JP5003686B2 - Sealant composition - Google Patents

Description

  The present invention relates to a room temperature curable sealant composition, and more particularly to a sealant composition having high elongation at break and excellent weather resistance.

  A curable composition containing an organic polymer having a room-temperature curable reactive group is used as a sealing material or an adhesive for buildings. For example, a curable composition based on an oxyalkylene-based polymer having a hydrolyzable silyl group has good workability and is widely used as a sealing material for buildings having a good balance of mechanical properties such as elongation at break and strength at break. It's being used. Since the sealing material for construction is used by filling a gap between members that expand and contract with time, such as a siding material and a metal curtain wall, a high elongation at break is required. In addition, weather resistance that maintains performance over a long period of time is also important, and various studies have been made so far.

For example, Japanese Patent Application Laid-Open No. 59-122541 (Patent Document 1) discloses a method in which an oxyalkylene polymer having a hydrolyzable silyl group and a vinyl polymer having a hydrolyzable silyl group are used in combination. Japanese Patent Application Laid-Open No. 2004-18748 (Patent Document 2) discloses that, as a vinyl polymer having a hydrolyzable silyl group, a polymer obtained by continuous bulk polymerization at high temperature and high pressure is particularly excellent in weather resistance. Yes. Further, JP-A-2004-2604 (Patent Document 3) discloses a curing comprising a vinyl polymer having a reactive silicon group, a polyoxyalkylene polymer having a reactive silicon group, and a plasticizer having an acrylic component. A sex composition is disclosed.
JP 2002-294022 A (Patent Document 4) has an acrylic component with respect to an oxyalkylene polymer having a hydrolyzable silyl group and a vinyl polymer having a hydrolyzable silyl group which are not compatible with each other. A curable composition in which a plasticizer such as a plasticizer, a phthalate ester, or a polyether polyol is added to be compatible is disclosed.
However, a sealing material containing a vinyl polymer having a hydrolyzable silyl group as described above tends to have a lower elongation at break than a sealing material consisting only of an oxyalkylene polymer, and has an elongation at break and weather resistance. There was a case where the balance of was insufficient.
Sho 59-122541 JP 2004-18748 A JP 2004-2604 A Japanese Patent Application Laid-Open No. 2002-294022

  An object of the present invention is to provide a sealing material composition having high elongation at break and excellent weather resistance.

  In order to solve the above problems, the present inventor has (A) an oxyalkylene polymer having a hydrolyzable silyl group, (B) a vinyl polymer having a crosslinkable functional group, and (C) a sealing material containing a plasticizer. Focusing on the mixed state of the composition, intensive studies have been made. As a result, after sufficiently mixing the mixture of (A), (B) and (C) and allowing to stand at room temperature conditions (15 to 23 ° C.) for 24 hours, the interface can be visually observed, or The white turbid state, that is, the composition in which the mixture of (A), (B) and (C) is incompatible is a sealing material composition having an excellent balance between physical properties of high elongation at break and weather resistance. The headline and the present invention were completed.

  That is, the invention according to claim 1 of the present invention includes (A) an oxyalkylene polymer having a hydrolyzable silyl group, (B) a vinyl polymer having a crosslinkable functional group, and (C) a sealing containing a plasticizer. A sealant composition characterized in that the mixture of (A), (B) and (C) is incompatible.

The invention according to claim 2 is the sealing material composition according to claim 1, wherein the vinyl polymer having a crosslinkable functional group is a (meth) acrylic polymer.
The invention according to claim 3 is characterized in that the vinyl polymer having a crosslinkable functional group contains 2-ethylhexyl (meth) acrylate unit and / or cyclohexyl unit (meth) acrylate as a constituent monomer unit. The sealant composition according to claim 2.

The invention according to claim 4 is the sealing material composition according to any one of claims 1 to 3, wherein the crosslinkable functional group of the vinyl polymer is an alkoxysilyl group.
The invention according to claim 5 is the sealing according to any one of claims 1 to 4, wherein the vinyl polymer is obtained by continuously polymerizing a raw material monomer at a temperature of 150 to 350 ° C. It is a material composition.

The invention according to claim 6 is the sealing material composition according to any one of claims 1 to 5, wherein the plasticizer is a plasticizer containing a (meth) acrylic polymer as a component.
The invention according to claim 7 is the sealing material composition according to claim 6, wherein the plasticizer comprising a (meth) acrylic polymer as a component is obtained by continuous polymerization at a temperature of 150 to 350 ° C. It is.
In the invention according to claim 8, the vinyl polymer having a crosslinkable functional group is based on 100 parts by mass of all monomer units constituting the vinyl polymer, and (meth) acrylic acid 2-ethylhexyl unit and (meta 4) The sealing material composition according to claim 3, wherein the total proportion of cyclohexyl acrylate units is 70 to 99 parts by mass.

  The sealing material composition of the present invention is a sealing material composition having high elongation at break and excellent physical property balance with weather resistance, and is suitably used as a sealing material or an adhesive for buildings.

  Hereinafter, the present invention will be described in detail. Acrylic or methacrylic is also referred to as (meth) acrylic.

The (A) oxyalkylene polymer having a hydrolyzable silyl group in the present invention is a polyoxyalkylene compound having a hydrolyzable silyl group at the terminal.
The hydrolyzable silyl group is not particularly limited, and examples thereof include an alkoxysilyl group. Examples of the alkoxysilyl group include trimethoxysilyl group, methyldimethoxysilyl group, dimethylmethoxysilyl group, triethoxysilyl group, and methyldiethoxysilyl group. And a methyldimethoxyethoxysilyl group, and among these, a trimethoxysilyl group and a methyldimethoxysilyl group are preferable from the viewpoint of the balance between curing speed and flexibility.

Examples of the oxyalkylene polymer include polymers containing an oxyalkylene unit having the structure shown below.
_{- (CH 2) n -O- (} n is an integer of from 1 to 10)
—CH ₂ CH (CH ₃ ) —O—
—CH ₂ CH (C ₂ H ₅ ) —O—
—CH ₂ C (CH ₃ ) ₂ —O—
—CH ₂ CH (CH═CH ₂ ) —O—

The oxyalkylene polymer may contain one or more of the above repeating units. Among these, a polymer having an oxyalkylene unit of —CH ₂ CH (CH ₃ ) —O— is preferable in terms of excellent workability.
The production method of the oxyalkylene polymer is not particularly limited. For example, using a corresponding epoxy compound or diol as a raw material, a polymerization method using an alkali catalyst such as KOH, a polymerization method using a transition metal compound-porphyrin complex catalyst And a polymerization method using a double metal cyanide complex catalyst and a polymerization method using phosphazene. The polymerization method using a composite metal cyanide complex catalyst using an epoxy compound as a raw material is suitable for obtaining a polymer having a high molecular weight and a narrow molecular weight distribution, and has an excellent balance between the viscosity of the sealing material composition and the elongation at break of the cured product. preferable.
The average number of hydrolyzable silyl groups per molecule of the oxyalkylene polymer having hydrolyzable silyl groups is preferably 1 to 4. If the number exceeds 4, the resulting composition may become hard, and if it is less than 1, the resulting composition may be insufficiently cured.

  The weight average molecular weight of the oxyalkylene polymer having a hydrolyzable silyl group is preferably 2,000 to 50,000 in terms of polystyrene by gel permeation chromatography (GPC). If the weight average molecular weight is less than 2,000, the flexibility of the cured product obtained by curing the sealing material composition may be insufficient, and if the weight average molecular weight exceeds 50,000, the viscosity of the composition increases. In some cases, workability may be reduced during the application of the sealing material composition.

  Specific examples of the oxyalkylene polymer having a hydrolyzable silyl group include “MS Polymer S203” (trade name), “MS Polymer S303” (trade name), “Syryl SAT200” (trade name), and “ Examples include “Silyl SAT30” (trade name), “Exester ESS2410” (tradename), “Exester ESS2420” (tradename) and “Excestar ESS3430” (tradename) manufactured by Asahi Glass Co., Ltd. Can be used.

The vinyl polymer having a crosslinkable functional group (B) in the present invention preferably has an average number of crosslinkable functional groups per molecule of 0.1 to 1. In order to increase the elongation at break, 0.1 to 0.6 is more preferable, and 0.1 to 0.3 is most preferable. When the average number of crosslinkable functional groups per molecule is less than 0.1, the sealing material composition may have insufficient curability, and the cured product may have insufficient weather resistance. It may become. If the average number of crosslinkable functional groups exceeds 1, the curability of the sealing material composition may be too strong, and the cured product may be insufficient in flexibility (elongation).
In the present invention, the average number of crosslinkable functional groups per molecule is determined as the product of the number average molecular weight (g / mol) in terms of polystyrene by GPC and the crosslinkable functional group concentration (mol / g).

  The vinyl polymer preferably has a polystyrene equivalent weight average molecular weight of 6,000 to 25,000 by GPC. From the viewpoint of the viscosity of the sealing material composition (influencing workability) and the balance between the weather resistance of the cured product and the elongation at break, 8,000 to 20,000 is more preferable, and 10,000 to 15,000 is most preferable. If the weight average molecular weight is less than 6,000, the sealing material composition may have insufficient curability, and the cured product may have insufficient weather resistance. The higher the weight average molecular weight, the more easily the cured product has excellent weather resistance. However, when the weight average molecular weight exceeds 25,000, the composition becomes highly viscous, and the sealing material composition manufacturing process or the sealing material composition coating Workability may be reduced.

The crosslinkable functional group is not particularly limited as long as it is a crosslinkable functional group. For example, a hydrolyzable silyl group, a hydroxyl group, an epoxy group, an alkenyl group, an amino group, a polymerizable carbon-carbon double bond, and the like. can give. Among these, a hydrolyzable silyl group is preferable because it can easily co-crosslink with an oxyalkylene polymer having a hydrolyzable silyl group.
Examples of the hydrolyzable silyl group include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, and a diisopropoxymethylsilyl group.
Examples of the method for introducing a crosslinkable silyl group include a method in which a monomer having these functional groups is copolymerized with another raw material vinyl monomer, and a method in which a functional group is introduced into a vinyl polymer by a polymer reaction. .
As a method for introducing a hydrolyzable silyl group, a monomer having a hydrolyzable silyl group is copolymerized with another raw material vinyl monomer, or a vinyl polymer having an alkenyl group is hydrolyzed using a hydrosilylation catalyst. A method of adding a hydrosilane compound having a decomposable silyl group, a method of reacting a vinyl polymer having a hydroxyl group with a compound having a group capable of reacting with a hydroxyl group such as a crosslinkable silyl group and an isocyanate group in one molecule, For example, a method using a chain transfer agent having a hydrolyzable silyl group or an initiator in synthesizing the compound may be used.

  Although it does not specifically limit as a vinyl monomer which comprises a vinyl polymer, From the point of the mechanical physical property as a sealing material composition, and a weather resistance, a (meth) acrylic-type monomer is preferable.

  As a preferable example of the vinyl polymer, (meth) acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms in the ester chain: 40 to 99.5 parts by mass, vinyl monomer having a crosslinkable functional group: 0.0. A polymer obtained by polymerizing 5 to 10 parts by mass and other vinyl monomers: 0 to 59.5 parts by mass is preferable. The more preferable ratio of each monomer is 60 to 99 parts by mass, 1 to 7 parts by mass, and 0 to 39 parts by mass (a ratio based on 100 parts by mass of all monomers used for producing the vinyl polymer). It is. As the monomer having a crosslinkable functional group, a vinyl monomer having an alkoxysilyl group is preferable.

  In the ratio of the raw material monomer of the vinyl polymer, when the (meth) acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms in the ester chain is less than 40 parts by mass, the glass transition temperature of the cured product becomes high. Therefore, the flexibility (elongation) of the cured product may be reduced. If it exceeds 99.5 parts by mass, the cured product becomes soft, and the strength of the cured product may be reduced. If the vinyl monomer having a crosslinkable functional group is less than 0.5 parts by mass, the crosslink density of the cured product is lowered, and the strength of the cured product may be reduced. If it exceeds 10 parts by mass, the crosslink density of the cured product becomes high, and the elongation of the cured product may be insufficient.

  Specific examples of the (meth) acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms in the ester chain include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth ) Isopropyl acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, neopentyl (meth) acrylate, (meth) acrylic acid 2 -Aliphatic alkyl acrylates such as ethylhexyl, cyclohexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, chloroethyl (meth) acrylate, trifluoro (meth) acrylate Including hetero atoms such as ethyl and tetrahydrofurfuryl (meth) acrylate Acrylic acid esters and the like, may be polymerized of one or two or more of these. Among these, 2-ethylhexyl (meth) acrylate and cyclohexyl (meth) acrylate are preferable.

  In particular, the total of 2-ethylhexyl (meth) acrylate and cyclohexyl (meth) acrylate is preferably 70 to 99 parts by mass (ratio based on 100 parts by mass of all monomers used for production of the vinyl polymer). 85-99 mass parts is further more preferable. In the present invention, (A) an oxyalkylene polymer having a hydrolyzable silyl group, (B) a vinyl polymer having a crosslinkable functional group, and (C) a mixture of plasticizers are incompatible with each other, resulting in high elongation at break. It is important to do. By making the total of 2-ethylhexyl (meth) acrylate and cyclohexyl (meth) acrylate within the above range, the mixture of (A), (B) and (C) becomes incompatible.

Examples of vinyl monomers having an alkoxysilyl group include vinyl silanes such as vinyl trimethoxysilane, vinyl triethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, (meth) acrylic acid trimethoxysilylpropyl, (meth) Silyl group-containing (meth) acrylic esters such as triethoxysilylpropyl acrylate and methyldimethoxysilylpropyl (meth) acrylate, silyl group-containing vinyl ethers such as trimethoxysilylpropyl vinyl ether, vinyl trimethoxysilylundecanoate, etc. Examples include silyl group-containing vinyl esters.
Among these, a (meth) acrylic acid ester having a methoxysilyl group or an ethoxysilyl group is preferable from the viewpoint of copolymerization with a (meth) acrylic acid ester and flexibility of the copolymer, and more preferably ( (Meth) methyldimethoxysilylpropyl methacrylate, (meth) trimethoxysilylpropyl methacrylate, (meth) methyldiethoxysilylpropyl methacrylate and (meth) triethoxysilylpropyl methacrylate.

  As functional group-containing monomers other than vinyl monomers having an alkoxysilyl group, hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxyethyl (meth) acrylate (Meth) acrylic acid hydroxyalkyls such as ε-caprolactone addition reaction product, epoxy group-containing monomers such as glycidyl (meth) acrylate and vinyl glycidyl ether, acrylic acid and methacrylic acid, acrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, methacrylamide, N-methylmethacrylamide, N, N-dimethylmethacrylamide and the like can be mentioned.

  Other monomers can be used as long as the physical properties of the vinyl polymer are not impaired. Examples of such monomers include (meth) acrylic acid alkyl esters having 9 or more alkyl groups and functional group-containing monomers.

  Examples of the (meth) acrylic acid alkyl ester having an alkyl group having 9 or more carbon atoms include nonyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, and stearyl (meth) acrylate. The

  Furthermore, α-olefins such as ethylene, propylene, 1-butene and isobutylene, chloroethylenes such as vinyl chloride and vinylidene chloride, and fluoroethylenes such as tetrafluoroethylene, trifluoroethylene, chlorotrifluoroethylene and vinylidene fluoride , Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether and cyclohexyl vinyl ether, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, Veova 9, Veova 10 (manufactured by Shell Chemical Co., Ltd., Vinyl esters having 9 and 10 carbon atoms) and vinyl esters such as vinyl laurate, and allyl ethers such as ethyl allyl ether and butyl allyl ether. It is.

The glass transition temperature of the vinyl polymer having a crosslinkable functional group in the present invention is -70 to 10 ° C.
It is preferable that it is -65--20 degreeC. If it exceeds 10 ° C, it may be hard to use in the winter, and if it is below -70 ° C, the stain resistance may be inferior.

The vinyl polymer having a crosslinkable functional group (B) in the present invention can be obtained by ordinary radical polymerization, and may be any of solution polymerization, bulk polymerization, and dispersion polymerization, and a living radical polymerization recently developed. It may be legal. The reaction process may be any of batch, semi-batch and continuous polymerization. Most preferably, however, those obtained by a high-temperature continuous polymerization method at 150 to 350 ° C. are preferred.
According to this method, since a cleavage reaction starting from a hydrogen abstraction reaction from a polymer chain occurs due to high temperature polymerization, the molecular weight can be easily produced without containing a large amount of impurities such as an initiator and a chain transfer agent. In the present invention, since the ratio of the crosslinkable functional group introduced into the vinyl polymer is small, the uniform introduction of the crosslinkable functional group into the polymer indicates that the resulting sealing material composition has excellent curability. It is important for developing performance such as weather resistance. It is preferable to use a stirred tank reactor as the reactor because a vinyl polymer having a relatively narrow composition distribution (distribution of crosslinkable functional groups) and molecular weight distribution can be obtained. Also, a process using a continuous stirred tank reactor is more preferable than a tubular reactor because the composition distribution and molecular weight distribution are narrowed.

  As the continuous polymerization method, known methods disclosed in JP-A-57-502171, JP-A-59-6207, JP-A-60-250007, JP-A-10-511992, and the like can be used. Follow it. 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 solvent is supplied to the reactor at a constant supply rate. In addition, a method may be mentioned in which the reaction liquid is extracted in an amount corresponding to the amount of the monomer mixture supplied, and the liquid level in the reactor is controlled to be constant. The liquid level in the reactor may be controlled so that a head space (gas phase portion) is formed above the reaction solution, or the reactor is filled with the reaction solution (gas phase portion cannot be formed). You may control so that it may be in a liquid state. A radical polymerization initiator can also be mix | blended with a monomer mixture as needed. In the case of blending, the blending amount is preferably 0.001 to 2 parts by mass with respect to 100 parts by mass of the monomer mixture.

From the reaction liquid extracted from the reactor, the polymer can be isolated by distilling off volatile components such as unreacted monomer, solvent, and low molecular weight oligomer by distillation or the like. A part of the volatile components such as unreacted monomer, solvent, and low molecular weight oligomer distilled off from the reaction solution can be returned to the raw material tank or directly returned to the reactor and used again for the polymerization reaction.
Thus, the method of recycling an unreacted monomer and a solvent is a preferable method from an economical viewpoint. In the case of recycling, it is necessary to determine the mixing ratio of newly supplied monomer mixture so as to maintain the desired monomer ratio and the desired amount of solvent in the reactor.
The proportion of the distillate returned to the raw material tank or the reactor is preferably 30 to 98%, more preferably 50 to 95%. If it exceeds 98%, gel may be generated in the reactor during polymerization, and scale may adhere. If it is less than 30%, the economic effect is low.

  The polymerization pressure depends on the reaction temperature and the boiling point of the monomer mixture and solvent to be 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 residence time exceeds 60 minutes, productivity may deteriorate. A more preferred residence time is 2 to 40 minutes, most preferably 5 to 20 minutes.

  In addition, when the polymerization temperature is less than 150 ° C., a branching reaction occurs to widen the molecular weight distribution, and a large amount of initiator and chain transfer agent are required to lower the molecular weight, so that weather resistance, heat resistance and durability are improved. Adversely affected. Moreover, in order to maintain reaction temperature, the problem that a big energy is needed for heat removal may arise. On the other hand, if it is higher than 350 ° C., a decomposition reaction occurs and the reaction solution is colored or the molecular weight is lowered. More preferably, it is 160 degreeC-220 degreeC, Most preferably, 160 degreeC-200 degreeC is good. By polymerizing in this temperature range, it is possible to efficiently produce a copolymer having an appropriate molecular weight, a low viscosity, no coloration and little impurities.

As the radical polymerization initiator, any initiator that generates radicals at a predetermined reaction temperature may be used. For example, diisopropyl peroxydicarbonate, di-2-ethoxyethyloxydicarbonate, tertiary butyl peroxypivalate, ditertiary butyl peroxide, ditertiary hexyl peroxide, ditertiary mil peroxide, benzoyl peroxide and lauroyl peroxide Peroxides such as oxides, or 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile) and 2,2′-azobis (2,4-dimethylvaleronitrile) And azo compounds such as inorganic peroxides such as ammonium persulfate and potassium persulfate, and metal complexes used in living polymerization. Further, a thermally initiated radical generated from styrene or the like may be used.
Particularly preferred are ditertiary butyl peroxide, ditertiary hexyl peroxide, ditertiary mil peroxide and azo-based initiators, which are inexpensive and the initiator radicals are less likely to cause hydrogen abstraction. When the hydrogen abstraction reaction occurs frequently, the molecular weight distribution becomes wide, a low molecular weight component into which no crosslinkable functional group is introduced is likely to be formed, and the resulting cured sealing material may have poor weather resistance.

  When an organic solvent is used as the reaction solvent, organic hydrocarbon compounds are suitable, cyclic ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbon compounds such as benzene, toluene and xylene, and esters such as ethyl acetate and butyl acetate. Examples thereof include 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 cannot sufficiently dissolve the (meth) acrylic acid ester copolymer, scales are likely to grow on the walls of the reactor, and production problems are likely to occur in the cleaning process. It is preferable that the usage-amount of a solvent shall be 80 mass parts or less with respect to 100 mass parts of monomer total amounts.

  Another essential component (C) constituting the sealant composition of the present invention functions as a plasticizer, and conventionally known plasticizers can be used. For example, it is obtained by continuously polymerizing phthalates such as bis (2-ethylhexyl) phthalate, polypropylene glycol having a weight average molecular weight of 1,000 to 50,000 and a vinyl monomer at a temperature of 150 to 350 ° C. A vinyl polymer having a weight average molecular weight of 800 to 15,000, a glass transition temperature of −70 to −10 ° C. and having no alkoxysilyl group is preferably used.

For polypropylene glycol having a weight average molecular weight of 1,000 to 50,000, the preferred weight average molecular weight is 3,000 to 20,000. If it is less than 1,000, the weather resistance of the cured sealant is insufficient, and if it exceeds 50,000, the viscosity of the sealant composition is high and workability may be reduced.
Commercially available products can be used as they are, and examples of such commercially available products include “Preminol 4010”, “Preminol 5005”, “Preminol 3010” (all trade names) manufactured by Asahi Glass Co., Ltd., “Uniol D4000”, “Uniol” manufactured by Nippon Oil & Fats Co., Ltd. "TG4000" (both are trade names) is exemplified.

  As the plasticizer, a vinyl polymer obtained by continuously polymerizing a vinyl monomer at a temperature of 150 to 350 ° C. is preferable. A (meth) acrylic polymer obtained by continuously polymerizing a raw material monomer at a temperature of 150 to 350 ° C. is more preferred, and a (meth) acrylic polymer obtained by continuous bulk polymerization at a temperature of 150 to 300 ° C. is more preferred. It is a coalescence. For example, an acrylate polymer described in JP-A No. 2001-207157 is preferably used.

  As the (meth) acrylic acid ester constituting the (meth) acrylic polymer, those having 1 to 20 carbon atoms are used. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) acrylic S-butyl acid, t-butyl (meth) acrylate, neopentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate And (meth) acrylate alkyl such as stearyl (meth) acrylate; (meth) acrylate alicyclic alkyl such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and tricyclodecynyl (meth) acrylate ; Hydroxyethyl (meth) acrylate, Hydroxy (meth) acrylate Hydroxyalkyl (meth) acrylate such as butyl, hydroxypropyl (meth) acrylate and ε-caprolactone addition reaction product of hydroxyethyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, dimethyl (meth) acrylate Examples include, but are not limited to, heteroatom-containing (meth) acrylates such as aminoethyl, chloroethyl (meth) acrylate, trifluoroethyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate. Moreover, you may superpose | polymerize 1 type, or 2 or more types of these.

  It is also possible to copolymerize a copolymerizable monomer other than (meth) acrylic acid ester. Examples thereof include vinyl monomers such as α-olefins, vinyl esters and vinyl ethers.

  Specific examples of the plasticizer containing the (meth) acrylic polymer as a component include ARUFON (registered trademark) “UP1000”, “UP1010”, “UP1020”, “UP1060”, “UP1080” manufactured by Toagosei Co., Ltd. “UP1110”, “UH2000”, “UH2130” (all are trade names) and the like are exemplified.

  In the present invention, the ratio of (A) the oxyalkylene polymer having a hydrolyzable silyl group and (B) the vinyl polymer having a crosslinkable functional group is based on a total amount of 100 parts by mass (A) / (B). = 10-90 parts by mass / 90-10 parts by mass is preferable, and (A) / (B) = 40-80 parts by mass / 60-20 parts by mass is more preferable. When (B) is less than 10 parts by mass, the weather resistance of the cured sealant may be insufficient, and when it exceeds 90 parts by mass, the flexibility of the cured sealant may be insufficient.

  (C) The proportion of the plasticizer is 20 to 100 masses with respect to 100 mass parts of the total amount of (A) the oxyalkylene polymer having a hydrolyzable silyl group and (B) the vinyl polymer having a crosslinkable functional group. Part. If it is less than 20 parts by mass, the plastic effect is insufficient, and if it exceeds 100 parts by mass, the cured sealant becomes too soft.

  In the present invention, it is necessary that the mixture of (A) an oxyalkylene polymer having a hydrolyzable silyl group, (B) a vinyl polymer having a crosslinkable functional group, and (C) a plasticizer is incompatible. is there. In the present invention, a boundary is formed by preparing a composition by sufficiently mixing these three kinds of components and allowing the components in the composition to separate after standing at room temperature (15 ° C. to 23 ° C.) for 24 hours. A state in which the surface can be visually confirmed or a state in which the composition is clouded (opaque) is defined as incompatible. When the composition containing these three components is completely compatible, the effect of the present invention is not exhibited.

  The sealing material composition of the present invention can contain components other than (A) to (C). Examples of such components include fillers, curing accelerators, adhesion promoters, dehydrators, light stabilizers, ultraviolet absorbers, thixotropic agents, and anti-aging agents.

  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 include zeolite, mica, silica, calcined clay, kaolin, bentonite, aluminum hydroxide and barium sulfate, glass balloon, silica balloon, and polymethyl methacrylate balloon. These fillers can improve mechanical properties and improve 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.

  The added amount of the filler is 50 to 300 parts by mass based on 100 parts by mass of the total amount of (A) the oxyalkylene polymer having a hydrolyzable silyl group and (B) the vinyl polymer having a crosslinkable functional group. preferable. More preferably, it is 100-250 mass parts. If the amount of the filler is too small or too large, the mechanical properties of the sealing material may be impaired.

  Curing accelerators include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diacetoacetonate, dibutyltin diethylhexanolate, dibutyltin dioctate, dibutyltin dimethylmalate, dibutyltin diethylmalate, dibutyltin dibutylmalate, dibutyl Tin diisooctylmalate, dibutyltin ditridecylmalate, dibutyltin dibenzylmalate, dibutyltin maleate, dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethylmalate, dioctyltin diisooctylma Tetravalent tin compounds such as rate, titanates such as tetrabutyl titanate and tetrapropyl titanate, aluminum trisacetylacetonate, aluminum trisethylacetate Organic aluminum compounds such as acetate and diisopropoxyaluminum ethyl acetoacetate, chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate, lead octylate, butylamine, octylamine, laurylamine, dibutylamine, monoethanol Amine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) Phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8- Amine compounds such as azabicyclo (5,4,0) undecene-7 (DBU), salts of these amine compounds with carboxylic acids, etc., low molecular weight polyamide resins obtained from excess polyamines and polybasic acids, Reaction product of excess polyamine and epoxy compound, silanol condensation catalyst such as silane coupling agent having amino group such as γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane, and Examples include known silanol condensation catalysts such as other acidic catalysts and basic catalysts. These curing accelerators may be used alone or in combination of two or more.

  Adhesion imparting agents such as amino silane and epoxy silane, dehydrating agents such as vinyl silane, methyl silanes, methyl orthoformate and methyl orthoacetate, light stabilizers such as hindered amine compounds, benzophenone compounds, benzotriazole compounds and oxalic acid anilide compounds UV absorbers such as amide waxes, silica-based thixotropic agents, hindered phenol-based antioxidants, or anti-aging agents that are mixtures thereof, and organic solvents may also be blended.

  As the additive, commercially available products can be used as they are. For example, as the ultraviolet absorber, Tinuvin 571, Tinuvin 1130, Tinuvin 327 (trade name, manufactured by Ciba Specialty), light As stabilizers, Tinuvin 292, Tinuvin 144, Tinuvin 123 (trade name, manufactured by Ciba Specialty), Sanol 770 (trade name, manufactured by Sankyo Co., Ltd.), and Irganox 1135, Irganox 1520 as thermal stabilizers, Irganox 1330 (trade name, manufactured by Ciba Specialty), a mixture of ultraviolet absorber / light stabilizer / heat stabilizer Tinuvin B75 (trade name, manufactured by Ciba Specialty) and the like.

As curing accelerators, U28, U100, U200, U220, U303 (trade name, manufactured by Nitto Kasei Co., Ltd.), SCAT-7, SCAT-46A, No918 (trade name, manufactured by Sansha Co., Ltd.), thixo Disperson 3600N, disparon 3800,
Dispalon 305, Disparon 6500 (trade name, manufactured by Enomoto Kasei Co., Ltd.), and as an anti-tack agent, Aronix M8030, M8060, M8100, which are acrylic oligomers,
M309 (trade name, manufactured by Toagosei Co., Ltd.), a mixture with a photopolymerization initiator, unsaturated fatty acid oil such as tung oil, linseed oil, R15HT (trade name, manufactured by Idemitsu Petroleum Co., Ltd.), PBB3000 (trade name) , Nippon Soda Co., Ltd.), Gossellac 500B (produced by Nippon Synthetic Chemical Co., Ltd.) and the like.

  Examples of aminosilane include A1100, A1102, A1120, A1122, Y9669, and A1160 (trade name, manufactured by Nihon Unicar Co., Ltd.), and examples of epoxysilane include A187 and A186 (trade name, manufactured by Nihon Unicar Co., Ltd.). Is done. Further, mercaptosilanes such as A189 and AZ6129 (trade name, manufactured by Nihon Unicar Co., Ltd.), vinyl group-containing silanes such as A151 and A174 (trade name, manufactured by Nihon Unicar Co., Ltd.), A1310, Y5187 (trade name, Japan) And isocyanate silanes such as Unicar Co., Ltd.

  The sealing composition of the present invention comprises essential components (A) an oxyalkylene polymer having a hydrolyzable silyl group, (B) a vinyl polymer having a crosslinkable functional group, and (C) a plasticizer. It can manufacture by mix | blending the additive illustrated above as needed, and mixing by a normal method.

  Hereinafter, a synthesis example and an Example are given and demonstrated concretely. Unless otherwise specified, “parts” means “parts by mass”. The raw material charge ratio in the table is also displayed in parts by mass.

<Synthesis Example 1>
A pressure stirred tank reactor having a capacity of 1000 ml equipped with an oil jacket was kept at a temperature of 200 ° C. While maintaining the reactor pressure constant, 10 parts of methyl methacrylate (hereinafter referred to as MMA), 10 parts of butyl acrylate (hereinafter referred to as BA), and 2-ethylhexyl acrylate (hereinafter referred to as HA) of 78 parts. .6 parts, 1.4 parts of γ-methacryloxypropyltrimethoxysilane (hereinafter referred to as MSi), 12 parts of isopropyl alcohol (hereinafter referred to as IPA), 8 parts of methyl orthoacetate (hereinafter referred to as MOA), 10 parts of methyl ethyl ketone The monomer mixture consisting of 0.2 part of ditertiary hexyl peroxide as a polymerization initiator was continuously fed from the raw material tank to the reactor at a constant feed rate (48 g / min, residence time: 12 minutes). The reaction liquid corresponding to the amount of monomer mixture fed was continuously withdrawn from the reactor. Immediately after the start of the reaction, once the reaction temperature decreased, a temperature increase due to the heat of polymerization was observed, but the reaction temperature was maintained at 163 to 165 ° C. by controlling the oil jacket temperature. The time when the temperature became stable from the start of the supply of the monomer mixture was taken as the reaction liquid collection start point, and the reaction was continued for 25 minutes. As a result, 1.2 kg of the monomer mixture was supplied, and 1.2 kg of reaction was started. The 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 concentrated solution (referred to as polymer 1). The number average molecular weight (hereinafter referred to as Mn) of the polymer 1 in terms of polystyrene measured by GPC using tetrahydrofuran as a solvent was 4,100, and the weight average molecular weight (hereinafter referred to as Mw) was 10,700. . The number of hydrolyzable silyl groups per molecule of polymer 1 was 0.23. The viscosity of the polymer 1 measured with an E-type viscometer at a temperature of 25 ° C. and a rotation speed of 5 rpm was 25700 mPa · s.

<Synthesis Example 2>
A pressure stirred tank reactor having a capacity of 1000 ml equipped with an oil jacket was kept at a temperature of 200 ° C. While maintaining the reactor pressure constant, MMA 10 parts, BA 10 parts, HA 77 parts, MSi 3 parts, IPA 4 parts, MOA 6 parts, and ditertiary hexyl peroxide as a polymerization initiator. The monomer mixture consisting of 0.1 part is continuously fed from the raw material tank to the reactor at a constant feed rate (48 g / min, residence time: 12 minutes), which corresponds to the feed amount of the monomer mixture. The reaction solution was continuously withdrawn from the reactor. Immediately after the start of the reaction, once the reaction temperature decreased, a temperature increase due to the heat of polymerization was observed, but the reaction temperature was maintained at 179 to 181 ° C. by controlling the oil jacket temperature. The time when the temperature became stable from the start of the supply of the monomer mixture was taken as the reaction liquid collection start point, and the reaction was continued for 25 minutes. As a result, 1.2 kg of the monomer mixture was supplied, and 1.2 kg of reaction was started. The 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 concentrated solution (referred to as polymer 2). Tetrahydrofuran was used as a solvent, and the Mn of the polystyrene-converted polymer 2 measured by GPC was 4,600 and Mw was 13,600. Further, the number of hydrolyzable silyl groups per molecule of the polymer 2 was 0.56.

<Synthesis Examples 3 and 4>
The type and ratio of the monomer and the reaction temperature were changed as shown in Table 1, and polymerization and treatment were performed in the same manner as in Synthesis Example 2 except that the polymerization initiator ditertiary hexyl peroxide was changed to 0.2 part. A copolymer was synthesized. The obtained polymers are referred to as polymers 3 and 4, respectively. The results of these analyzes are shown in Table 1.

<Synthesis Examples 5 and 6>
A copolymer was synthesized by performing polymerization and treatment in the same manner as in Synthesis Example 1 except that the conditions were changed as shown in Table 1. The obtained polymers are referred to as polymers 5 and 6, respectively. The results of these analyzes are shown in Table 1.

<Example 1>
Method for evaluating compatibility 70 parts ES-S2420 (trade name, manufactured by Asahi Glass Co., Ltd.) as a polyoxyalkylene polymer having a hydrolyzable silyl group, and polymer 1 as a vinyl polymer having a hydrolyzable silyl group A composition comprising (A), (B) and (C) components obtained by mixing 30 parts, 50 parts of ARUFON UP1000 (trade name, manufactured by Toagosei Co., Ltd.) as a plasticizer and sufficiently stirring. Sealed in a glass jar. After standing at room temperature (23 ° C.) for 24 hours, the appearance was visually evaluated, and compatibility was evaluated based on whether or not a boundary surface could be confirmed in the composition or whether it was cloudy. The compatibility evaluation results are shown in Table 2.

Tensile test A composition comprising components (A), (B), (C), a curing accelerator, an adhesion-imparting agent, and a dehydrating agent was prepared with the formulation shown in Table 2. The composition was cured for 1 week under conditions of 23 ° C. and 50% RH to prepare a cured sheet having a thickness of 2 mm. A dumbbell for tensile test (JIS K 6251 No. 3 type) was prepared from the obtained cured sheet, and elongation at break was measured with a tensile tester (manufactured by Toyo Seiki Co., Ltd., Tensilon 200) (tensile speed was 50 mm / min). ). Table 2 shows the measurement results of elongation at break.

<Examples 2 to 4, Comparative Examples 1 and 2>
As in Example 1, the compatibility of the composition comprising the components (A), (B) and (C) was evaluated.
Further, in the same manner as in Example 1, the elongation at break of a cured product sheet obtained by curing a composition comprising the components (A), (B), (C), a curing accelerator, an adhesion promoter, and a dehydrating agent. Was evaluated.
These results are shown in Table 2.
In Examples 1 to 4, the appearance of the composition comprising the components (A), (B) and (C) was cloudy and not compatible, but in Comparative Examples 1 and 2, the appearance of the composition was transparent It was compatible. In Examples 1 to 4, which were incompatible in the compatibility evaluation, compared with Comparative Examples 1 and 2, which were compatible, a sealing material composition to which a curing accelerator, an adhesion-imparting agent and a dehydrating agent were added ( The cured product obtained by curing the curable composition) showed a high elongation at break.

<Examples 5-9, Comparative Examples 3-4>
A sealing material composition (curable composition) in which components of the types and proportions shown in Table 3 were blended was prepared. The composition was cured for 1 week under conditions of 23 ° C. and 50% RH to prepare a cured sheet having a thickness of 2 mm. A dumbbell for tensile test (JIS K 6251 No. 3 type) was prepared from the obtained cured sheet, and elongation at break was measured with a tensile tester (manufactured by Toyo Seiki Co., Ltd., Tensilon 200) (tensile speed was 50 mm / min). ). Table 3 shows the measurement results of elongation at break.

Weather resistance test A sealing material composition (curable composition) containing the components in the types and proportions shown in Table 3 was prepared. The composition was cured for 1 week under conditions of 23 ° C. and 50% RH to prepare a cured sheet having a thickness of 2 mm. Using the resulting cured sheet as a test piece, an accelerated weather resistance test was conducted with a metalling weather meter (DAIPLA METAL WEATHER KU-R5NCI-A, manufactured by Daipura Wintes Co., Ltd.), and the surface condition after 500 hours had elapsed Was visually evaluated. The criteria for surface condition are as follows. The weather resistance evaluation results are shown in Table 3.
○: No change (no cracks).
Δ: There were minute cracks.

  The sealing material composition of the present invention is a sealing material composition in which the obtained cured product has an excellent balance between physical properties of high elongation at break and weather resistance, and can be used as a sealing material or an adhesive for buildings. It is.

Claims (9)

  A sealant composition comprising (A) an oxyalkylene polymer having a hydrolyzable silyl group, (B) a vinyl polymer having a crosslinkable functional group, and (C) a plasticizer, wherein (A) and (B) And a mixture of (C) is not compatible.   The sealing material composition according to claim 1, wherein the vinyl polymer having a crosslinkable functional group is a (meth) acrylic polymer.   The sealing according to claim 1 or 2, wherein the vinyl polymer having a crosslinkable functional group contains a 2-ethylhexyl (meth) acrylate unit and / or a cyclohexyl (meth) acrylate unit as a constituent monomer unit. Material composition.   The sealing material composition according to any one of claims 1 to 3, wherein the crosslinkable functional group of the vinyl polymer is an alkoxysilyl group.   The sealing material composition according to any one of claims 1 to 4, wherein the vinyl polymer having a crosslinkable functional group is obtained by continuously polymerizing a raw material monomer at a temperature of 150 to 350 ° C. .   The sealing material composition according to any one of claims 1 to 5, wherein the plasticizer is a plasticizer containing a (meth) acrylic polymer as a component.   The sealing material composition according to claim 6, wherein the plasticizer comprising a (meth) acrylic polymer as a component is obtained by continuously polymerizing a raw material monomer at a temperature of 150 to 350 ° C.   The vinyl polymer having a crosslinkable functional group has a total proportion of 2-ethylhexyl (meth) acrylate unit and cyclohexyl unit (meth) acrylate based on 100 parts by mass of all monomer units constituting the vinyl polymer. It is 70-99 mass parts, The sealing material composition of Claim 3. The sealing according to any one of claims 1 to 5, wherein the vinyl polymer having a crosslinkable functional group has an average of 0.1 to 1 crosslinkable functional group per molecule. Material composition.