WO2008059873A1

WO2008059873A1 - Sealing material composition

Info

Publication number: WO2008059873A1
Application number: PCT/JP2007/072092
Authority: WO
Inventors: Koutarou Yoneda; Michihiro Kaai; Katsunobu Mochizuki
Original assignee: Toagosei Co., Ltd.
Priority date: 2006-11-16
Filing date: 2007-11-14
Publication date: 2008-05-22
Also published as: JPWO2008059873A1; JP5003686B2

Abstract

Disclosed is a sealing material composition which is curable at room temperature, while having high elongation at break and excellent weather resistance. Specifically disclosed is a sealing material composition characterized by containing an oxyalkylene polymer (A) having a hydrolyzable silyl group, a vinyl polymer (B) having a crosslinkable functional group, and a plasticizer (C). This sealing material composition is further characterized in that the mixture of the oxyalkylene polymer (A) having a hydrolyzable silyl group, the vinyl polymer (B) having a crosslinkable functional group and the plasticizer (C) is not compatible.

Description

Specification

Sealant composition

Technical field

The present invention relates to a sealing material composition that can be cured at room temperature, and more particularly to a sealing material composition that has high elongation at break and excellent weather resistance.

Background art

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

[0003] For example, in Japanese Patent Application Laid-Open No. 59-122541 (Patent Document 1), there is a method in which an oxyalkylene polymer having a hydrolyzable silyl group and a bur polymer having a hydrolyzable silyl group are used in combination. It is disclosed. In addition, JP 2004-18748 A (Patent Document 2) discloses that a bull polymer having a hydrolyzable silyl group obtained by continuous bulk polymerization at high temperature and high pressure is particularly excellent in weather resistance. Yes. Furthermore, Japanese Patent Application Laid-Open No. 2004-2604 (Patent Document 3) includes a bulle polymer having a reactive cage group, a polyoxyalkylene polymer having a reactive cage group, and a plasticizer having an acrylic component. Such curable compositions are disclosed.

In JP 2002-294022 (Patent Document 4), an acrylic component is added to an oxyalkylene polymer having a hydrolyzable silyl group and a bur polymer having a hydrolyzable silyl group which are not compatible with each other. A curable composition in which a plasticizer having a plasticizer, such as phthalates, polyether polyol, or the like, is added and dissolved is disclosed.

However, it contains a bulle polymer having a hydrolyzable silyl group as described above. Compared to a sealant made only of an oxyalkylene polymer, the sealant has a lower fracture elongation and soon the balance between the elongation at break and the weather resistance may be insufficient.

Yes

Patent Document 1: Sho 59-122541

Patent Document 2: JP 2004-18748 A

Patent Document 3: Japanese Patent Laid-Open No. 2004-2604

Patent Document 4: Japanese Patent Laid-Open No. 2002-294022

Disclosure of the invention

Problems to be solved by the invention

[0004] An object of the present invention is to provide a sealing material composition having a high elongation at break and excellent weather resistance.

Means for solving the problem

[0005] In order to solve the above problems, the present inventor has (A) an oxyalkylene polymer having a hydrolyzable silyl group, (B) a bulle polymer having a crosslinkable functional group, and (C) a plastic. We have made extensive studies focusing on the mixed state of the sealing material composition containing the agent. As a result, after thoroughly mixing the mixture of (A), (B) and (C) and allowing to stand for 24 hours at room temperature (15-23 ° C), the interface can be visually observed Or a cloudy state, that is, a composition strength S in which the mixture of (A), (B) and (C) is incompatible, and a sealing material composition having an excellent balance of physical properties of high elongation at break and weather resistance. As a result, the present invention was completed.

That is, the invention described in claim 1 of the present invention includes (A) an oxyalkylene polymer having a hydrolyzable silyl group, (B) a bulle polymer having a crosslinkable functional group, and (C) a plastic. A sealing material composition comprising an agent, wherein the mixture of (A), (B) and (C) is incompatible.

[0007] The invention according to claim 2 is the sealing material composition according to claim 1, wherein the bulle polymer having a crosslinkable functional group is a (meth) acrylic polymer.

In the invention according to claim 3, the butyl polymer having a crosslinkable functional group is composed of (meth) acrylic acid 2-ethylhexyl unit and / or (meth) acrylic acid silane as a constituent monomer unit. The sealant composition according to claim 1 or 2, comprising a chlorhexyl unit.

Yes

[0008] 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 bulle polymer is an alkoxysilyl group. The invention according to claim 5 is the invention according to any one of claims 1 to 4, wherein the bull polymer is obtained by continuously polymerizing a raw material monomer at a temperature of 150 to 350 ° C. It is a sealing material composition.

[0009] 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 has a plasticizer power of 150-35 comprising a (meth) acrylic polymer as a component.

7. The sealing material composition according to claim 6, wherein the composition is obtained by continuous polymerization at a temperature of 0 ° C.

In the invention according to claim 8, the bulle polymer having a crosslinkable functional group is based on 100 parts by mass of all monomer units constituting the bulle polymer. 4. The sealing material composition according to claim 3, wherein the total proportion of cyclohexyl units of (meth) acrylate is 70 to 99 parts by mass.

The invention's effect

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 an adhesive for building sealing materials.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail. Acrylic or methacrylic is also called (meth) acryl.

[0012] 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 a trimethoxysilyl group, a methyldimethoxysilyl group, a dimethylmethoxysilyl group, a triethoxysilyl group, and a methyljetoxysilyl group. Group, methyldimeth A xyloxysilyl group may be mentioned, and among these, a trimethoxysilyl group and a methyldimethoxysilyl group are preferable from the balance of curing speed and flexibility.

[0013] Examples of the oxyalkylene polymer include polymers containing an oxyalkylene unit having the structure shown below.

-(CH) —〇1 (n is an integer from! To 10)

2 n

CH CH (CH) — O—

twenty three

-CH CH (C H) — O—

-CH C (CH) O—

-CH CH (CH = CH) O—

[0014] The oxyalkylene polymer may contain one or more of the above repeating units. Among these, -CH CH (CH) —O

twenty three

Preference is given to polymers having salkylene units!

The production method of the oxyalkylene polymer is not particularly limited, but for example, using a corresponding epoxy compound or diol as a raw material, a polymerization method using an alkali catalyst such as KOH, a transition metal compound using a borphyrin complex catalyst. Examples thereof include a polymerization method, a composite metal, a polymerization method using a 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. Therefore, it is preferable.

The average number of hydrolyzable silyl groups per molecule of the oxyalkylene polymer having a hydrolyzable silyl group 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.

[0015] The weight average molecular weight of the oxyalkylene polymer having a hydrolyzable silyl group is preferably 2,000 to 500,000 in terms of polystyrene by gel permeation chromatography (GPC). If the weight average molecular weight is less than 2,000, the cured product obtained by curing the sealing material composition may lack flexibility, and if the weight average molecular weight exceeds 50 000, the viscosity of the composition increases. Therefore, when applying the sealant composition Workability may be reduced.

[0016] Specific examples of the oxyalkylene polymer having a hydrolyzable silyl group include “MS Polymer S203” (trade name), “MS Polymer S303” (trade name), “Syryl SA T200J ( "Product name)" and "Cyrill SAT30" (product name), "Etasester ESS2410" (product name), "Etasester ESS2420" (product name), "Etasester ESS3430" (product name), etc. manufactured by Asahi Glass Co., Ltd. These can be used in the invention.

[0017] The BUL polymer having a crosslinkable functional group (B) in the present invention preferably has an average number of crosslinkable functional groups per molecule of 0.; In order to increase the elongation at break, 0.1 to 0.6 ί solid strength is more preferable, and 0;;! To 0.3 ί solid strength is most preferable. If 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. May occur. When the average number of crosslinkable functional groups is exceeded, the curability of the sealing material composition is 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 polystyrene-reduced number average molecular weight (g / mol) and crosslinkable functional group concentration (mol / g) by GPC. It is done.

[0018] The bull polymer preferably has a polystyrene equivalent weight average molecular weight of 6,000 to 25,000 by GPC. Viscosity of sealant composition (influencing workability), durability and rupture of cured product, and the strength of non-removal, etc., 8,000 to 20,000, more preferably 10, 00 0- Most preferred is 15,000. 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 becomes more resistant to weathering. However, if the weight average molecular weight exceeds 25,000, the composition becomes highly viscous, and the sealing material composition manufacturing process and the sealing material composition coating There is a risk that workability during construction will be reduced.

[0019] The crosslinkable functional group is not particularly limited as long as it is a functional group having crosslinkability. For example, a hydrolyzable silyl group, a hydroxyl group, an epoxy group, an alkenyl group, an amino group, a polymerizable carbon-carbon double bond Etc. Of these, hydrolyzable silyl groups are preferred because they are easy to co-crosslink with oxyalkylene polymers having hydrolyzable silyl groups! 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.

As a method for introducing a crosslinkable silyl group, 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 bulle polymer by a polymer reaction. Is mentioned.

As a method for introducing a hydrolyzable silyl group, a monomer having a hydrolyzable silyl group is copolymerized with another raw material bull monomer, and a butyl 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 butyl 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. In addition, a method using a chain transfer agent or an initiator having a hydrolyzable silyl group in the synthesis of a bulle polymer can be used.

[0020] The bull monomer constituting the bull polymer is not particularly limited! /, But from the viewpoint of mechanical properties and weather resistance as a sealing material composition, a (meth) acrylic monomer is used. preferable

Yes

[0021] As a preferred example of the bulle polymer, (meth) acrylic acid alkyl ester having an alkyl group of 1 to 8 carbon atoms in the ester chain: 40 to 99.5 parts by mass, a bifunctional crosslinkable functional group. Preferred is a polymer obtained by polymerizing 0.5 to 10 parts by mass of the monomer, and other 5 to 59.5 parts by mass of the other bull monomer. The more preferable ratio of each monomer is 60 to 99 parts by mass;! To 7 parts by mass and 0 to 39 parts by mass (the ratio based on 100 parts by mass of the total monomer used for the production of the bull polymer). ). As the monomer having a crosslinkable functional group, a butyl monomer having an alkoxysilyl group is preferred.

[0022] When the proportion of the raw monomer of the bulle polymer is less than 40 parts by mass of (meth) acrylic acid alkyl ester having an alkyl group with carbon number of 8 to 8 in the ester chain, the glass transition of the cured product Since the temperature increases, the flexibility (elongation) of the cured product may decrease. When the content exceeds 99.5 parts by mass, the cured product becomes soft and the strength of the cured product may be reduced. When less than 0.5 parts by mass of the bulle monomer having a crosslinkable functional group, the cured product is crosslinked. Since the density decreases, the strength of the cured product may decrease. If the amount exceeds 10 parts by mass, the crosslink density of the cured product will increase, and the cured product may not be sufficiently stretched.

[0023] Specific examples of (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, and propyl (meth) acrylate. , (Meth) acrylic acid isopropyl, (meth) butyl acrylate, (meth) acrylic acid isobutyl, (meth) acrylic acid s-butyl, (meth) acrylic acid t-butyl, (meth) atalinoleic acid neopentyl, (meth) acrylic 2-ethylethyl hexyl, aliphatic alkyl acrylates such as cyclohexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, chloroethyl (meth) acrylate, (Meth) acrylic acid trifluorate octylyl and (meth) acrylic acid tetrahydrofurfuryl Hetero atom-containing acrylic esters such as these may be mentioned, and one or more of these may be polymerized. Among these, (meth) acrylic acid 2-ethylhexyl and (meth) acrylic acid cyclohexyl are preferable.

[0024] In particular, the total of 2-ethylhexyl (meth) acrylate and cyclohexyl (meth) acrylate is 70 to 99 parts by mass (based on 100 parts by mass of all monomers used in the production of the bull polymer) 85 to 99 parts by mass is 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 a plasticizer is incompatible. It is important to increase the growth. The mixture of (A), (B), and (C) becomes incompatible by setting the total of 2-methyhexyl (meth) acrylate and cyclohexyl (meth) acrylate within the above range.

[0025] Examples of the butyl monomer having an alkoxysilyl group include butylsilanes such as butyltrimethoxysilane, butyltriethoxysilane, butylmethyldimethoxysilane, butyldimethylmethoxysilane, trimethoxysilylpropyl (meth) acrylate, Trimethy (meth) acrylate

Examples include methacrylic acid esters, silyl group-containing butyl ethers such as trimethoxysilylpropyl butyl ether, and silyl group-containing butyl esters such as trimethoxysilyl decanoic acid butyl.

Among these, the copolymerizability with (meth) acrylic acid ester and the flexibility of the copolymer From the viewpoint, a (meth) acrylic acid ester having a methoxysilyl group or an ethoxysilyl group is more preferred, (meth) methacrylic acid methyldimethoxysilylpropyl, (meth) methacrylic acid trimethoxysilylpropyl, (meth) Methyl methacrylate

[0026] As a functional group-containing monomer other than a butyl monomer having an alkoxysilyl group, hydroxymethyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypropyl (meth) acrylate and (meth) Ε-strength prolatatone addition reaction product of hydroxyethyl acrylate, hydroxyalkyl (meth) acrylates such as methacrylic acid, epoxy group-containing monomers such as glycidyl (meth) acrylate and vinyl glycidyl ether, acrylic acid and methacrylic acid, Examples include attalinoleamide, メチル methyl acrylamide, Ν, ジメチル dimethyl acrylamide, ジェ, チル dimethylacrylamide, methacrylamide, メチル methyl methacrylamide and Ν, ジメチル dimethyl methacrylamide.

[0027] Other monomers can be used in a range that does not impair the physical properties of the bull polymer. Examples of such monomers include (meth) acrylic acid alkyl esters having an alkyl group having 9 or more carbon atoms and functional group-containing monomers.

[0028] The (meth) acrylic acid alkyl ester having an alkyl group having 9 or more carbon atoms includes (meth) acrylic acid noel, (meth) acrylic acid lauryl, (meth) acrylic acid tridecyl and (meth) acrylic acid stearyl. Etc. are exemplified.

[0029] Further, α-olefins such as ethylene, propylene, 1-butene and isobutylene, chloroethylenes such as butyl chloride and vinylidene chloride, tetrafluoroethylene, trifluoroethylene, chlorotrifluoroethylene, fluoride Fluoroethylenes such as vinylidene, methinolevinoleateol, ethinolevinoleateol, butinolevinoleatenol, butyl ethers such as isobutyl butyl ether and cyclohexyl butyl ether, butyl acetate, butyl propionate, Butyl esters such as butyrate, caproate, force prillate, Beva 9, Beova 10 (manufactured by Shell Chemical Co., Ltd., fatty acid vinyl having 9 and 10 carbon atoms) and laurate such as laurate Tyraryl ether and butyral ether Like Arirueteru such is.

[0030] The glass transition temperature of the bull polymer having a crosslinkable functional group in the present invention is 70 to The force is preferably S, more preferably 1 65 20 ° C. If it exceeds 10 ° C, it may become hard in winter and may not be used. If it is below 70 ° C, contamination resistance may be poor.

[0031] The BUL 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 has been developed in recent years. Living radical polymerization may be used. The reaction process may be any of batch, semi-batch and continuous polymerization. Most preferably, it can be obtained by a high temperature continuous polymerization method at 150 to 350 ° C! /.

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 bulle polymer is small, the uniform introduction of the crosslinkable functional group into the polymer indicates that the resulting sealing material composition has excellent curing properties. It is important to develop performance such as durability and weather resistance. It is preferable to use a stirred tank reactor as the reactor because a bull 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 than a tubular reactor because the composition distribution and molecular weight distribution are narrowed.

[0032] As the continuous polymerization method, there are known methods disclosed in JP-A-57-502171, JP-A-59-6207, JP-A-60-215007, JP-A-10-511992, and the like. You can follow this method. 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 fed to the reactor at a constant supply rate. There may be mentioned a method in which the reaction liquid is supplied and an amount of the reaction liquid corresponding to the supply amount of the monomer mixture is extracted to control the liquid level in the reactor to be constant. The liquid level in the reactor may be controlled so that a head space (gas phase portion) is formed at the top of 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 be blended in the monomer mixture as necessary. The blending amount when blended is 0.001 to 100 parts by mass of the monomer mixture. ~ 2 parts by weight is preferred!

[0033] From the reaction liquid withdrawn from the reactor, the polymer can be isolated by distilling off volatile components such as unreacted monomers, solvents, and low molecular weight oligomers. The 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, a method of recycling unreacted monomers and solvents is a preferable method from the viewpoint of economy. When recycling, it is necessary to determine the mixing ratio of the 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 form in the reactor during polymerization, and scale may adhere. If it is less than 30%, the economic effect is low.

[0034] 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 from !! 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.

[0035] Also, when the polymerization temperature is less than 150 ° C, a branching reaction occurs and the molecular weight distribution is widened, and a large amount of initiator and chain transfer agent are required to lower the molecular weight. Adversely affects durability. In addition, there may be a problem that a large amount of energy is required for heat removal to maintain the reaction temperature. 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 ° C to 220 ° C, and most preferably 160 ° C to 200 ° C. By polymerizing in this temperature range, it is possible to efficiently produce a non-colored and low-contamination copolymer having an appropriate molecular weight and low viscosity. [0036] The radical polymerization initiator may be anything as long as it is an initiator that generates radicals at a predetermined reaction temperature. For example, diisopropyl peroxydicarbonate, di-2-etoxy shechinolate aged didicarbonate, tertiary butino liveroxybivalate, ditertiary butyl peroxide, ditertiary hex silver oxide, ditertiary milperoxide, benzoylperper Peroxides such as oxide and lauroyl peroxide, or 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile) and 2,2'-azobis (2,4-dimethyl) Azo compounds such as valeronitrile), inorganic peroxides such as ammonium persulfate and potassium persulfate, and metal complexes used in living polymerization. It may also be a thermally initiated radical generated from styrene or the like.

Particularly preferred are di-tertiary butyl peroxide, di-tertiary hexoxide, di-tertiary mil peroxide and azo-type 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, and a low molecular weight component without a crosslinkable functional group can be produced or a cured sealing material obtained immediately may have poor weather resistance.

[0037] 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, ethyl acetate. And esters such as butyl acetate, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, and alcohols such as methanol, ethanol, and isopropanol are exemplified, and one or more of these should be used. Power S can be. Solvents that cannot sufficiently dissolve (meth) acrylic acid ester copolymers are prone to scale growth on the walls of the reactor, and production problems are likely to occur during the cleaning process. The amount of the solvent used is preferably 80 parts by mass or less with respect to 100 parts by mass of the total amount of monomers.

[0038] 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, phthalates such as bis (2-ethylhexyl) phthalate, polypropylene glycol and weight monomers with a weight average molecular weight of 1,000-50,000 at a temperature of 150-350 ° C. Continuous weight A butyl polymer having a weight average molecular weight of 800 to 15,000, a glass transition temperature of 70 ° C. and not having an alkoxysilyl group is preferably used.

[0039] 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 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, such as “Preminor 4010”, “Preminore 5005”, “Preminore 3010” (Lesson is also a trade name), manufactured by Asahi Glass Co., Ltd. Examples include “unior D4000” and “unior TG4000” (both are trade names).

[0040] The plasticizer is preferably a bull polymer obtained by continuously polymerizing a bull monomer at a temperature of 150 to 350 ° C. A (meth) acrylic polymer obtained by continuously polymerizing raw material monomers 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 polymer. For example, an acrylate polymer described in JP-A-2001-207157 is preferably used.

[0041] As the (meth) acrylic acid ester constituting the (meth) acrylic polymer, those having 120 carbon atoms are used. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, (meth) isobutyl acrylate, (meth) acrylic Acid s butyl, (meth) acrylic acid t-butyl, (meth) acrylic acid neopentyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid isodecyl, (meth) acrylic acid lauryl, (meth) acrylic acid Tridecyl and (meth) acrylic acid (meth) acrylic acid such as stearyl; (meth) acrylic such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and tricyclodecynyl (meth) acrylate Oxaliphatic cyclic alkyl; hydroxymethyl (meth) acrylate, hydroxybut (meth) acrylate Ε, the best of propyl, (meth) acrylic acid hydroxypropyl and (meth) acrylic acid hydroxyethyl; Prolataton addition reaction products such as hydroxyalkyl (meth) acrylate; (meth) acrylic acid 2-methoxyethyl, (meth) acrylic acid Dimethylaminoethyl, chloroethyl (meth) acrylate, trifluoroethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, etc. Forces including, but not limited to, heteroatom-containing (meth) acrylates. One or more of these may be polymerized.

[0042] It is also possible to copolymerize a copolymerizable monomer other than (meth) acrylic acid ester. Examples thereof include bulu monomers such as α-olefins, buyl esters and buyl ethers.

[0043] Specific examples of the plasticizer containing the (meth) acrylic polymer as a component include ARUFON (registered trademark) "UP1000", "UP1010", "UP1020", "UP1060" manufactured by Toagosei Co., Ltd. “UP1080”, “UP1110”, “UH2000”, “UH2130” (the label is also a quotient name) is displayed.

[0044] In the present invention, the ratio of (A) the oxyalkylene polymer having a hydrolyzable silyl group and (B) the bull polymer having a bridging functional group is based on a total amount of 100 parts by mass (A ) / (B) = 10-90 mass parts / 90-; 10 mass parts are preferred (A) / (B) = 40-80 mass parts / 60-20 mass parts is more preferred. When (B) is less than 10 parts by mass, the weather resistance of the cured sealing material may be insufficient, and when it exceeds 90 parts by mass, the flexibility of the cured sealing material may be insufficient.

[0045] The proportion of (C) the plasticizer is based on 100 parts by mass of the total amount of (A) an oxyalkylene polymer having a hydrolyzable silyl group and (B) a bur polymer having a crosslinkable functional group. 20 to; preferably 100 parts by mass. 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 is too soft.

In the present invention, (A) an oxyalkylene polymer having a hydrolyzable silyl group,

It is necessary that the mixture of (B) the bulle polymer having a crosslinkable functional group and (C) the plasticizer is incompatible. In the present invention, a composition is prepared by sufficiently mixing these three kinds of components, and after standing at room temperature (15 ° C to 23 ° C) for 24 hours, the components in the composition are separated. It is defined as incompatible with a state in which the formed boundary surface can be visually confirmed, or a state in which the composition is cloudy (non-transparent). When the composition containing these three components is completely compatible, the effects of the present invention are not exhibited.

[0047] The sealing material composition of the present invention may contain components other than (A) to (C). Ingredients include fillers, curing accelerators, adhesion promoters, dehydrating agents, light stabilizers, ultraviolet light Examples thereof include an absorbent, a thixotropic agent, and an antiaging agent.

[0048] As the filler, light calcium carbonate having an average particle size of about 0.02-2.0 m, heavy calcium carbonate having an average particle size of about 1.0 to 5.0 m, titanium oxide, carbon black, synthesis Examples include caytic acid, talc, zeolite, my strength, 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 are highly effective in improving physical properties, are preferable.

[0049] The addition amount of the filler is 50 to 50 based on 100 parts by mass of the total amount of (A) the oxyalkylene polymer having a hydrolyzable silyl group and (B) the butyl polymer having a crosslinkable functional group. 300 parts by mass is preferred. More preferably, it is 100-250 mass parts. If the amount of filler is too small or too large, the mechanical properties of the sealant may be impaired.

[0050] Dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diacetatetonate, dibutyltin diethylhexanolate, dibutyltin dioctate, dibutyltin dimethylmalate, dibutyltin diethylmalate, dibutyltin dibutylmalate, Dibutyltin diisooctylmalate, dibutyltin ditridecylmalate, dibutyltin dibenzylmalate, dibutyltin maleate, dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethylmalate, dioctyltin diisoio Tetravalent tin compounds such as octyl malate, titanates such as tetrabutyl titanate and tetrapropyl titanate, and organics such as aluminum triacetyl acetyl acetate Luminium compounds, chelate compounds such as zirconium tetraacetyl tartrate, titanium tetraacetyl tartrate, lead octylate, butyramine, octylamine, laurylamine, dibutylamine, monoethanolamine, diethanolamine, triethanol Amines, diethylenetriamines, triethylenetetramines, olamines, cyclohexylamines, benzylamines, jetylaminopropylamines, xylylenediamines, triethylenediamines, guanidines, diphenyldaanidins, 2, 4, 6-tris (dimethylaminomethinole) phenol, morpholine, N-methylmorpholine, 2- Amino compounds such as Chinoley 4-Metinoreidamidole, 1,8 diazabicyclo (5, 4, 0) undecene 7 (DB U), or salts of these amine compounds with carboxylic acids, excess polyamines Low molecular weight polyamide resin obtained from _polyaniline and polybasic acid, reaction product of excess polyamine and epoxy compound, _{Ί —aminopropyltrimethoxysilane} , _Ν— (/ 3-aminoenoyl) aminopropylmethyldimethoxysilane, etc. Examples thereof include silanol condensation catalysts such as silane coupling agents having an amino group, and other 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.

[0051] Adhesion imparting agents such as amino silane and epoxy silane, dehydrating agents such as bur silane, methyl silanes methyl methyl formate and orthoacetate, light stabilizers such as hindered amine compounds, benzophenone compounds, benzotriazole compounds and Contains UV absorbers such as oxalic anilide compounds, amide wax, silica thixotropic agents, antioxidants such as hindered phenols, or anti-aging agents that are mixtures thereof, and organic solvents. Even if it is good.

[0052] Commercially available products can be used as they are as the additive. For example, as the ultraviolet absorber, Tinuvin 571, Tinuvin 1130, Tinuvin 327 (trade name, Ciba Specialty) ), As light stabilizer, Tinuvin 292, Tinuvin 144, Tinuvin 123 (trade name, manufactured by Ciba Specialty), Sanol 770 (trade name, manufactured by Sankyo Co., Ltd.), and Ilganox as heat stabilizer 1135, Irganox 1520, Irganox 1330 (trade name, manufactured by Ciba Specialty), UV absorber / light stabilizer / thermal stabilizer mixture Tinuvin Β75 (trade name, manufactured by Ciba Specialty).

[0053] IJJ is U28, U100, U200, U220, U303 (trade name, manufactured by Pingtung Co., Ltd.), SCAT-7, SCAT-46A, No918 (trade name, three shares) Condition

Manufactured by Seishin Co., Ltd.), Dispalon 3600N, Disparon 3800, Disparon 305, Disparon 6500 (trade name, manufactured by Enomoto Kasei) M8060, M8100, M309 (trade name, manufactured by Toagosei Co., Ltd.), or a mixture with a photopolymerization initiator, tung oil, linseed oil Unsaturated fatty acid oils such as R15HT (trade name, manufactured by Idemitsu Petroleum Co., Ltd.), PBB3000 (trade name, manufactured by Nippon Soda Co., Ltd.), Goselac 500B (manufactured by Nippon Synthetic Chemical Co., Ltd.), etc.

[0054] As amino silanes, AlOO, A1102, A1120, A1122, Y9669, A1160 (trade names, manufactured by Nippon Tunica Co., Ltd.) are used, and as epoxy silanes, A187, A186 (trade names, manufactured by Nippon Tunica Co., Ltd.). And the like. In addition, mercaptosilanes such as A189 and AZ6129 (trade name, manufactured by Nippon Tunica), vinyl group-containing silanes such as A151 and A174 (trade name, manufactured by Nippon Tunica), A1310, Y5187 (trade name, Isocyanato silane, etc. (manufactured by Nippon Tunica Co., Ltd.).

[0055] The sealing composition of the present invention comprises essential components (A) an oxyalkylene polymer having a hydrolyzable silyl group, (B) a bur polymer having a crosslinkable functional group, and (C) a plastic. In addition to the agent, the additives exemplified above are blended as necessary, and they are manufactured by mixing them in the usual manner.

[0056] Hereinafter, the synthesis examples and examples will be specifically described. Unless otherwise specified, part means part by mass. The raw material charge ratio in the table is also displayed in parts by mass.

Yes

Example

[0057] <Synthesis Example 1>

A 1000 ml pressurized stirred tank reactor 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) 78.6 parts, γ-methacryloxypropyltrimethoxysilane (hereinafter referred to as MSi) 1 to 4 parts, isopropyl alcohol (hereinafter referred to as IPA) 12 parts, methyl orthoacetate (hereinafter referred to as MOA) 8 parts , A monomer mixture consisting of 10 parts of methyl ethyl ketone and 0.2 part of ditertiary hexyloxide as a polymerization initiator from the raw material tank at a constant feed rate (48 g / min, residence time: 12 minutes) Continuous supply to the reactor was started, and a reaction solution corresponding to the supply amount of the monomer mixture was continuously withdrawn from the reactor. Immediately after the start of the reaction, once the reaction temperature decreased, an increase in temperature due to the heat of polymerization was observed. By controlling the jacket temperature, the reaction temperature was kept from 163 to 165 ° C. The time when the temperature became stable from the start of monomer mixture supply was taken as the reaction collection start point, and the reaction was continued for 25 minutes.As a result, 1.2 kg of monomer mixture was supplied, and 1.2 kg The reaction solution was recovered.

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 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. It was. 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.

A 1000 ml pressurized stirred tank reactor equipped with an oil jacket was kept at a temperature of 200 ° C. While maintaining the reactor pressure constant, 10 parts MMA, 10 parts BA, 77 parts HA, 3 parts MSi, 4 parts IPA, 6 parts MOA, ditertiary hexyl peroxide as a polymerization initiator 0.1 part of the monomer mixture is continuously fed from the raw material tank to the reactor at a constant feed rate (48 g / min, residence time: 12 minutes), corresponding to the monomer mixture feed rate The reaction solution was continuously extracted 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. By controlling the oil jacket temperature, the reaction temperature was maintained between 179 and 181 ° C. When the temperature at which the monomer mixture supply start force stabilizes was taken as the reaction collection start point, and the reaction was continued for 25 minutes, 1.2 kg of the monomer mixture was supplied. The reaction solution 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 Mn of polystyrene-converted polymer 2 measured by GPC was 4,600 and Mw was 13,600. In addition, the number of hydrolyzable silyl groups per molecule of Polymer 2 was 0.56.

[0059] <Synthesis Examples 3 and 4>

Polymerization and polymerization were performed in the same manner as in Synthesis Example 2 except that the monomer type and ratio, and the reaction temperature were changed as shown in Table 1 and that the polymerization initiator ditertiary hexyloxide was changed to 0.2 part. And 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.

[0060] <Synthesis Examples 5 and 6>

Polymerization and treatment were carried out in the same manner as in Synthesis Example 1 except that the conditions were changed as shown in Table 1, and a copolymer was synthesized. The obtained polymers are referred to as polymers 5 and 6, respectively. The results of these analyzes are shown in Table 1.

[0061] [Table 1]

Compatibility evaluation method

70 parts ES-S 2420 (trade name, manufactured by Asahi Glass Co., Ltd.) as a polyoxyalkylene polymer having hydrolyzable silyl groups, 30 parts of polymer 1 as a bulle polymer having hydrolyzable silyl groups, plastic Mixing 50 parts of ARUFON UP1000 (trade name, manufactured by Toagosei Co., Ltd.) as an agent and mixing the resulting mixture with components (A), (B) and (C) into a glass bottle. Put in and sealed. After standing at room temperature (23 ° C) for 24 hours, the appearance was visually evaluated, and the 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.

[0063] Tensile test

A composition having components (A), (B), (C), a curing accelerator, an adhesion-imparting agent and a dehydrating agent with the formulation shown in Table 2 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 the elongation at break was measured with a tensile tester (Tensilon 200, manufactured by Toyo Seiki Co., Ltd.) Min). Table 2 shows the measurement results of elongation at break.

In the same manner as in Example 1, the compatibility of the composition comprising the components (A), (B) and (C) was evaluated.

Further, as in Example 1, the elongation at break of a cured sheet obtained by curing a composition comprising (A), (B), (C) component, a curing accelerator, an adhesion promoter, and a dehydrating agent. The evaluation was fi.

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. Examples 1-4, which were incompatible in the compatibility evaluation, were compared with Comparative Examples 1 and 2 in which the curing accelerator, adhesion promoter, and dehydrating agent were added. The cured product obtained by curing the product (curable composition) showed high / high elongation at break. <Examples 5 to 9, Comparative Examples 3 to 4>

A sealing material composition (curable composition) containing the components in the types and proportions shown in Table 3 was prepared. The composition was cured at 23 ° C. and 50% RH for 1 week to prepare a cured sheet having a thickness of 2 mm. The resulting cured product sheet to create a more tensile test dumbbell (JIS K 6251 3 No. type), tensile tester (Toyo Seiki Co., Tensilon ² 00) were measured elongation at break by (a tensile speed of 50 mm / Min). Table 3 shows the measurement results of elongation at break.

[0066] 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 at 23 ° C. and 50% RH for 1 week 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 using a metering weather meter (DAIPLA METAL WEATHER KU-R5NC to A, manufactured by Daipura Wintes Co., Ltd.), and the surface condition after 500 hours had passed. Visually evaluated. The criteria for surface condition are as follows. Table 3 shows the weather resistance evaluation results.

Δ: There were minute cracks.

[0067] [Table 2]

D¾00683

1) Curing accelerator: Dibutyltin diacetyl etherate

2) Adhesion-imparting agent: N-2- (aminoethyl) l-3-aminomino trimethylsilane

3) Dehydrating agent: Vinoretrimethoxysilane

1): Calcium

2) Curing accelerator: Dibutyl-diacetylacetonate

3) Adhesion-imparting agent: N-2- (aminoethyl) -1-3-aminopropyl trimethoxysilane

4) Dehydrating agent: Vinyltrimethoxysilane

5) Light stabilizer: Sanol LS—770 (manufactured by Sankyo)

6) UV absorber: Tinuvin 327 (manufactured by Ciba Specialty Chemicals Co., Ltd.)

7) Thixotropic agent: Disparon 6500 (manufactured by Enomoto Kasei Co., Ltd.)

Claims

The scope of the claims

[1] A sealing material composition comprising (A) an oxyalkylene polymer having a hydrolyzable silyl group, (B) a bulle polymer having a crosslinkable functional group, and (C) a plasticizer, A sealant composition characterized in that the mixture of (B) and (C) is incompatible.

[2] The sealing material composition according to claim 1, wherein the bull polymer having a crosslinkable functional group is a (meth) acrylic polymer.

[3] The bulle polymer having a crosslinkable functional group contains (meth) acrylic acid 2-ethylhexyl units and / or (meth) acrylic acid cyclohexyl units as constituent monomer units. Or the sealing material composition of Claim 2.

[4] The sealant composition according to any one of claims 1 to 3, wherein the crosslinkable functional group of the bulle polymer is an alkoxysilyl group.

[5] The bull polymer having a crosslinkable functional group is obtained by continuously polymerizing a raw material monomer at a temperature of 150 to 350 ° C. Sealing material composition.

[6] 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.

[7] The sealant composition according to claim 6, wherein the plasticizer comprising the (meth) acrylic polymer as a component is obtained by continuously polymerizing the raw material monomer at a temperature of 150 to 350 ° C. .

[8] The bull polymer having a crosslinkable functional group is composed of all monomer units constituting the bull polymer.

The sealing material composition according to claim 3, wherein the total proportion of 2-methylhexyl (meth) acrylate unit and cyclohexyl unit (meth) acrylate is 70 to 99 parts by mass based on 00 parts by mass. object.