Sealant composition

Abstract

To provide a sealing material composition capable of producing a cured product which has sufficient elongation properties (normal-state adhesiveness) at the initial stage of curing and suppresses a decrease in modulus even after being immersed in hot water (has hot water resistance).SOLUTION: The sealing material composition of the present invention contains a polyoxyalkylene-based polymer (A) having a hydrolyzable silyl group, a siloxane oligomer (B) having a phenyl group and a hydrolyzable functional group, a filler (C), and a catalyst (D). The content of the siloxane oligomer (B) is 0.01-0.1.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a sealing material composition. [Background technology]

[0002] Modified silicone sealant compositions containing polyoxyalkylene polymers having hydrolyzable silyl groups are widely used as sealants and adhesives because they are safe as they do not generate toxic substances during curing, and the cured products have excellent flexibility (stretchability).

[0003] Common applications for sealants include water-related areas such as kitchens, bathrooms, toilets, and washrooms, where water resistance, especially resistance to hot water, is often required.

[0004] Patent Document 1 discloses a filler for calcium carbonate-based resins, characterized in that the surface of calcium carbonate particles is coated with amorphous calcium phosphate. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2011-11924 [Overview of the project] [Problems that the invention aims to solve]

[0006] However, the calcium carbonate-based resin filler disclosed in Patent Document 1 has the problem of having a low modulus retention rate after immersion in hot water, which can cause poor adhesion in wet applications exposed to water and moisture.

[0007] The present invention provides a sealing material composition that can produce a cured product that has sufficient elongation properties and adhesive strength (normal adhesion) in the initial stages of curing, and in which the decrease in modulus is suppressed even after immersion in hot water (hot water resistance).

Means for Solving the Problems

[0008] The sealing material composition of the present invention comprises a polyoxyalkylene polymer (A) having a number average molecular weight of 10,000 or more and a hydrolyzable silyl group, a siloxane oligomer (B) having a phenyl group and a hydrolyzable functional group, a filler (C), and a catalyst (D), and the mass ratio of the content of the siloxane oligomer (B) having a phenyl group and a hydrolyzable functional group to the total content of the polyoxyalkylene polymer (A) having a number average molecular weight of 10,000 or more and a hydrolyzable silyl group and the siloxane oligomer (B) having a phenyl group and a hydrolyzable functional group [content of the siloxane oligomer (B) having a phenyl group and a hydrolyzable functional group / (total content of the polyoxyalkylene polymer (A) having a number average molecular weight of 10,000 or more and a hydrolyzable silyl group and the siloxane oligomer (B) having a phenyl group and a hydrolyzable functional group)] is 0.01 to 0.1.

[0009] [Polyoxyalkylene Polymer (A) Having a Hydrolyzable Silyl Group] The sealing material composition contains a polyoxyalkylene polymer (A) having a number average molecular weight of 10,000 or more and a hydrolyzable silyl group (hereinafter sometimes simply referred to as "polyoxyalkylene polymer (A)"). According to the polyoxyalkylene polymer (A) having a hydrolyzable silyl group with a number average molecular weight of 10,000 or more, it is possible to provide a sealing material composition that can be cured (moisture-cured) by moisture present in the atmosphere or at joints.

[0010] The polyoxyalkylene polymer (A) has a hydrolyzable silyl group in the molecule, and preferably has a hydrolyzable silyl group at the molecular terminal. It is more preferable that the hydrolyzable silyl group is bonded to only one of the two terminals of the main chain or to both terminals. When the hydrolyzable silyl group is bonded to the terminal of the main chain, excellent normal state adhesiveness can be imparted while maintaining the excellent flexibility (elongation physical properties) of the cured product of the sealing material composition. When the polyoxyalkylene polymer (A) has a plurality of hydrolyzable silyl groups in the molecule, the hydrolyzable silyl groups may be the same or different from each other.

[0011] In the present invention, the hydrolyzable silyl group refers to a group that causes a condensation reaction by using a catalyst etc. as necessary in the presence of moisture or a crosslinking agent, such as a silicon-containing group having a hydrolyzable group bonded to a silicon atom or a silanol group. The silanol group means a functional group (≡Si-OH) in which a hydroxyl group is directly bonded to a silicon atom.

[0012] The hydrolyzable group of the hydrolyzable silyl group is not particularly limited, and examples thereof include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, an alkenyloxy group, etc.

[0013] Among them, as the hydrolyzable silyl group, an alkoxysilyl group is preferable because it can impart excellent hot water resistance while maintaining the normal state adhesiveness of the cured product of the sealing material composition.

[0014] The alkoxysilyl group preferably has a structure represented by -SiR 2 j (OR 3 ) 3-j In the formula, R 2 represents an alkyl group having 1 to 20 carbon atoms which may have a substituent or a hydrogen atom. R 3 represents an alkyl group having 1 to 6 carbon atoms. j represents an integer of 0 to 2.

[0015] Examples of alkoxysilyl groups include trialkoxysilyl groups such as trimethoxysilyl, triethoxysilyl, triisopropoxysilyl, and triphenoxysilyl; dialkoxysilyl groups such as propyldimethoxysilyl, methyldimethoxysilyl, and methyldiethoxysilyl; and monoalkoxysilyl groups such as dimethylmethoxysilyl and dimethylethoxysilyl. Among these, dialkoxysilyl and trialkoxysilyl groups are preferred, more preferably dialkoxysilyl and more preferably dimethoxysilyl, because they can impart excellent hot water resistance to the cured product of the sealing material composition.

[0016] The polyoxyalkylene polymer (A) has, on average, 1.0 to 4.0, more preferably 1.0 to 3.0 hydrolyzable silyl groups per molecule. When the number of hydrolyzable silyl groups in the polyoxyalkylene polymer (A) is 1.0 or more, the maximum load strength (adhesive strength) of the cured sealant composition in normal adhesion is improved. Furthermore, when the number of hydrolyzable silyl groups in the polyoxyalkylene polymer (A) is 3.0 or less, the maximum load elongation (stretch property) of the cured sealant composition in normal adhesion is improved.

[0017] In this invention, the average number of hydrolyzable silyl groups per molecule in the polyoxyalkylene polymer is 1 It can be calculated based on the concentration of hydrolyzable silyl groups in the polyoxyalkylene polymer determined by 1H-NMR and the number-average molecular weight of the polyoxyalkylene polymer determined by GPC.

[0018] A polyoxyalkylene polymer (A) having a hydrolyzable silyl group can be produced, for example, by reacting a polyoxyalkylene polymer having a functional group such as a hydroxyl group at its terminus with an organic compound having an active group and an unsaturated group that are reactive to this functional group, and then reacting the resulting reaction product with a hydrosilane having a hydrolyzable group to hydrosilylate it.

[0019] The main chain of the polyoxyalkylene polymer (A) is preferably a polymer containing a repeating unit represented by the general formula (1). -(O-R 1 ) n - (1) (In the formula, R 1 represents an alkylene group having 1 to 14 carbon atoms, and n is the number of repeating units and is a positive integer.)

[0020] The main chain of the polyoxyalkylene polymer (A) may consist of only one kind of repeating unit or may consist of two or more kinds of repeating units.

[0021] In the present invention, the alkylene group is a divalent atomic group formed by removing two hydrogen atoms bonded to two different carbon atoms in an aliphatic saturated hydrocarbon, and includes both linear and branched atomic groups.

[0022] Examples of the alkylene group include an ethylene group, a propylene group [-CH(CH3)-CH2-], a trimethylene group [-CH2-CH2-CH2-], a butylene group, an amylene group [-(CH2)5-], a hexylene group, and the like.

[0023] Examples of the main chain skeleton of the polyoxyalkylene polymer (A) include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, a polyoxyethylene-polyoxypropylene copolymer, and a polyoxypropylene-polyoxybutylene copolymer. Since the rubber elasticity of the cured product of the sealing material composition is improved, polyoxypropylene is preferred.

[0024] Polyoxyalkylene polymers (A) having hydrolyzable silyl groups are preferred because the cured sealant composition has excellent hot water resistance. Therefore, polyoxypropylene polymers with a polyoxypropylene main chain skeleton and branched chains, and with dimethoxysilyl groups as hydrolyzable silyl groups at the ends of the main chain skeleton, are preferred. The main chain skeleton of polyoxyalkylene polymer (A) refers to the longest molecular chain in the molecule. The length of a molecular chain can be determined by the number of atoms constituting the molecular chain. A branched chain refers to a molecular chain composed of two or more carbon atoms bonded together; methyl groups, which have one carbon atom, are not included in branched chains.

[0025] The number average molecular weight of the polyoxyalkylene polymer (A) having hydrolyzable silyl groups is 10,000 or more, preferably 20,000 or more, more preferably 22,000 or more, more preferably 25,000 or more, and more preferably 28,000 or more. The number average molecular weight of the polyoxyalkylene polymer (A) having hydrolyzable silyl groups is preferably 40,000 or less, more preferably 38,000 or less, more preferably 35,000 or less, and more preferably 33,000 or less. When the number average molecular weight of the polyoxyalkylene polymer (A) is 10,000 or more, the cured product of the sealing material composition has excellent normal adhesion and excellent elongation at maximum load. When the number average molecular weight of the polyoxyalkylene polymer (A) is 40,000 or less, the hot water resistance of the cured product of the sealing material composition is improved.

[0026] The molecular weight distribution (Mw / Mn) of the polyoxyalkylene polymer (A) having hydrolyzable silyl groups is preferably 2.0 or less, more preferably 1.8 or less, and even more preferably 1.5 or less. When the molecular weight distribution (Mw / Mn) of the polyoxyalkylene polymer (A) having hydrolyzable silyl groups is 2.0 or less, the cured product of the sealing material composition has excellent maximum load elongation in normal adhesion.

[0027] In this invention, the number-average molecular weight and weight-average molecular weight of the polyoxyalkylene polymer are polystyrene-converted values ​​measured by GPC (gel permeation chromatography). Specifically, 6 to 7 mg of the polyoxyalkylene polymer is taken, the taken polyoxyalkylene polymer is supplied to a test tube, and then an o-DCB (orthodichlorobenzene) solution containing 0.05% by mass of BHT (dibutylhydroxytoluene) is added to the test tube to dilute the polyoxyalkylene polymer to a concentration of 1 mg / mL to prepare a diluted solution.

[0028] Using a dissolution filtration apparatus, the above diluted solution is shaken at 145°C at a rotation speed of 25 rpm for 1 hour to dissolve the polyoxyalkylene polymer in an o-DCB solution containing BHT, which is then used as the measurement sample. The number-average molecular weight and weight-average molecular weight of the polyoxyalkylene polymer can be measured using this measurement sample by the GPC method.

[0029] In this invention, the number-average molecular weight and weight-average molecular weight of the polyoxyalkylene polymer can be measured, for example, using the following measuring device and conditions. Measuring device: TOSOH Corporation, product name "HLC-8121GPC / HT" Measurement conditions: Column: TSKgelGMHHR-H(20)HT x 3 TSKguardcolumn-HHR(30)HT x 1 bottle Mobile phase: o-DCB 1.0mL / min Sample concentration: 1 mg / mL Detector: Blythe refractometer Standard material: Polystyrene (manufactured by TOSOH Corporation, molecular weight: 500-8,420,000) Elution conditions: 145℃ SEC temperature: 145℃

[0030] [Siloxane oligomer (B) having a phenyl group and a hydrolyzable functional group] The sealant composition contains a siloxane oligomer (B) having a phenyl group and a hydrolyzable functional group (hereinafter sometimes simply referred to as "siloxane oligomer (B)"). The siloxane oligomer (B) contains a polysiloxane skeleton-(O-Si)p- (where p is the number of repeating units and is a positive integer) and has a phenyl group and a hydrolyzable functional group. When the sealant composition contains the siloxane oligomer (B), the polyoxyalkylene polymer (A) and the siloxane oligomer (B) form a crosslinked structure, thereby incorporating the siloxane oligomer (B) into the cured product of the sealant composition, and imparting excellent hot water resistance to the cured product of the sealant composition.

[0031] Furthermore, since the siloxane oligomer (B) has a phenyl group in its molecule and exhibits excellent compatibility with the polyoxyalkylene polymer (A), the siloxane oligomer (B) and the polyoxyalkylene polymer (A) form a uniform crosslinked structure in the cured product of the sealant composition, and the cured product of the sealant composition has excellent resistance to hot water.

[0032] The main chain skeleton of siloxane oligomer (B) is preferably a linear structure containing a polysiloxane skeleton -(O-Si)p-, and more preferably a polysiloxane skeleton -(O-Si)p-. The siloxane oligomer (B) and the polyoxyalkylene polymer (A) form a uniform crosslinked structure in the cured product of the sealant composition, and the cured product of the sealant composition has excellent hot water resistance. The main chain skeleton of siloxane oligomer (B) refers to the longest molecular chain in the molecule. The length of the molecular chain can be determined to be longer as the number of atoms constituting the molecular chain increases.

[0033] In the main chain skeleton of siloxane oligomer (B), the content of the polysiloxane skeleton-(O-Si)p- is preferably 80% by mass or more, more preferably 85% by mass or more, more preferably 90% by mass or more, more preferably 95% by mass or more, and more preferably 100% by mass, so that the cured product of the sealing material composition has excellent resistance to hot water.

[0034] In the siloxane oligomer (B), the hydrolyzable functional group can be any functional group that can react with the hydrolyzable silyl group of the polyoxyalkylene polymer (A) to form a crosslinked structure. As the hydrolyzable functional group, an alkoxy group is preferred because it can impart excellent hot water resistance while maintaining the normal adhesion of the cured sealant composition. Examples of alkoxy groups include methoxy groups, ethoxy groups, and isopropoxy groups. Among these, methoxy groups and ethoxy groups are preferred, and methoxy groups are more preferred, because they can impart excellent hot water resistance to the cured sealant composition.

[0035] Siloxane oligomers (B) can be obtained, for example, by partially hydrolyzing and de-alcoholizing a polyfunctional alkoxysilane compound in the presence of a known catalyst such as an acid, a base, an organotin compound, or an organotitanium compound. Specifically, examples include siloxane oligomers having hydrolyzable functional groups at the ends of the molecular chain or in the side chains, and having a linear main chain skeleton or a three-dimensional network structure.

[0036] As the siloxane oligomer (B), a partially hydrolyzed condensate of an alkoxysilane compound represented by formula (2) is preferred. R 4 m-Si(OR 5 ) 4-m (2)

[0037] R 4 m-Si(OR 5 ) 4-m Medium, R 4 , R 5 Each of these is independently an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group having 1 to 8 carbon atoms and which may have substituents. 4 If multiple R molecules exist in the molecule, then multiple R molecules 4 They may be identical or different from one another. 5 If multiple R molecules exist in the molecule, then multiple R molecules 5 They may be identical or different from one another. Substituent R 4Of these, at least one substituent is a phenyl group. m is 1 or 2. m is preferably 1 because the cured product of the sealant composition has excellent resistance to hot water.

[0038] Since the hot water resistance of the cured sealant composition is improved, if the main chain skeleton of siloxane oligomer (B) is a linear structure containing a polysiloxane skeleton-(O-Si)p-(where p is the number of repeating units and is a positive integer), it is preferable that siloxane oligomer (B) has phenyl groups in its side chains.

[0039] Since the hot water resistance of the cured sealant composition is improved, if the main chain skeleton of siloxane oligomer (B) is a linear structure containing a polysiloxane skeleton-(O-Si)p-(where p is the number of repeating units and is a positive integer), it is preferable that siloxane oligomer (B) has an alkoxy group at the end of the main chain. As mentioned above, examples of alkoxy groups include methoxy groups, ethoxy groups, and isopropoxy groups. Methoxy groups and ethoxy groups are preferred, and methoxy groups are more preferred, as they can impart excellent hot water resistance to the cured sealant composition.

[0040] As a method for producing siloxane oligomer (B), 4 m-Si(OR 5 ) 4-m It can be produced by adding a known catalyst for hydrolysis to an alkoxysilane compound represented by [formula] and performing partial hydrolysis condensation by stirring while heating in the presence of water.

[0041] In the alkoxysilane compound represented by formula (2), when m is 1, if the hydrolysis condensate of the alkoxysilane compound represented by formula (2) has a linear structure, then the side chain contains (-OR 5 It has an alkoxy group represented by ).

[0042] In the alkoxysilane compound represented by formula (2), when m is 1, if the hydrolysis condensate of the alkoxysilane compound represented by formula (2) forms a three-dimensional network structure, then the three-dimensional network structure partially contains (-OR 5 It contains an alkoxy group represented by ).

[0043] The alkoxysilane compound represented by formula (2) may contain an alkoxysilane compound represented by formula (2) where m is 2, but the siloxane oligomer (B) may be effectively (-OR 5 Since it is possible to include an alkoxy group represented by ) and improve the hot water resistance of the cured product of the sealing material composition, it is preferable that m is 1 in the alkoxysilane compound represented by formula (2).

[0044] The content of hydrolyzable functional groups in siloxane oligomer (B) is preferably 10% by mass or more, and more preferably 15% by mass or more. The content of hydrolyzable functional groups in siloxane oligomer (B) is preferably 30% by mass or less. When the content of hydrolyzable functional groups is 10% by mass or more, the hot water resistance of the cured sealant composition is improved. When the content of hydrolyzable functional groups is 30% by mass or less, the normal adhesion of the cured sealant composition is improved.

[0045] Furthermore, the content of hydrolyzable functional groups in siloxane oligomer (B) is: 1 This refers to values ​​measured by 1H-NMR and 29Si-NMR. The content of hydrolyzable functional groups in siloxane oligomer (B) can be measured, for example, using the following measuring apparatus and conditions. < 1 H-NMR measurement conditions> Measurement device: Bruker Biospin, product name "AVANCE 400" Measurement conditions: Probe: Prodigy (BBO) Rotation speed: 20Hz Measurement pulse: Single pulse Solvent: Deuterated chloroform Concentration:1 H...approximately 1wt / vol% Temperature: 25℃ (298K) Number of scans: 64 Chemical shift reference: Chloroform 7.26 ppm < 29 Si-NMR measurement conditions> Measurement device: Bruker Biospin, product name "AVANCE 400" Measurement conditions: Probe: Prodigy (BBO) Rotation speed: 20Hz Measurement pulse: Single pulse Solvent: Deuterated chloroform Concentration: 29 Si‥‥Approx. 5wt / vol% Temperature: 25℃ (298K) Number of scans: 360 Chemical shift standard: TMS 0.0 ppm

[0046] The siloxane oligomer (B) preferably has phenyl groups in the side chains bonded to the linear main chain skeleton, and more preferably has phenyl groups directly bonded to the main chain skeleton as side chains. Having phenyl groups in the side chains bonded to the main chain skeleton is preferable because it improves the compatibility between the polyoxyalkylene polymer (A) and the siloxane oligomer (B), and the cured product of the sealant composition has excellent resistance to hot water.

[0047] In a sealing material composition, the mass ratio of the content of siloxane oligomer (B) having phenyl groups and hydrolyzable functional groups to the total content of polyoxyalkylene polymer (A) having a number average molecular weight of 10,000 or more and hydrolyzable silyl groups, and the siloxane oligomer (B) having phenyl groups and hydrolyzable functional groups [Content of siloxane oligomer (B) having phenyl groups and hydrolyzable functional groups / (Total content of polyoxyalkylene polymer (A) having a number average molecular weight of 10,000 or more and hydrolyzable silyl groups, and siloxane oligomer (B) having phenyl groups and hydrolyzable functional groups)] (hereinafter sometimes simply referred to as "siloxane oligomer content") is 0.01 or more, more preferably 0.02 or more, more preferably 0.03 or more, and more preferably 0.04 or more. When the siloxane oligomer content is 0.01 or more, the cured product of the sealing material composition has excellent hot water resistance and normal adhesion.

[0048] In the sealing material composition, the mass ratio of the content of siloxane oligomer (B) having phenyl groups and hydrolyzable functional groups to the total content of polyoxyalkylene polymer (A) having a number average molecular weight of 10,000 or more and hydrolyzable silyl groups, and the siloxane oligomer (B) having phenyl groups and hydrolyzable functional groups [Content of siloxane oligomer (B) having phenyl groups and hydrolyzable functional groups / (Total content of polyoxyalkylene polymer (A) having a number average molecular weight of 10,000 or more and hydrolyzable silyl groups, and siloxane oligomer (B) having phenyl groups and hydrolyzable functional groups)] is 0.1 or less, preferably 0.09 or less, more preferably 0.08 or less, more preferably 0.07 or less, and more preferably 0.06 or less. When the siloxane oligomer content is 0.1 or less, the cured product of the sealing material composition has excellent hot water resistance and normal adhesion.

[0049] In a sealing material composition, by setting the siloxane oligomer content to 0.01 to 0.1 and the number-average molecular weight of the polyoxyalkylene polymer (A) to 10,000 or more, preferably 20,000 to 40,000, the normal adhesion and hot water resistance of the cured product of the sealing material composition can be further improved.

[0050] [Filler (C)] The sealant composition contains a filler. When the sealant composition contains a filler, the cured product of the sealant composition has excellent normal adhesion.

[0051] The filler material is not particularly limited, and examples include calcium carbonate, magnesium carbonate, calcium oxide, hydrated silicic acid, anhydrous silicic acid, finely powdered silica, calcium silicate, titanium dioxide, clay, talc, carbon black, and glass balloons. These fillers (C) may be used alone or in combination of two or more. Among these, calcium carbonate is preferably used as the filler material.

[0052] Precipitating calcium carbonate and heavy calcium carbonate are preferred. Precipitating calcium carbonate includes light calcium carbonate and colloidal calcium carbonate.

[0053] As the calcium carbonate, either precipitated calcium carbonate or heavy calcium carbonate may be used, or both may be used. In particular, the use of precipitated calcium carbonate and heavy calcium carbonate is preferred. By using precipitated calcium carbonate and heavy calcium carbonate in combination, the cured product of the sealant composition can be given appropriate flexibility (stretchability) and excellent normal adhesion.

[0054] When heavy calcium carbonate and precipitated calcium carbonate are used as fillers, the content of precipitated calcium carbonate in the sealant composition is preferably 10 parts by mass or more per 100 parts by mass of the total content of the polyoxyalkylene polymer (A) having hydrolyzable silyl groups and the siloxane oligomer (B) having phenyl groups and hydrolyzable functional groups. When heavy calcium carbonate and precipitated calcium carbonate are used as fillers, the content of precipitated calcium carbonate in the sealant composition is preferably 300 parts by mass or less, and more preferably 200 parts by mass or less, per 100 parts by mass of the total content of the polyoxyalkylene polymer (A) having hydrolyzable silyl groups and the siloxane oligomer (B) having phenyl groups and hydrolyzable functional groups. When the content of precipitated calcium carbonate is 10 parts by mass or more, the maximum load strength in the normal adhesive state of the cured sealant composition is improved. When the content of precipitated calcium carbonate is 300 parts by mass or less, the elongation under maximum load in the normal adhesive state of the cured sealant composition is improved.

[0055] When heavy calcium carbonate and precipitated calcium carbonate are used as fillers, the content of heavy calcium carbonate in the sealant composition is preferably 30 parts by mass or more per 100 parts by mass of the total content of the polyoxyalkylene polymer (A) having hydrolyzable silyl groups and the siloxane oligomer (B) having phenyl groups and hydrolyzable functional groups. When heavy calcium carbonate and precipitated calcium carbonate are used as fillers, the content of heavy calcium carbonate in the sealant composition is preferably 500 parts by mass or less, more preferably 350 parts by mass or less, and more preferably 150 parts by mass or less per 100 parts by mass of the total content of the polyoxyalkylene polymer (A) having hydrolyzable silyl groups and the siloxane oligomer (B) having phenyl groups and hydrolyzable functional groups. When the content of heavy calcium carbonate is 30 parts by mass or more, the elongation at maximum load in the normal adhesion of the cured sealant composition is improved. When the heavy calcium carbonate content is 500 parts by mass or less, the maximum load strength in the normal adhesive state of the cured sealant composition is improved.

[0056] The content of precipitated calcium carbonate in the sealant composition is preferably 10 parts by mass or more per 100 mass of the total content of the polyoxyalkylene polymer (A) and siloxane oligomer (B). The content of precipitated calcium carbonate in the sealant composition is preferably 300 parts by mass or less, and more preferably 200 parts by mass or less, per 100 mass of the total content of the polyoxyalkylene polymer (A) and siloxane oligomer (B). When the content of precipitated calcium carbonate is 10 parts by mass or more, the maximum load strength in the normal adhesive state of the cured sealant composition is improved. When the content of precipitated calcium carbonate is 300 parts by mass or less, the maximum load elongation in the normal adhesive state of the cured sealant composition is improved.

[0057] The content of heavy calcium carbonate in the sealing material composition is preferably 30 parts by mass or more per 100 mass of the total content of the polyoxyalkylene polymer (A) and siloxane oligomer (B). The content of heavy calcium carbonate in the sealing material composition is preferably 500 parts by mass or less, more preferably 350 parts by mass or less, and even more preferably 150 parts by mass or less, per 100 mass of the total content of the polyoxyalkylene polymer (A) and siloxane oligomer (B). When the content of heavy calcium carbonate is 30 parts by mass or more, the elongation at maximum load in the normal adhesive state of the cured sealing material composition is improved. When the content of heavy calcium carbonate is 500 parts by mass or less, the strength at maximum load in the normal adhesive state of the cured sealing material composition is improved.

[0058] The average particle size of calcium carbonate is preferably 0.01 to 5 μm, and more preferably 0.05 to 2.5 μm. Calcium carbonate having such an average particle size improves the normal adhesion of the cured sealant composition. The average particle size of calcium carbonate refers to the 50% cumulative particle size in the volume-based particle size distribution determined by laser scattering.

[0059] It is preferable that the calcium carbonate is surface-treated with fatty acids or fatty acid esters. Surface-treated calcium carbonate can impart thixotropy to the sealant composition and suppress the aggregation of calcium carbonate.

[0060] The content of inorganic filler in the sealing material composition is preferably 1 part by mass or more, preferably 30 parts by mass or more, more preferably 50 parts by mass or more, more preferably 80 parts by mass or more, and more preferably 100 parts by mass or more, per 100 parts by mass of the total content of polyoxyalkylene polymer (A) and siloxane oligomer (B). The content of inorganic filler in the sealing material composition is preferably 800 parts by mass or less, preferably 600 parts by mass or less, more preferably 450 parts by mass or less, more preferably 300 parts by mass or less, and more preferably 200 parts by mass or less, per 100 parts by mass of the total content of polyoxyalkylene polymer (A) and siloxane oligomer (B). When the inorganic filler content is 1 part by mass or more, the normal adhesion of the cured product of the sealing material composition is improved. When the inorganic filler content is 800 parts by mass or less, the increase in viscosity of the sealing material composition is suppressed, and the coatability of the sealing material composition is improved.

[0061] [catalyst] The sealing material composition contains a catalyst. The catalyst is used to promote the dehydration condensation reaction between the hydrolyzable silyl group of the polyoxyalkylene polymer (A) and the hydrolyzable functional group of the siloxane oligomer (B).

[0062] Preferred catalysts include silanol condensation catalysts, organotin compounds such as 1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distanoxane, dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin phthalate, bis(dibutyltin laurate) oxide, dibutyltin bis(acetylacetonate), dibutyltin bis(monoester maleate), tin octoate, dibutyltin octoate, dioctyltin oxide, dibutyltin bis(triethoxysilicate), bis(dibutyltin bistriethoxysilicate) oxide, and dibutyltin oxybisethoxysilicate; and organotitanium compounds such as tetra-n-butoxytitanate and tetraisopropoxytitanate. These silanol condensation catalysts may be used individually or in combination of two or more.

[0063] As the silanol condensation catalyst, 1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distanoxane is preferred. With such a silanol condensation catalyst, the curing speed of the sealant composition can be easily adjusted.

[0064] The catalyst content in the sealant composition is preferably 1 to 10 parts by mass, and more preferably 1 to 5 parts by mass, per 100 parts by mass of the total content of the polyoxyalkylene polymer (A) and siloxane oligomer (B). If the catalyst content is 1 part by mass or more, the curing speed of the sealant composition can be increased and the moisture-curing properties of the sealant composition can be improved. If the catalyst content is 10 parts by mass or less, the sealant composition will have an appropriate curing speed and the handling properties of the sealant composition can be improved.

[0065] [Plasticizer] The sealing material composition preferably contains a plasticizer. Examples of plasticizers include phthalate esters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, din-normal hexyl phthalate, bis(2-ethylhexyl) phthalate, din-normal octyl phthalate, diisononyl phthalate, dinonyl phthalate, diisodecyl phthalate, diisoundecyl phthalate, and bis-butylbenzyl phthalate; and polyalkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, and polypropylene glycol. Among these, polyalkylene glycol is preferred, and polypropylene glycol is more preferred. The plasticizer is suitable for use at 23°C and 1.01 × 10⁻⁶ 5 It is preferable that the state be liquid at Pa (1 atmosphere).

[0066] When the plasticizer is a polymer, the number-average molecular weight of the plasticizer is preferably 1000 or more, and more preferably 2000 or more. When the plasticizer is a polymer, the number-average molecular weight of the plasticizer is preferably 10000 or less, and more preferably 5000 or less. When the number-average molecular weight of the plasticizer is within the above range, the cured product of the sealing material composition has excellent resistance to hot water.

[0067] In this invention, when the plasticizer is a polymer, the number-average molecular weight of the plasticizer is measured by GPC (gel permeation chromatography) and converted to polystyrene equivalent. The specific measurement method and conditions are the same as those for the polyoxyalkylene polymer (A) described above.

[0068] The content of plasticizer in the sealing material composition is preferably 1 part by mass or more, more preferably 10 parts by mass or more, per 100 parts by mass of the total content of polyoxyalkylene polymer (A) and siloxane oligomer (B). The content of plasticizer in the sealing material composition is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, and more preferably 70 parts by mass or less, per 100 parts by mass of the total content of polyoxyalkylene polymer (A) and siloxane oligomer (B).

[0069] [Dehydrating agent] The sealant composition preferably contains a dehydrating agent. The dehydrating agent helps to prevent the sealant composition from hardening due to moisture contained in the air or other sources while it is being stored.

[0070] Examples of dehydrating agents include silane compounds such as vinyltrimethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, phenyltrimethoxysilane, and diphenyldimethoxysilane; and ester compounds such as methyl orthoformate, ethyl orthoformate, methyl orthoacetate, and ethyl orthoacetate. These dehydrating agents may be used alone or in combination of two or more. Among these, vinyltrimethoxysilane is preferred.

[0071] The content of the dehydrating agent in the sealing material composition is preferably 0.5 to 20 parts by mass, and more preferably 1 to 15 parts by mass, per 100 parts by mass of the total content of the polyoxyalkylene polymer (A) and siloxane oligomer (B). When the content of the dehydrating agent is 0.5 parts by mass or more, the effect of the dehydrating agent is sufficiently obtained. Furthermore, when the content of the dehydrating agent is 20 parts by mass or less, the sealing material composition has excellent curability.

[0072] [Other additives] The sealing material composition may contain other additives such as thixotropic agents, antioxidants, UV absorbers, pigments, dyes, anti-settlement agents, and solvents. Among these, thixotropic agents, UV absorbers, and antioxidants are particularly preferred.

[0073] [Tixotropic agents] The thixotropic agent can be any agent capable of inducing thixotropy in the sealing material composition. Preferred thixotropic agents include hydrogenated castor oil, fatty acid bisamides, and fumed silica.

[0074] The content of the thixotropic agent in the sealing material composition is preferably 0.1 to 200 parts by mass, and more preferably 1 to 150 parts by mass, based on 100 parts by mass of the total content of the polyoxyalkylene polymer (A) and siloxane oligomer (B). When the content of the thixotropic agent is 0.1 parts by mass or more, thixotropy can be effectively imparted to the sealing material composition. Furthermore, when the content of the thixotropic agent is 200 parts by mass or less, the sealing material composition has an appropriate viscosity, and the handling of the sealing material composition is improved.

[0075] [UV absorber] Examples of UV absorbers include benzotriazole-based UV absorbers and benzophenone-based UV absorbers, with benzotriazole-based UV absorbers being preferred. The content of the UV absorber in the sealing material composition is preferably 0.1 to 20 parts by mass, and more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the total content of the polyoxyalkylene polymer (A) and siloxane oligomer (B).

[0076] [Antioxidant] Examples of antioxidants include hindered phenol antioxidants, monophenol antioxidants, bisphenol antioxidants, and polyphenol antioxidants, with hindered phenol antioxidants being preferred. The content of the antioxidant in the sealing material composition is preferably 0.1 to 20 parts by mass, and more preferably 0.3 to 10 parts by mass, per 100 parts by mass of the total content of the polyoxyalkylene polymer (A) and siloxane oligomer (B).

[0077] [Light stabilizer] The sealing material composition preferably contains a hindered amine-based light stabilizer. A hindered amine-based light stabilizer makes it possible to provide a sealing material composition that can maintain excellent rubber elasticity for a longer period after curing.

[0078] Examples of hindered amine-based light stabilizers include a mixture of bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, dibutylamine·1,3,5-triazine·N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N-(2,2,6,6 Examples include polycondensates with (-tetramethyl-4-piperidyl)butylamine, poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidyl)imino}], and polycondensates of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol.

[0079] As a hindered amine light stabilizer, a NOR-type hindered amine light stabilizer is preferred. Using a NOR-type hindered amine light stabilizer makes it possible to provide a sealing material composition in which the decrease in rubber elasticity over time after curing is suppressed.

[0080] NOR-type hindered amine light stabilizers have a NOR structure in which an alkyl group (R) is bonded to a nitrogen atom (N) in the piperidine ring skeleton via an oxygen atom (O). The number of carbon atoms in the alkyl group in the NOR structure is preferably 1 to 20, more preferably 1 to 18, and particularly preferably 18. Examples of alkyl groups include linear alkyl groups, branched alkyl groups, and cyclic alkyl groups (saturated alicyclic hydrocarbon groups).

[0081] Examples of linear alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, and n-decyl groups. Examples of branched alkyl groups include isopropyl, isobutyl, sec-butyl, and tert-butyl groups. Examples of cyclic alkyl groups (saturated alicyclic hydrocarbon groups) include cyclopentyl, cyclohexyl, and cyclooctyl groups. Furthermore, the hydrogen atoms constituting the alkyl group may be substituted with halogen atoms (e.g., fluorine, chlorine, bromine, etc.) or hydroxyl groups.

[0082] Examples of NOR-type hindered amine light stabilizers include the hindered amine light stabilizer shown in the following formula (3).

[0083] [ka]

[0084] When using a NOR-type hindered amine light stabilizer, it is preferable to use the NOR-type hindered amine light stabilizer in combination with a benzotriazole-based ultraviolet absorber or a triazine-based ultraviolet absorber. This makes it possible to provide a sealing material composition in which the decrease in rubber elasticity over time after curing is more suppressed.

[0085] The content of the hindered amine-based light stabilizer in the sealing material composition is preferably 0.01 to 20 parts by mass, and more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the total content of the polyoxyalkylene polymer (A) and siloxane oligomer (B).

[0086] [Aminosilane coupling agent] The sealant composition preferably contains an aminosilane coupling agent. By using an aminosilane coupling agent, the normal adhesion of the cured sealant composition can be improved. An aminosilane coupling agent refers to a compound containing a silicon atom to which an alkoxy group is bonded and a functional group containing a nitrogen atom in one molecule.

[0087] Examples of aminosilane coupling agents include 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N,N'-bis-[3-(trimethoxysilyl)propyl]ethylenediamine, N,N'-bis-[3-(triethoxysilyl)propyl]ethylenediamine, N,N'-bis-[3-(methyldimethoxysilyl)propyl]ethylenediamine, N,N'-bis-[3-(trimethoxysilyl)propyl]hexamethylenediamine, and N,N'-bis-[3-(triethoxysilyl)propyl]hexamethylenediamine. These aminosilane coupling agents may be used alone or in combination of two or more.

[0088] Among these, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and N-(2-aminoethyl)-3-aminopropyltriethoxysilane are preferred as aminosilane coupling agents, with N-(2-aminoethyl)-3-aminopropyltrimethoxysilane being more preferred.

[0089] The content of the aminosilane coupling agent in the sealing material composition is preferably 1 to 10 parts by mass, and more preferably 1 to 5 parts by mass, per 100 parts by mass of the total content of the polyoxyalkylene polymer (A) and siloxane oligomer (B). When the content of the aminosilane coupling agent is within the above range, the normal adhesion of the cured product of the sealing material composition is improved.

[0090] [Sealant composition] The sealing material composition can be manufactured by uniformly mixing a polyoxyalkylene polymer (A), a siloxane oligomer (B), a filler (C), a catalyst (D), and additives as needed, using general-purpose means under a vacuum atmosphere.

[0091] The sealing material composition hardens due to moisture (water) contained in the air or structures, forming a cured product that has excellent adhesion under normal conditions and maintains excellent rubber elasticity for a long period of time, making it suitable for use as a sealing material.

[0092] In particular, the cured product obtained by curing the sealant composition with moisture has excellent resistance to hot water. Kitchens, bathrooms, toilets, washrooms, and other wet areas are often exposed to water and moisture, but because the cured product of the sealant composition has excellent resistance to hot water, even in wet areas, the cured product of the sealant composition can maintain excellent modulus despite exposure to moisture and maintain excellent rubber elasticity over a long period of time.

[0093] Methods for obtaining a sealing structure by filling the sealing material composition into the sealing portion of a building structure include methods in which the sealing material composition is filled into the sealing portion, then cured, and then moisture-hardened by moisture in the air or contained in the structure.

[0094] The resulting sealing structure comprises structural members of a building structure and a hardened sealant composition filled into the sealing portion formed between adjacent structural members. Examples of structural members of a building structure include walls such as exterior walls, interior walls, and ceilings, as well as washbasins, bathtubs, and system kitchen bodies. The sealant composition is preferably used by filling the sealing portion formed in areas with water. [Effects of the Invention]

[0095] Because the sealing material composition of the present invention has the above-described structure, the cured product has excellent normal adhesion, maintains a state of strong adhesion to the structural member forming the sealing portion for a long period of time, and can maintain a stable closed state of the sealing portion for a long period of time.

[0096] Furthermore, the sealant composition of the present invention exhibits excellent resistance to hot water in its cured product, maintaining excellent modulus even after immersion in hot water. This allows it to maintain excellent rubber elasticity even when exposed to water and moisture in wet areas, and to maintain a stable seal over the sealed area. [Modes for carrying out the invention]

[0097] The present invention will be described more specifically below with reference to examples, but the present invention is not limited thereto. [Examples]

[0098] The following raw materials were used in the production of the sealing material compositions of the examples and comparative examples. [Polyoxyalkylene polymer having hydrolyzable silyl groups (A)] • Polyoxyalkylene polymer (A1) (a polyoxypropylene polymer whose main chain is polyoxypropylene and has branched chains; hydrolyzable silyl groups (bonded to the ends of the main chain): dimethoxysilyl groups; average number of dimethoxysilyl groups per molecular weight: 3.0; number of carbon atoms in branched chains: 2 or more and 12 or less; number average molecular weight: 30000; molecular weight distribution (Mw / Mn): 1.1; manufactured by AGC Inc., product name "Excester S6735D")

[0099] • Polyoxyalkylene polymer (A2) (a polyoxypropylene polymer whose main chain is polyoxypropylene and has branched chains; hydrolyzable silyl groups (bonded to the ends of the main chain): dimethoxysilyl groups; average number of dimethoxysilyl groups per molecular weight: 3.0; number of carbon atoms in branched chains: 2 or more and 12 or less; number average molecular weight: 8000; molecular weight distribution (Mw / Mn): 1.1; manufactured by AGC Inc., product name "Excestar S6250")

[0100] [Siloxane oligomer having hydrolyzable functional groups (B1)] • Siloxane oligomer (B1) (Main chain skeleton: linear polysiloxane skeleton -(O-Si)p-, with phenyl groups directly bonded to the main chain skeleton as side chains, and methoxy groups as hydrolyzable functional groups at the ends of the polylinear polysiloxane skeleton constituting the main chain, manufactured by Momentive Performance Materials Japan, product name "XR31-B2230", hydrolyzable functional group content per molecule: 30% by mass)

[0101] [Siloxane oligomer having hydrolyzable functional groups (B2)] • Siloxane oligomer (B2) (Main chain skeleton: linear polysiloxane skeleton -(O-Si)p-, with phenyl groups directly bonded to the main chain skeleton as side chains, and methoxy groups as hydrolyzable functional groups at the ends of the polylinear polysiloxane skeleton constituting the main chain, manufactured by Momentive Performance Materials Japan, trade name "TSR165", hydrolyzable functional group content per molecule: 15% by mass)

[0102] [Siloxane oligomer having hydrolyzable functional groups (B3)] • Siloxane oligomer (B3) (Main chain skeleton: linear polysiloxane skeleton -(O-Si)p-, with phenyl groups directly bonded to the main chain skeleton as side chains, and methoxy groups as hydrolyzable functional groups at the ends of the polylinear polysiloxane skeleton constituting the main chain, manufactured by Momentive Performance Materials Japan, trade name "XC96-C2814", hydrolyzable functional group content per molecule: 8% by mass)

[0103] [Siloxane oligomer having hydrolyzable functional groups (B4)] • Siloxane oligomer (B4) (Main chain skeleton: linear polysiloxane skeleton -(O-Si)p-, methyl groups directly bonded to the main chain skeleton as side chains, methoxy groups as hydrolyzable functional groups at the ends of the linear polysiloxane skeleton constituting the main chain, no phenyl groups in the molecule, manufactured by Momentive Performance Materials Japan, trade name "XR31-B2733", hydrolyzable functional group content per molecule: 15% by mass)

[0104] [Filling material] • Precipitating calcium carbonate (manufactured by Maruo Calcium Co., Ltd., product name "Calfine 200M", average particle size: 0.5 μm) • Heavy calcium carbonate (manufactured by Nitto Funka Co., Ltd., product name "NCC2310", average particle size: 1.0 μm)

[0105] [Plasticizer] • Plasticizer (polypropylene glycol, without hydrolyzable silyl groups, number average molecular weight 3000, manufactured by AGC Inc., product name "Exenol 3020")

[0106] [Dehydrating agent] • Vinyltrimethosilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM-1003")

[0107] [catalyst] • Silanol condensation catalyst (1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distanoxane, manufactured by Nitto Chemical Co., Ltd., product name "Neostan U-130")

[0108] [Aminosilane coupling agent] • Aminosilane coupling agent (N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM-603")

[0109] (Examples 1-5, Comparative Examples 1-4) A sealing material composition was obtained by mixing a polyoxyalkylene polymer (A) having a hydrolyzable silyl group, a siloxane oligomer having a hydrolyzable functional group, a filler, a plasticizer, vinyltrimethoxysilane, a silanol condensation catalyst, and an aminosilane coupling agent in the amounts shown in Table 1, under reduced pressure in a sealed stirrer until homogeneous.

[0110] In Table 1, "siloxane oligomers having hydrolyzable functional groups" are simply referred to as "siloxane oligomers."

[0111] The initial maximum load elongation, initial 50% modulus, and initial maximum load strength of the obtained sealing material composition were measured according to the following procedure, and the results are shown in Table 1.

[0112] The hot water resistance of the cured sealant composition was measured according to the following procedure, and the results are shown in Table 1.

[0113] (Initial elongation at maximum load, initial strength at maximum load, and initial 50% modulus of the cured material) An H-shaped test specimen was prepared using a curable composition in accordance with JIS A1439 4.21. Specifically, two anodized aluminum plates (50 mm long x 50 mm wide x 3 mm thick) were used, and a spacer was placed between them to form a rectangular parallelepiped space (12 mm long x 50 mm wide x 12 mm high) in the center of the space between the aluminum plates. The sealing material composition was filled into this space so as not to contain any air, and left for 14 days in an atmosphere of 23°C and 50% relative humidity. Furthermore, the curable composition was allowed to cure by leaving the sealing material composition in an atmosphere of 30°C and 50% relative humidity for another 14 days, thereby creating an H-shaped test specimen in which the two aluminum plates were bonded together by the cured sealing material composition.

[0114] Then, immediately after fabrication, the H-type test specimens were subjected to tensile testing at a tensile speed of 50 mm / min in an atmosphere of 23°C and 50% relative humidity, in accordance with JIS A1439, and the elongation at maximum load (initial maximum load elongation) [%] and strength at maximum load (initial maximum load strength) [N / mm] were determined. 2 ] and 50% modulus (initial 50% modulus) [N / mm 2 The following parameters were measured. The results obtained are shown in Table 1 as "Initial Elongation at Maximum Load (%)" and "Initial Strength at Maximum Load (N / mm²)". 2 ) and "Initial 50% Modulus (N / mm 2 I wrote each of them in the column labeled ")".

[0115] (Hot water resistance) H-type test specimens were prepared in the same manner as for normal adhesion, and then immersed in hot water at 50°C for 7 days. The 50% modulus (modulus after hot water immersion) of the H-type test specimens after this immersion was determined [N / cm]. 2 The 50% modulus retention rate of the cured sealant composition after hot water immersion was calculated based on the following formula. 50% Modulus Maintenance Rate (%) = 100 × (50% modulus after hot water immersion / 50% modulus initial)

[0116] [Table 1]

Claims

1. A polyoxyalkylene polymer (A) having a number average molecular weight of 10,000 to 40,000 and hydrolyzable silyl groups, Siloxane oligomer (B) having a phenyl group and a hydrolyzable functional group, Filler (C), Includes catalyst (D), The mass ratio of the content of the siloxane oligomer (B) having the phenyl group and hydrolyzable functional group to the total content of the polyoxyalkylene polymer (A) having a number average molecular weight of 10,000 to 40,000 and hydrolyzable silyl group, and the siloxane oligomer (B) having the phenyl group and hydrolyzable functional group [Content of siloxane oligomer (B) having the phenyl group and hydrolyzable functional group / (Total content of polyoxyalkylene polymer (A) having a number average molecular weight of 10,000 to 40,000 and hydrolyzable silyl group, and siloxane oligomer (B) having the phenyl group and hydrolyzable functional group)] is 0.01 to 0.

1. The siloxane oligomer (B) having the above-mentioned phenyl group and hydrolyzable functional group is a sealing material composition characterized in that the main chain is a linear polysiloxane skeleton-(O-Si)p- and has phenyl groups directly bonded to the main chain skeleton as side chains. However, in the above-mentioned polysiloxane skeleton-(O-Si)p-, p is the number of repeating units and is a positive integer.

2. The sealing material composition according to claim 1, characterized in that the content of the hydrolyzable functional group of the siloxane oligomer (B) having a phenyl group and a hydrolyzable functional group is 10 to 30% by mass.

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