit value and the lower limit value described above. For example, the viscosity range is 500 mPa · s or more and 100,000 mPa · s or less, and 800 mPa · s or more and 50,000 mPa · s or less. 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 of solution polymerization, bulk polymerization, and dispersion polymerization may be adopted, and living radical polymerization may be used. The reaction process may be a batch type, a semi-batch type, or a continuous polymerization method. Among these, the high temperature continuous polymerization method at 100 to 350 ° C. is preferable.

  Generally, when a crosslinkable functional group is uniformly introduced into the polymer, the curability of the curable composition containing the polymer and the physical properties such as weather resistance of the obtained cured product are improved. In this respect, it is preferable to use a stirred tank reactor as the 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 that the composition distribution and the molecular weight distribution are narrowed.

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 used.
For example, a pressurizable reactor is filled with a solvent, and a predetermined temperature is set under pressure, and then a monomer mixture consisting of each monomer and, if necessary, a polymerization solvent is fed at a constant supply rate. And a withdrawal of an amount of the polymerization liquid commensurate with the amount of the monomer mixture supplied.
Further, a polymerization initiator may be added to the monomer mixture if necessary. The blending amount in the case of blending 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 the solvent used, and does not affect the reaction, but may be any pressure at which the reaction temperature can be maintained. 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 be deteriorated. The preferred residence time is 2 to 40 minutes.

The polymerization initiator used to obtain 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-hexyl peroxy-2-ethyl hexanoate, t-butyl peroxy-2-ethyl hexanoate, cumene hydroper Organic peroxides such as oxide and t-butyl hydroperoxide, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2-methylbutyronitrile), azobiscyclohexacarbonitrile, Examples thereof include azo compounds such as azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-amidinopropane) dihydrochloride and 4,4′-azobis (4-cyanovaleric acid).
As the polymerization initiator, one of these 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 concentration of double bonds in the obtained polymer tends to increase. For example, when an organic peroxide is used rather than an azo compound, a polymer having a high double bond concentration tends to be obtained.
The amount of the polymerization initiator used can be appropriately adjusted depending on the types of the polymerization initiator and the monomer, the desired molecular weight, the polymerization conditions, etc., but generally, it is based on 100 parts by mass of the monomer used. It is 0.001 to 10 parts by mass. When a polymer having the same molecular weight is obtained, the smaller the amount of the polymerization initiator used, the higher the double bond concentration in the obtained polymer tends to be.

When using an organic solvent for the production of the (meth) acrylic acid ester polymer, organic hydrocarbon compounds are suitable, cyclic ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbon compounds such as benzene, toluene and xylene, Examples thereof 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. In a solvent that does not dissolve the (meth) acrylic acid ester copolymer well, scales are likely to grow on the wall of the reactor, and production problems are likely to occur in the washing process and the like. Further, when an organic solvent having a high chain transfer ability such as isopropanol is used, the double bond concentration in the obtained polymer tends to be low.
The amount of the solvent used is preferably 80 parts by mass or less based on 100 parts by mass of all vinyl monomers. When the amount is 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. Further, a dehydrating agent such as trimethyl orthoacetate or trimethyl orthoformate may be added.

  A known chain transfer agent may be used in the production of the (meth) acrylic acid ester polymer.

<(B-1) divalent tin compound>
The divalent tin compound acts as a curing catalyst for the crosslinking of hydrolyzable silyl groups. Usually, divalent and tetravalent tin compounds are present, but in the case of a tetravalent tin compound, since it is stable, it continues to exist while maintaining catalytic activity even after construction and curing. As a result, an excessive crosslinking reaction progresses over time and the cured product becomes hard, which causes a problem of impairing the flexibility of the cured product.
On the other hand, a divalent tin compound is characterized in that it is oxidized over time and its catalytic activity decreases, so that an excessive crosslinking reaction does not occur and the initial flexibility can be maintained for a long period of time.
Specific examples of the divalent tin compound include tin (II) acetate, tin (II) propionate, tin (II) butanoate, tin (II) 2-ethylhexanoate, tin (II) stearate and versatic acid. Examples include tin (II), but are not limited thereto. Among these, tin (II) 2-ethylhexanoate is preferable from the viewpoint of the activity of the catalyst and the solubility in the resin.

<(B-2) Amine compound>
The amine compound is added together with the divalent tin compound to accelerate the crosslinking reaction of the hydrolyzable silyl group.
Specific examples of the amine compound include propylamine, butylamine, 2-ethylhexylamine, laurylamine, stearylamine, dipropylamine, dibutylamine, ethanolamine, diethanolamine, triethanolamine, ethylenediamine, hexylenediamine, triethylenediamine, diethylenetriamine. , Triethylenetetramine, benzylamine, morpholine, N-methylmorpholine, 1,8-diazabicyclo (5,4,0) undecene-7 and the like, and one or more of these may be used in combination. .
Among these, laurylamine and stearylamine are preferable from the viewpoint of low odor and solubility in resins.

<(B-3) Hydrolyzable silyl group-free (meth) acrylic acid ester polymer>
The (meth) acrylic acid ester polymer not containing a hydrolyzable silyl group of (B-3) is the same as the above (A-2). 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 hydrolysis It is preferable that the total amount of the (meth) acrylic acid ester copolymer (B-3) containing no functional silyl group is 20 parts by mass or more and 150 parts by mass or less. When it is at least 20 parts by mass, workability during construction will be good, and when it is at most 150 parts by mass, the weather resistance of the cured product will be good. The amount is preferably 25 parts by mass or more and 100 parts by mass, and more preferably 30 parts by mass or more and 70 parts by mass or less.
The addition amount of the divalent tin compound (B-1) 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 rapidly cured, and when the amount is 10 parts by mass or less, the tensile properties are good.
The addition amount of the amine compound (B-2) is preferably 0.1 to 10 parts by mass when the oxyalkylene polymer (A-1) having a hydrolyzable silyl group is 100 parts by mass. When the amount is 0.1 parts by mass or more, the resin is rapidly cured, and when the amount is 10 parts by mass or less, the tensile properties are good.

<Other components in component A>
In addition to the above, a filler, a plasticizer other than (A-2), an epoxy resin, an antioxidant, a tack preventer, water for accelerating curing, and the like can be added to the component A in the present invention.

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

  As the plasticizer, a liquid polyurethane resin, a polyester-based plasticizer obtained from a dicarboxylic acid and a diol; an etherified product or esterified product of a polyalkylene glycol such as polyethylene glycol or polypropylene glycol; a sugar polyhydric alcohol such as sucrose; Polyether plasticizer such as saccharide-based polyether obtained by addition polymerization of alkylene oxide such as oxide or propylene oxide, and then etherification or esterification; polystyrene-based plasticizer such as poly-α-methylstyrene; crosslinkability Examples thereof include poly (meth) acrylates having no functional group.

As the anti-aging agent, a benzophenone-based compound, a UV absorber such as a benzotriazole-based compound and an oxalic acid anilide-based compound, a light stabilizer such as a hindered amine-based compound, an antioxidant such as a hindered phenol-based compound, a heat stabilizer, or An antioxidant, which is a mixture of these, can be used.
Examples of the ultraviolet absorber include trade names “Tinuvin 571”, “Tinuvin 1130” and “Tinuvin 327” manufactured by BASF. Examples of the light stabilizer include trade names “Tinuvin 292”, “Tinuvin 144” and “Tinuvin 123” manufactured by the same company, and trade name “Sanol 770” manufactured by Sankyosha.
Examples of the heat stabilizer include trade names "IRGANOX 1135", "IRGANOX 1520" and "IRGANOX 1330" manufactured by BASF.
A trade name “Tinuvin B75” manufactured by BASF, which is a mixture of an ultraviolet absorber / a light stabilizer / a heat stabilizer, may be used.

  As the anti-tack agent, trade name "Aronix M8030", "M8100" and "M309" manufactured by Toagosei Co., Ltd., which is an acrylic oligomer, or a mixture with a photopolymerization initiator, a saturated fatty acid oil such as tung oil and flaxseed 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 "Go-Serac 500B" manufactured by Nippon Synthetic Chemical Company.

  Examples of the epoxy resin 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.

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

The two-component curable composition of the present invention has the following advantages as compared with the one-component type.
Since the one-component type is hardened during storage, it is necessary to store it in a dehydrated state. Immediately after coating, it is in a dehydrated state, and hardening gradually progresses from the surface, so it takes time to harden the deep part, and the joint width may change due to temperature changes etc. during that time, 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 an advantage that it cures deeply quickly.
Further, 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.
The two-component curable resin composition of the present invention is prepared by mixing the components A and B and storing them separately. Immediately before coating, the components A and B may be mixed at a predetermined ratio and sufficiently mixed with a stirrer such as a disper, and then the mixture may be coated.

Hereinafter, the present invention will be specifically described based on Examples. The present invention is not limited to these examples. In the following, "part" and "%" mean "part by mass" and "% by mass" unless otherwise specified.
The method for analyzing the polymers obtained in Production Examples, Examples and Comparative Examples, and the method for evaluating the cured product obtained from the curable composition are described below.

<Molecular weight measurement>
The number average molecular weight (Mn) and the weight average molecular weight (Mw) in terms of polystyrene were obtained under the following conditions using a gel permeation chromatograph (model name "HLC-8320", manufactured by Tosoh Corporation). Further, the molecular weight distribution (Mw / Mn) was calculated from the obtained values.
○ Measurement condition column: Tosoh TSKgel SuperMultipore HZ-M x 4 columns Temperature: 40 ° C
Eluent: Tetrahydrofuran Detector: RI

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

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

<Production of (meth) acrylic acid ester polymer (A-2) containing no hydrolyzable silyl group>
(Production Example 1)
The temperature of a pressure type stirred tank reactor equipped with an oil jacket and having a capacity of 1000 mL was maintained at 263 ° C. Next, 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"). And 20 parts of di-t-butyl peroxide (manufactured by NOF CORPORATION, trade name "Perbutyl D", hereinafter referred to as "DTBP") as a polymerization initiator, and a constant mixture rate of a monomer mixture consisting of 2 parts. (48 g / min, residence time: 12 minutes), continuous supply was started from the raw material tank to the reactor, and the reaction liquid corresponding to the supply amount of the monomer mixture was continuously withdrawn from the outlet. Immediately after the reaction was started, the reaction temperature was once lowered and then increased by the heat of polymerization, but the reaction temperature was kept at 254 to 256 ° C. by controlling the temperature of the oil jacket.
The point at which the temperature became stable from the start of supplying the monomer mixture was taken as the starting point for collecting the reaction solution, and as a result of continuing the reaction for 25 minutes from this, 1.2 kg of the monomer mixture solution was supplied and 1.2 kg of the reaction solution was obtained. The liquid was collected. After that, the reaction liquid was introduced into a thin film evaporator, and volatile components such as unreacted monomers were separated to obtain a (meth) acrylic acid ester polymer A-2-1. The properties of the obtained polymer are shown in Table 1.

(Production Examples 2 to 8 and Comparative Production Example 1)
A (meth) acrylic polymer A-2-2 to A-2-9 was obtained by the same operation as in Production Example 1 except that the raw material supply composition and the reactor internal temperature were changed as shown in Table 1. .

In Table 1, the meanings of the abbreviations are as follows.
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 (NOF Corporation, trade name "Perbutyl D")
DTHP: di-t-hexyl peroxide (NOF Corporation, trade name "Perhexyl D")
Mw: mass average molecular weight Mn: number average molecular weight

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

<Viscosity measurement of compound>
From Table 2, the same mixing operation as described above was performed in the state where B-1 or the curing catalyst was removed, and immediately after that, the viscosity was measured. The conditions for measuring the viscosity were the same as those for measuring the viscosity of the (meth) acrylic acid ester polymer, and the rotation speed was fixed at 1 rpm.

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

<Weather resistance test>
The obtained cured product having a thickness of 2 mm was put into a metal weather meter (“DAIPLA METAL WEATHER KU-R5NCI-A” manufactured by Daipla Wintes Co., Ltd.) and an accelerated weathering test was performed. The conditions were irradiation of 63 ° C., 70% RH, and illuminance of 80 mW / cm 2, and the test was conducted by showering for 2 minutes once every 2 hours. The time when the appearance of abnormality such as cracks was recorded.

<Heat resistance test>
The obtained sheet having a thickness of 2 mm was heated in an atmosphere of 100 ° C. for 1 week, taken out, and then conditioned for one day at 23 ° C. and 50% RH. Then, 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, the abbreviations have the following meanings.
ESS2420: manufactured by AGC, trade name "Exester-S2420" (straight chain modified silicone)
ESS3430: manufactured by AGC, trade name "Exester S3430" (branched modified silicone)
PPG: Propylene glycol (molecular weight 3000)
CCR: Light calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd. under the product name "Shiragika CCR")
Super SS: Heavy calcium carbonate (product name "Super SS", manufactured by Shiraishi Calcium Co., Ltd.)
R820: Titanium oxide (made by Ishihara Sangyo Co., Ltd.)
Tinuvin B75: Antiaging agent (manufactured by BASF)
M-8100: Polyfunctional acrylate (trade name "Aronix M-8100" manufactured by Toagosei Co., Ltd.)

As can be seen from the results of Tables 2 and 3, when Examples 1 to 11 and Comparative Example 1 are compared, the Example shows a 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 with each other, the Example shows that the tensile properties are substantially equivalent to those of Comparative Example 2 and the weather resistance is excellent.
Regarding Example 3 and Comparative Example 3, the example using divalent tin has less change in tensile properties after the heat resistance test than the initial value, as compared with Comparative Example 3 using tetravalent tin. Therefore, when divalent tin is used, excellent heat resistance is obtained.
In the comparison among Examples 1 to 11, the higher the molecular weight is, the more excellent the weather resistance is, but the viscosity of the blend tends to be higher. On the other hand, there is no significant change in tensile properties.

  Since the two-component curable composition of the present invention has a low viscosity and excellent workability, and has excellent mechanical properties and high weather resistance after curing, it is suitable for use as a two-component sealing material or adhesive. To be

Claims (4)

  A two-component type curable resin composition containing a component (A) and a component (B), wherein the component (A) contains a hydrolyzable silyl group-containing oxyalkylene polymer (A-1) and a hydrolyzate. It contains a (meth) acrylic acid ester polymer (A-2) that does not contain a degradable silyl group, and contains a divalent tin compound (B-1) and an amine compound (B-2) as the component (B). 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 are included. The two-component curable resin composition according to claim 1.   The two-component curable resin composition according to claim 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.   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 water The two components according to any one of claims 1 to 3, wherein the total amount of the (meth) acrylic acid ester polymer (B-3) containing no degradable silyl group is 20 parts by mass or more and 200 parts by mass or less. Mold-curable resin composition.