Curable composition

Abstract

An object of the present invention is to provide a curable composition that can be used as sealing materials, adhesives, and the like, has excellent curing properties, and gives a cured product excellent in elongation properties. The object can be attained by means of a curable composition comprising: a reactive silyl group-containing polyether polymer (A) that contains a reactive silyl group with high activity (e.g., (ClCH.sub.2)(CH.sub.3O).sub.2Si, (CH.sub.3OCH.sub.2)(CH.sub.3O).sub.2Si, or CH.sub.3(CH.sub.3O).sub.2SiCH.sub.2NHC(O)); and a reactive silyl group-containing polyether polymer (B) that contains a reactive silyl group (e.g., CH.sub.3(CH.sub.3O).sub.2Si or (CH.sub.3O).sub.3Si) different from that mentioned above and/or a (meth)acrylic polymer (C) containing a reactive silyl group that is not particularly limited.

Claims

1. A curable composition, comprising: a polyether polymer (A) containing a reactive silyl group represented by the following formula (1); and at least one of a polyether polymer (B) containing a reactive silyl group represented by the following formula (2) and a (meth)acrylic polymer (C) containing a reactive silyl group represented by the following formula (3):
WCH.sub.2SiR.sup.1.sub.aR.sup.2.sub.bX.sub.c (1) wherein R.sup.1 is a methoxymethyl group; R.sup.2 represents a C1 to C20 hydrocarbon group, a C6 to C20 aryl group, a C7 to C20 aralkyl group, or a triorganosiloxy group represented by R.sup.0.sub.3SiO wherein each of three R.sup.0s is a C1 to C20 hydrocarbon group and they may be the same as or different from each other; X represents a hydroxy or hydrolyzable group; W represents a linking group selected from OR.sup.8, OCON(R.sup.9), N(R.sup.9)COO, N(R.sup.9)CON(R.sup.9), SCONH, NHCOS, and S wherein R.sup.8 represents a divalent C1 to C8 hydrocarbon group, and R.sup.9 represents hydrogen or a C1 to C18 hydrocarbon group optionally substituted with halogen; in the case that W is OR.sup.8, a is 1 or 2, b is 0 or 1, and c is 1 or 2, provided that a+b+c =3 is satisfied; in the case that W is a group other than OR.sup.8-, a is 0, 1, or 2, b is 0, 1, or 2, and c is 1, 2, or 3, provided that a+b+c=3 is satisfied; and in the case that a plurality of R.sup.1s, R.sup.2s, or Xs exist, they may be the same as or different from each other,
VSiR.sup.2.sub.dX.sub.3-d (2) wherein R.sup.2 and X are defined as mentioned in formula (1); V represents a divalent C2 to C8 hydrocarbon group; d represents any of 0, 1, and 2; and in the case that a plurality of R.sup.2s or Xs exist, they may be the same as or different from each other, and
Z(CH.sub.2).sub.nSiR.sup.1.sub.aR.sup.2.sub.bX.sub.c (3) wherein R.sup.1.[.,.]. .Iadd.of Formula (3) is a C1 to C20 hydrocarbon group wherein at least one hydrogen atom on carbon atoms at positions 1 to 3 is replaced with halogen, OR.sup.3, NR.sup.4R.sup.5, NR.sup.6, SR.sup.7 (in which each of R.sup.3, R.sup.4, R.sup.5, and R.sup.7 is a hydrogen atom or a C1 to C20 substituted or unsubstituted hydrocarbon group, and R.sup.6 is a divalent C1 to C20 substituted or unsubstituted hydrocarbon group), a C1 to C20 perfluoroalkyl group, or a cyano group; .Iaddend.R.sup.2.[.,.]. and X are defined as mentioned in formula (1); Z represents a linking group selected from COO, OCON(R.sup.9), N(R.sup.9)COO, N(R.sup.9)CON(R.sup.9), SCONH, NHCOS, and S wherein R.sup.9 is defined as mentioned in formula (1); n represents a number of 1 to 8; a is 0,1, or 2, b is 0, 1, or 2, and c is 1, 2, or 3, provided that the condition: a+b+c =3 is satisfied; and in the case that a plurality of R.sup.1s, R.sup.2s, or Xs exist, they may be the same as or different from each other.

2. The curable composition according to claim 1, wherein W in formula (1) is OR.sup.8 wherein R.sup.8 is a divalent C1 to C8 hydrocarbon group.

3. The curable composition according to claim 1, wherein the polyether polymer (A) is a polyoxypropylene polymer.

4. The curable composition according to claim 1, wherein the polyether polymer (A) is a linear polymer having no branch.

5. The curable composition according to claim 1, wherein a backbone structure of the polyether polymer (B) is a polyoxypropylene polymer.

6. The curable composition according to claim 1, wherein the reactive silyl group of formula (2) is a dimethoxymethylsilyl group.

7. The curable composition according to claim 1, wherein the (meth)acrylic polymer (C) is at least one of a reactive silyl group-containing alkyl (meth)acrylate polymer and copolymer.

8. A curable composition, which comprises a polyether polymer (A) containing a reactive silyl group represented by the following formula (1); a polyether polymer (B) containing a reactive silyl group represented by the following formula (2); and a (meth)acrylic polymer (C) containing a reactive silyl group represented by the following formula (3):
WCH.sub.2SiR.sup.1.sub.aR.sup.2.sub.bX.sub.c (1) wherein R.sup.1 is a C1 to C20 hydrocarbon group wherein at least one hydrogen atom on carbon atoms at positions 1 to 3 is replaced with halogen, OR.sup.3, NR.sup.4R.sup.5, NR.sup.6, SR.sup.7 (in which each of R.sup.3, R.sup.4, R.sup.5, and R.sup.7 is a hydrogen atom or a C1 to C20 substituted or unsubstituted hydrocarbon group, and R.sup.6 is a divalent C1 to C20 substituted or unsubstituted hydrocarbon group), a C1 to C20 perfluoroalkyl group, or a cyano group; R.sup.2 represents a C1 to C20 hydrocarbon group, a C6 to C20 aryl group, a C7 to C20 aralkyl group, or a triorganosiloxy group represented by R.sup.0.sub.3SiO wherein each of three R.sup.0s is a C1 to C20 hydrocarbon group and they may be the same as or different from each other; X represents a hydroxy or hydrolyzable group; W represents a linking group selected from OR.sup.8, OCON(R.sup.9), N(R.sup.9)COO, N(R.sup.9)CON(R.sup.9), SCONH, NHCOS, and S wherein R.sup.8 represents a divalent C1 to C8 hydrocarbon group, and R.sup.9 represents hydrogen or a C1 to C18 hydrocarbon group optionally substituted with halogen; in the case that W is OR.sup.8, a is 1 or 2, b is 0 or 1, and c is 1 or 2, provided that a+b+c =3 is satisfied; in the case that W is a group other than OR.sup.8, a is 0, 1, or 2, b is 0, 1, or 2, and c is 1, 2, or 3, provided that a+b+c =3 is satisfied; and in the case that a plurality of R.sup.1s, R.sup.2s, or Xs exist, they may be the same as or different from each other,
VSiR.sup.2.sub.dX.sub.3-d (2) wherein R.sup.2 and X are defined as mentioned in formula (1); V represents a divalent C2 to C8 hydrocarbon group; d represents any of 0, 1, and 2; and in the case that a plurality of R.sup.2s or Xs exist, they may be the same as or different from each other, and
Z(CH.sub.2).sub.nSiR.sup.1.sub.aR.sup.2.sub.bX.sub.c (3) wherein R.sup.1, R.sup.2, and X are defined as mentioned in formula (1); Z represents a linking group selected from COO, OCON(R.sup.9), N(R.sup.9)COO, N(R.sup.9)CON(R.sup.9), SCONH, NHCOS, and S wherein R.sup.9 is defined as mentioned in formula (1); n represents a number of 1 to 8; a is 0, 1, or 2, b is 0, 1, or 2, and c is 1, 2, or 3, provided that the condition: a+b+c =3 is satisfied; and in the case that a plurality of R.sup.1s, R.sup.2s, or Xs exist, they may be the same as or different from each other.

9. The curable composition according to claim 8, wherein the polyether polymer (A) has a number average molecular weight of 22,000 or higher.

10. The curable composition according to claim 8, wherein the polyether polymer (A) and the polyether polymer (B) are contained at a ratio of (A):(B)=50:50 to 5:95 (parts by weight).

11. The curable composition according to claim 8, further comprising: at least one of an amine compound (d1) and an organic dialkyltin compound (d2) as a condensation catalyst (D).

12. A sealing material, comprising the curable composition according to claim 8 as a component.

13. An adhesive, comprising the curable composition according to claim 8 as a component.

14. A contact adhesive, comprising the curable composition according to claim 8 as a component.

.[.15. The contact adhesive according to claim 8, comprising the polyether polymer (A) and the polyether polymer (B)..].

16. A cured product, obtained by curing the curable composition according to claim 8.

17. A contact adhesive, comprising the curable composition according to claim 1 as a component.

.Iadd.18. The contact adhesive according to claim 17, comprising the polyether polymer (A) and the polyether polymer (B). .Iaddend.

Description

EXAMPLES

(1) Hereinafter, the present invention will be described in more detail with reference to specific examples. They are, however, by no means limitative of the scope of the present invention.

(2) Chloromethyldimethoxysilane used in the following synthesis examples was synthesized by synthesizing chloromethyldichlorosilane by the method described in Example 41 of WO 2010/004948 and methoxylating the compound by the method described in Example 55 thereof.

Synthesis Example 1

(3) Propylene oxide was polymerized in the presence of polyoxypropylene diol having a molecular weight of about 2,000 as an initiator and a zinc hexacyanocobaltate glyme complex catalyst to provide polyoxypropylene diol having a number average molecular weight of 21,100 (polystyrene-equivalent molecular weight determined with a solvent delivery system: HLC-8120 GPC produced by TOSOH; a column: TSK-GEL H type produced by TOSOH; and a solvent: THF). To this polyoxypropylene diol was then added a methanol solution of NaOMe in an amount of 1.2 equivalents relative to the hydroxy groups of the polyoxypropylene diol, and the methanol was distilled off. 3-Chloro-1-propene was then added to the residue, and thereby the terminal hydroxy group was converted to an allyl group. To 100 parts by weight of the obtained allyl-terminated polyoxypropylene polymer were then added 72 ppm of a platinum-divinyldisiloxane complex (isopropanol solution having a platinum content of 3% by weight) and 1.29 parts by weight of trimethyl orthoformate and then gradually added dropwise 1.51 parts of (chloromethyl)dimethoxysilane with stirring. The mixed solution was reacted at 90 C. for 2 hours to provide a chloromethyldimethoxysilyl-terminated linear polyoxypropylene polymer (A-1) containing 1.5 reactive silyl groups on average per molecule and having a number average molecular weight of 21,100.

Synthesis Example 2

(4) Propylene oxide was polymerized in the presence of polyoxypropylene diol having a molecular weight of about 2,000 as an initiator and a zinc hexacyanocobaltate glyme complex catalyst to provide polyoxypropylene diol having a number average molecular weight of 28,500 (calculated in the same way as in Synthesis Example 1). To this polyoxypropylene diol was then added a methanol solution of NaOMe in an amount of 1.2 equivalents relative to the hydroxy groups of the polyoxypropylene diol, and the methanol was distilled off. 3-Chloro-1-propene was then added to the residue, and thereby the terminal hydroxy group was converted to an allyl group. To 100 parts by weight of the obtained allyl-terminated polyoxypropylene polymer were then added 72 ppm of a platinum-divinyldisiloxane complex (isopropanol solution having a platinum content of 3% by weight) and 1.05 parts by weight of trimethyl orthoformate and then gradually added dropwise 1.22 parts of (chloromethyl)dimethoxysilane with stirring. The mixed solution was reacted at 90 C. for 2 hours to provide a (chloromethyl)dimethoxysilyl-terminated linear polyoxypropylene polymer (A-2) containing 1.5 reactive silyl groups on average per molecule and having a number average molecular weight of 28,500.

Synthesis Example 3

(5) Propylene oxide was polymerized in the presence of polyoxypropylene triol having a number average molecular weight of about 3,000 as an initiator and a zinc hexacyanocobaltate glyme complex catalyst to provide polyoxypropylene triol having a number average molecular weight of 26,200 (calculated in the same way as in Synthesis Example 1). To this polyoxypropylene triol was then added a methanol solution of NaOMe in an amount of 1.2 equivalents relative to the hydroxy groups of the polyoxypropylene triol, and the methanol was distilled off. 3-Chloro-1-propene was then added to the residue, and thereby the terminal hydroxy group was converted to an allyl group. To 100 parts by weight of the obtained allyl-terminated polyoxypropylene polymer were then added 72 ppm of a platinum-divinyldisiloxane complex (isopropanol solution having a platinum content of 3% by weight) and 0.79 parts by weight of trimethyl orthoformate and then gradually added dropwise 1.83 parts by weight of (chloromethyl)dimethoxysilane with stirring. The mixed solution was reacted at 90 C. for 2 hours to provide a chloromethyl dimethoxysilyl-terminated branched polyoxypropylene polymer (A-3) containing 2.3 reactive silyl groups on average per molecule and having a number average molecular weight of 26,200.

Synthesis Example 4

(6) Propylene oxide was polymerized in the presence of polyoxypropylene diol having a number average molecular weight of about 2,000 as an initiator and a zinc hexacyanocobaltate glyme complex catalyst to provide polyoxypropylene diol having a number average molecular weight of 14,600 (calculated in the same way as in Synthesis Example 1). To this polyoxypropylene diol was then added a methanol solution of NaOMe in an amount of 1.2 equivalents relative to the hydroxy groups of the polyoxypropylene diol, and the methanol was distilled off. 3-Chloro-1-propene was then added to the residue, and thereby the terminal hydroxy group was converted to an allyl group. To 100 parts by weight of the obtained allyl-terminated polyoxypropylene polymer were then added 72 ppm of a platinum-divinyldisiloxane complex (isopropanol solution having a platinum content of 3% by weight) and 2.01 parts by weight of trimethyl orthoformate and then was gradually added dropwise 2.35 parts by weight of (chloromethyl)dimethoxysilane with stirring. The mixed solution was reacted at 90 C. for 2 hours to provide a (chloromethyl)dimethoxysilyl-terminated linear polyoxypropylene polymer (A-4) containing 1.5 reactive silyl groups on average per molecule and having a number average molecular weight of 14,600.

Synthesis Example 5

(7) Acetyl chloride (4 molar equivalents) was allowed to act on (methoxymethyl)trimethoxysilane produced with reference to the method described in Example 2 of JP-T 2007-513203, in the presence of 0.02 molar equivalent of zinc chloride as a catalyst. (Methoxymethyl)trichlorosilane was synthesized by reaction for 36 hours under reflux conditions by heating.

(8) (Methoxymethyl)trichlorosilane purified by distillation was mixed with 1 molar equivalent of methyldichlorosilane (LS-50, a product of Shin-Etsu Chemical Co., Ltd.). To the mixture was then added 0.05 molar equivalent of methyl tributylammonium chloride. The mixture was then allowed to react for 3 hours under reflux conditions by heating. As a result, methoxymethyldichlorosilane was obtained at a conversion rate of about 50%.

(9) To a reaction vessel was added trimethyl orthoacetate in an amount of 2.5 molar equivalents relative to (methoxymethyl)dichlorosilane purified by distillation, and was further gradually added (methoxymethyl)dichlorosilane with sufficient stirring. The addition rate was adjusted so as to keep the reaction solution at a temperature of not higher than 50 C. After the completion of addition, it was confirmed from .sup.1H-NMR spectra (measured in a CDCl.sub.3 solvent with JNM-LA400 produced by JEOL Ltd.; analysis was conducted with the peak of CHCL.sub.3 as 7.26 ppm) that (methoxymethyl)dichlorosilane was almost quantitatively converted to (methoxymethyl)dimethoxysilane. The resultant was purified by distillation under reduced pressure to obtain (methoxymethyl)dimethoxysilane.

(10) .sup.1HNMR spectral assignment: 4.52 (t, 1H), 3.60 (s, 6H), 3.35 (s, 3H), 3.19 (d, 2H).

Synthesis Example 6

(11) Propylene oxide was polymerized in the presence of polyoxypropylene diol having a number average molecular weight of about 2,000 as an initiator and a zinc hexacyanocobaltate glyme complex catalyst to provide polyoxypropylene diol having a number average molecular weight of 14,600 (calculated in the same way as in Synthesis Example 1). To this hydroxy-terminated polyoxypropylene diol was then added a methanol solution of NaOMe in an amount of 1.2 equivalents relative to the hydroxy groups of the polyoxypropylene diol, and the methanol was distilled off. 3-Chloro-1-propene was then added to the residue, and thereby the terminal hydroxy group was converted to an allyl group. To 100 parts by weight of the obtained allyl-terminated polyoxypropylene polymer were then added 72 ppm of a platinum-divinyldisiloxane complex (isopropanol solution having a platinum content of 3% by weight) and 2.01 parts by weight of trimethyl orthoformate and then was gradually added dropwise 2.28 parts by weight of (methoxymethyl)dimethoxysilane synthesized in Synthesis Example 5 with stirring. The mixed solution was reacted at 90 C. for 2 hours to provide a (methoxymethyl)dimethoxysilyl-terminated linear polyoxypropylene polymer (A-5) containing 1.5 reactive silyl groups on average per molecule and having a number average molecular weight of 14,600.

Synthesis Example 7

(12) A reactor was charged with 71.1 g (0.88 mol) of potassium cyanate and purged with nitrogen. To the reactor were added 500 ml of N,N-dimethylformamide and then 125.0 g (0.75 mol) of chloromethyl-dimethoxymethylsilane and 50.2 g (1.56 mol) of methanol while the mixture was sufficiently stirred. The resulting mixture was heated to 90 C., then heated to 120 C. over 4 hours, and further stirred for 3 hours. The deposited potassium chloride was filtered off, and the N,N-dimethylformamide was distilled off using an evaporator. The residue was then purified by distillation to provide methyl(N-dimethoxymethylsilylmethyl)carbamate (MeCO.sub.2NHCH.sub.2Si(OMe).sub.2Me) (yield: 116.2 g).

(13) A reactor connected with a fractionating column and a condenser was charged with 100 g (0.52 mol) of the obtained methyl(N-dimethoxymethylsilylmethyl)carbamate and 13 mg (0.002 mmol) of dibutyltin dilaurate, and the pressure in the system was reduced to 45 mmHg. The mixture was heated to 170 C. While the degradation reaction product methanol was separated and collected, (isocyanatomethyl)dimethoxymethylsilane (OCNCH.sub.2SiCH.sub.3(OCH.sub.3).sub.2) was synthesized over 5 hours. The resultant was purified by distillation under reduced pressure to obtain (isocyanatomethyl)dimethoxymethylsilane (yield: 50 g).

Synthesis Example 8

(14) Propylene oxide was polymerized in the presence of polyoxypropylene diol having a number average molecular weight of about 2,000 as an initiator and a zinc hexacyanocobaltate glyme complex catalyst to provide polyoxypropylene diol having a number average molecular weight of 14,600 (calculated in the same way as in Synthesis Example 1). To 100 parts by weight of the obtained polyoxypropylene diol was added 30 ppm of dibutyltin dilaurate and was then gradually added dropwise (isocyanatomethyl)dimethoxymethylsilane (3.1 parts by weight) synthesized in Synthesis Example 7 with stirring. The mixed solution was reacted at 90 C. for 3 hours and then deaerated for 2 hours to provide a dimethoxymethylsilyl-terminated linear polyoxypropylene polymer (A-6) containing 1.8 reactive silyl groups on average per molecule and having a number average molecular weight of 14,600.

Synthesis Example 9

(15) Propylene oxide was polymerized in the presence of polyoxypropylene diol having a number average molecular weight of about 2,000 as an initiator and a zinc hexacyanocobaltate glyme complex catalyst to provide polyoxypropylene diol having a number average molecular weight of 28,500 (calculated in the same way as in Synthesis Example 1). To the obtained polyoxypropylene diol was then added a methanol solution of NaOMe in an amount of 1.2 equivalents relative to the hydroxy groups of the polyoxypropylene diol, and the methanol was distilled off. 3-Chloro-2-methyl-1-propene was then added to the residue, and thereby the terminal hydroxy group was converted to a methallyl group. The container was then purged with 6% O.sub.2/N.sub.2. To 100 parts by weight of the obtained methallyl-terminated polyoxypropylene polymer were then added 100 ppm of sulfur (0.25 wt % solution in hexane), 100 ppm of a platinum-divinyldisiloxane complex (isopropanol solution having a platinum content of 3% by weight), and 1.37 parts by weight of trimethyl orthoformate and then gradually added dropwise 1.60 parts by weight of (chloromethyl)dimethoxysilane with stirring. The mixed solution was reacted at 100 C. for 5 hours to provide a (chloromethyl)dimethoxysilyl-terminated linear polyoxypropylene polymer (A-7) containing 1.9 reactive silyl groups on average per molecule and having a number average molecular weight of 28,500.

Synthesis Example 10

(16) Propylene oxide was polymerized in the presence of butanol as an initiator and a zinc hexacyanocobaltate glyme complex catalyst to provide polyoxypropylene oxide having a number average molecular weight of 7,000 (calculated in the same way as in Synthesis Example 1). To this hydroxy-terminated polyoxypropylene oxide was then added a methanol solution of NaOMe in an amount of 1.2 equivalents relative to the hydroxy groups of the hydroxy-terminated polyoxypropylene oxide, and the methanol was distilled off. 3-Chloro-1-propene was then added to the residue, and thereby the terminal hydroxy group was converted to an allyl group. To 100 parts by weight of the obtained allyl-terminated polyoxypropylene polymer were then added 72 ppm of a platinum-divinyldisiloxane complex (isopropanol solution having a platinum content of 3% by weight), and 1.95 parts by weight of trimethyl orthoformate and then gradually added dropwise 2.28 parts by weight of (chloromethyl)dimethoxysilane with stirring. The mixed solution was reacted at 90 C. for 2 hours to provide a chloromethyldimethoxysilyl-terminated linear polyoxypropylene polymer (A-8) containing 0.7 reactive silyl groups on average per molecule and having a number average molecular weight of 7,000.

Synthesis Example 11

(17) Propylene oxide was polymerized in the presence of polyoxypropylene diol having a number average molecular weight of about 2,000 as an initiator and a zinc hexacyanocobaltate glyme complex catalyst to provide polyoxypropylene diol having a number average molecular weight of 7,200 (calculated in the same way as in Synthesis Example 1). To the obtained polyoxypropylene diol was then added a methanol solution of NaOMe in an amount of 1.2 equivalents relative to the hydroxy groups of the polyoxypropylene diol, and the methanol was distilled off. 3-Chloro-1-propene was then added to the residue, and thereby the terminal hydroxy group was converted to an allyl group. To 100 parts by weight of the obtained allyl-terminated polyoxypropylene polymer were then added 72 ppm of a platinum-divinyldisiloxane complex (isopropanol solution having a platinum content of 3% by weight), and 3.83 parts by weight of trimethyl orthoformate and then gradually added dropwise 4.49 parts by weight of (chloromethyl)dimethoxysilane with stirring. The mixed solution was reacted at 90 C. for 2 hours to provide a (chloromethyl)dimethoxysilyl-terminated linear polyoxypropylene polymer (A-9) containing 1.5 reactive silyl groups on average per molecule and having a number average molecular weight of 7,400.

Synthesis Example 12

(18) Propylene oxide was polymerized in the presence of polyoxypropylene diol having a molecular weight of about 2,000 as an initiator and a zinc hexacyanocobaltate glyme complex catalyst to provide polyoxypropylene diol having a number average molecular weight of 21,100 (calculated in the same way as in Synthesis Example 1). To the obtained polyoxypropylene diol was then added a methanol solution of NaOMe in an amount of 1.2 equivalents relative to the hydroxy groups of the polyoxypropylene diol, and the methanol was distilled off. 3-Chloro-1-propene was then added to the residue, and thereby the terminal hydroxy group was converted to an allyl group. To 100 parts by weight of the obtained allyl-terminated polyoxypropylene polymer was added 36 ppm of a platinum-divinyldisiloxane complex (isopropanol solution having a platinum content of 3% by weight), and was then gradually added dropwise 1.15 parts by weight of dimethoxymethylsilane with stirring. The mixed solution was reacted at 90 C. for 2 hours to provide a dimethoxymethylsilyl-terminated linear polyoxypropylene polymer (B-1) containing 1.5 reactive silyl groups on average per molecule and having a number average molecular weight of 21,100.

Synthesis Example 13

(19) Propylene oxide was polymerized in the presence of polyoxypropylene diol having a molecular weight of about 2,000 as an initiator and a zinc hexacyanocobaltate glyme complex catalyst to provide polyoxypropylene diol having a number average molecular weight of 28,500 (calculated in the same way as in Synthesis Example 1). To the obtained polyoxypropylene diol was then added a methanol solution of NaOMe in an amount of 1.2 equivalents relative to the hydroxy groups of the polyoxypropylene diol, and the methanol was distilled off. 3-Chloro-1-propene was then added to the residue, and thereby the terminal hydroxy group was converted to an allyl group. To 100 parts by weight of the obtained allyl-terminated polyoxypropylene polymer were then added 36 ppm of a platinum-divinyldisiloxane complex (isopropanol solution having a platinum content of 3% by weight), and then gradually added dropwise 0.96 parts by weight of dimethoxymethylsilane with stirring. The mixed solution was reacted at 90 C. for 2 hours to provide a dimethoxymethylsilyl-terminated linear polyoxypropylene polymer (B-2) containing 1.5 reactive silyl groups on average per molecule and having a number average molecular weight of 28,500.

Synthesis Example 14

(20) Propylene oxide was polymerized in the presence of polyoxypropylene triol having a number average molecular weight of about 3,000 as an initiator and a zinc hexacyanocobaltate glyme complex catalyst to provide polyoxypropylene triol having a number average molecular weight of 26,200 (calculated in the same way as in Synthesis Example 1). To the obtained polyoxypropylene triol was then added a methanol solution of NaOMe in an amount of 1.2 equivalents relative to the hydroxy groups of the polyoxypropylene triol, and the methanol was distilled off. 3-Chloro-1-propene was then added to the residue, and thereby the terminal hydroxy group was converted to an allyl group. To 100 parts by weight of the obtained allyl-terminated polyoxypropylene polymer were then added 36 ppm of a platinum-divinyldisiloxane complex (isopropanol solution having a platinum content of 3% by weight), and then gradually added dropwise 1.29 parts by weight of dimethoxymethylsilane with stirring. The mixed solution was reacted at 90 C. for 2 hours to provide a dimethoxymethylsilyl-terminated branched polyoxypropylene polymer (B-3) containing 2.3 reactive silyl groups on average per molecule and having a number average molecular weight of 26,200.

Synthesis Example 15

(21) Propylene oxide was polymerized in the presence of polyoxypropylene diol having a number average molecular weight of about 2,000 as an initiator and a zinc hexacyanocobaltate glyme complex catalyst to provide polyoxypropylene diol having a number average molecular weight of 28,500 (calculated in the same way as in Synthesis Example 1). To the obtained polyoxypropylene diol was then added a methanol solution of NaOMe in an amount of 1.2 equivalents relative to the hydroxy groups of the polyoxypropylene diol, and the methanol was distilled off. 3-Chloro-2-methyl-1-propene was then added to the residue, and thereby the terminal hydroxy group was converted to a methallyl group. The container was then purged with 6% O.sub.2/N.sub.2. To 100 parts by weight of the obtained methallyl-terminated polyoxypropylene polymer were then added 100 ppm of sulfur (0.25 wt % solution in hexane), 100 ppm of a platinum-divinyldisiloxane complex (isopropanol solution having a platinum content of 3% by weight), and then gradually added dropwise 2.30 parts by weight of dimethoxymethylsilane with stirring. The mixed solution was reacted at 100 C. for 5 hours to provide a dimethoxymethylsilyl-terminated linear polyoxypropylene polymer (B-4) containing 1.9 reactive silyl groups on average per molecule and having a number average molecular weight of 28,500.

Synthesis Example 16

(22) Propylene oxide was polymerized in the presence of polyoxypropylene diol having a number average molecular weight of about 2,000 as an initiator and a zinc hexacyanocobaltate glyme complex catalyst to provide polyoxypropylene diol having a number average molecular weight of 28,500 (calculated in the same way as in Synthesis Example 1). To the obtained polyoxypropylene diol was then added a methanol solution of NaOMe in an amount of 1.2 equivalents relative to the hydroxy groups of the polyoxypropylene diol, and the methanol was distilled off. 3-Chloro-1-propene was then added to the residue, and thereby the terminal hydroxy group was converted to an allyl group. To 100 parts by weight of the obtained allyl-terminated polyoxypropylene polymer was added 36 ppm of a platinum-divinyldisiloxane complex (isopropanol solution having a platinum content of 3% by weight) and was then gradually added dropwise TES (triethoxysilane) (1.48 parts by weight) with stirring. The mixed solution was reacted at 90 C. for 2 hours. Then 20 parts by weight of methanol and 12 ppm of HCl were further added to the reaction solution, and thereby the terminal ethoxy group was converted to a methoxy group to provide a trimethoxysilyl-terminated linear polyoxypropylene polymer (B-5) containing 1.6 reactive silyl groups on average per molecule and having a number average molecular weight of 28,500.

Synthesis Example 17

(23) Propylene oxide was polymerized in the presence of butanol as an initiator and a zinc hexacyanocobaltate glyme complex catalyst to provide polyoxypropylene oxide having a number average molecular weight of 7,000 (calculated in the same way as in Synthesis Example 1). To this hydroxy-terminated polyoxypropylene oxide was then added a methanol solution of NaOMe in an amount of 1.2 equivalents relative to the hydroxy groups of the hydroxy-terminated polyoxypropylene oxide, and the methanol was distilled off. 3-Chloro-1-propene was then added to the residue, and thereby the terminal hydroxy group was converted to an allyl group. To 100 parts by weight of the obtained allyl-terminated polyoxypropylene polymer were then added 36 ppm of a platinum-divinyldisiloxane complex (isopropanol solution having a platinum content of 3% by weight), and then gradually added dropwise 1.72 parts by weight of dimethoxymethylsilane with stirring. The mixed solution was reacted at 90 C. for 2 hours to provide a dimethoxymethylsilyl-terminated linear polyoxypropylene polymer (B-6) containing 0.7 reactive silyl groups on average per molecule and having a number average molecular weight of 7,000.

Synthesis Example 18

(24) Propylene oxide was polymerized in the presence of polyoxypropylene diol having a molecular weight of about 2,000 as an initiator and a zinc hexacyanocobaltate glyme complex catalyst to provide polyoxypropylene diol having a number average molecular weight of 14,500 (calculated in the same way as in Synthesis Example 1). To the obtained polyoxypropylene diol was then added a methanol solution of NaOMe in an amount of 1.2 equivalents relative to the hydroxy groups of the polyoxypropylene diol, and the methanol was distilled off. 3-Chloro-1-propene was then added to the residue, and thereby the terminal hydroxy group was converted to an allyl group. To 100 parts by weight of the obtained allyl-terminated polyoxypropylene polymer were then added 36 ppm of a platinum-divinyldisiloxane complex (isopropanol solution having a platinum content of 3% by weight), and then gradually added dropwise 1.77 parts by weight of dimethoxymethylsilane with stirring. The mixed solution was reacted at 90 C. for 2 hours to provide a dimethoxymethylsilyl-terminated linear polyoxypropylene polymer (B-7) containing 1.5 reactive silyl groups on average per molecule and having a number average molecular weight of 14,500.

Synthesis Example 19

(25) To polyoxypropylene diol having a number average molecular weight of 4,200 (calculated in the same way as in Synthesis Example 1) was added a methanol solution of NaOMe in an amount of 1.2 equivalents relative to the hydroxy groups of the polyoxypropylene diol, and the methanol was distilled off. 3-Chloro-1-propene was then added to the residue, and thereby the terminal hydroxy group was converted to an allyl group. To 100 parts by weight of the obtained allyl-terminated polyoxypropylene polymer were then added 36 ppm of a platinum-divinyldisiloxane complex (isopropanol solution having a platinum content of 3% by weight), and then gradually added dropwise 3.80 parts by weight of dimethoxymethylsilane with stirring. The mixed solution was reacted at 90 C. for 2 hours to provide a dimethoxymethylsilyl-terminated linear polyoxypropylene polymer (B-8) containing 1.0 reactive silyl groups on average per molecule and having a number average molecular weight of 4,200.

Synthesis Example 20

(26) A four-neck flask equipped with a stirrer was charged with 44.7 parts by weight of isobutanol, and the internal temperature of the flask was raised to 105 C. in a nitrogen atmosphere. To the flask was then added dropwise over 5 hours a mixed solution containing 72.9 parts by weight of methyl methacrylate, 6.5 parts by weight of butyl acrylate, 14.6 parts by weight of stearyl methacrylate, 6.0 parts by weight of 3-methacryloxypropylmethyldimethoxysilane, 7.9 parts by weight of 3-mercaptopropylmethyldimethoxysilane, and 2.7 parts by weight of 2,2-azobis(2-methylbutyronitrile) dissolved in 24.3 parts by weight of isobutanol. The reaction mixture was then subjected to polymerization at 105 C. for 2 hours to provide an isobutanol solution (solid content: 60%) of a reactive silyl group-containing (meth)acrylic polymer (C-1) containing 1.6 silyl groups on average per molecule and having a number average molecular weight of 2,000 (calculated in the same way as in Synthesis Example 1).

Synthesis Example 21

(27) A four-neck flask equipped with a stirrer was charged with 45.5 parts by weight of isobutanol, and the internal temperature of the flask was raised to 105 C. in a nitrogen atmosphere. To the flask was then added dropwise over 5 hours a mixed solution containing 72.5 parts by weight of methyl methacrylate, 6.5 parts by weight of butyl acrylate, 14.6 parts by weight of stearyl methacrylate, 6.4 parts by weight of 3-methacryloxypropyltrimethoxysilane, 8.6 parts by weight of 3-mercaptopropyltrimethoxysilane, and 2.7 parts by weight of 2,2-azobis(2-methylbutyronitrile) dissolved in 24.3 parts by weight of isobutanol. The reaction mixture was then subjected to polymerization at 105 C. for 2 hours to provide an isobutanol solution (solid content: 60%) of a reactive silyl group-containing (meth)acrylic polymer (C-2) containing 1.6 silyl groups on average per molecule and having a number average molecular weight of 2,000 (calculated in the same way as in Synthesis Example 1).

Synthesis Example 22

(28) A four-neck flask equipped with a stirrer was charged with 45.4 parts by weight of isobutanol, and the internal temperature of the flask was raised to 105 C. in a nitrogen atmosphere. To the flask was then added dropwise over 5 hours a mixed solution containing 59.5 parts by weight of methyl methacrylate, 6.5 parts by weight of butyl acrylate, 14.6 parts by weight of stearyl methacrylate, 19.4 parts by weight of methacryloxymethyltrimethoxysilane, 8.9 parts by weight of n-dodecylmercaptan, and 2.7 parts by weight of 2,2-azobis (2-methylbutyronitrile) dissolved in 24.3 parts by weight of isobutanol. The reaction mixture was then subjected to polymerization at 105 C. for 2 hours to provide an isobutanol solution (solid content: 60%) of a reactive silyl group-containing (meth)acrylic polymer (C-3) containing 2.0 silyl groups on average per molecule and having a number average molecular weight of 2,000 (calculated in the same way as in Synthesis Example 1).

Synthesis Example 23

(29) To a deoxygenated reactor were added 0.72 parts by weight of cuprous bromide, 13.4 parts by weight of butyl acrylate, 5.0 parts by weight of ethyl acrylate, and 1.6 parts by weight of stearyl acrylate, and the mixture was heated with stirring. Then 8.8 parts by weight of acetonitrile as a polymerization solvent and 1.50 parts by weight of diethyl 2,5-dibromoadipate as an initiator were added to the mixture and mixed therewith. When the temperature of the mixed solution was adjusted to about 80 C., polymerization reaction was started by the addition of pentamethyldiethylenetriamine (hereinafter abbreviated to triamine). The polymerization reaction was then promoted by the addition of 53.6 parts by weight of butyl acrylate, 20 parts by weight of ethyl acrylate, and 6.4 parts by weight of stearyl acrylate in order. During the polymerization, triamine was appropriately added to adjust the polymerization rate. The total amount of triamine used in this polymerization was 0.15 parts by weight. When the monomer conversation rate (polymerization reaction rate) reached about 95% or more, the volatile matter was removed by evaporation under reduced pressure to provide a polymer concentrate.

(30) To the concentrate were then added 21 parts by weight of 1,7-octadiene and 35 parts by weight of acetonitrile and was further added 0.34 parts by weight of triamine. While the internal temperature was adjusted to about 80 C. to about 90 C., the mixture was stirred under heating for some hours to react the polymer end with the octadiene. The acetonitrile and unreacted octadiene were removed by evaporation under reduced pressure to provide a concentrate containing an alkenyl-terminated polymer.

(31) The concentrate was diluted with toluene. A filter aid, an adsorbent (Kyowaad 700SEN; product of Kyowa Chemical Industry Co., Ltd.), and hydrotalcite (Kyowaad 500SH; product of Kyowa Chemical Industry Co., Ltd.) were added thereto, and the mixture was heated to about 80 to 100 C. and stirred. Then, solid components were filtered off. The filtrate was concentrated under reduced pressure to provide a crude polymer.

(32) The crude polymer, a thermal stabilizer (SUMILIZER GS; product of Sumitomo Chemical Co., Ltd.), and adsorbents (Kyowaad 700SEN and Kyowaad 500SH) were mixed. The mixture was evaporated under reduced pressure while being stirred under heating. The temperature was raised by heating, and the mixture was stirred under heating at a temperature of as high as about 170 C. to about 200 C. for several hours while being evaporated under reduced pressure. The reaction mixture was diluted with butyl acetate, and the adsorbents were filtered off. The filtrate was then concentrated to obtain a polymer containing alkenyl groups at both terminals.

(33) To 100 parts by weight of the polymer thus obtained were then added 300 ppm of a platinum-divinyldisiloxane complex (isopropanol solution having a platinum content of 3% by weight) and 0.9 parts by weight of trimethyl orthoformate and then gradually added dropwise 1.7 parts by weight of dimethoxymethylsilane with stirring. The mixed solution was reacted at 100 C. for 1 hour, and unreacted dimethoxymethylsilane was then distilled off under reduced pressure to provide a dimethoxymethylsilyl-terminated linear acrylic ester polymer (C-4) containing 1.9 reactive silyl groups on average per molecule and having a number average molecular weight of 24,000.

Synthesis Example 24

(34) To 40 parts by weight of toluene heated to 105 C. was added dropwise over 5 hours a solution prepared by dissolving in 15 parts by weight of toluene 67 parts by weight of methyl methacrylate, 5 parts by weight of butyl acrylate, 15 parts by weight of stearyl methacrylate, 5 parts by weight of 3-methacryloxypropylmethyldimethoxysilane, 8 parts by weight of -mercaptopropylmethyldimethoxysilane, and 3 parts by weight of 2,2-azobisisobutyronitrile as a polymerization initiator, and the mixture was then stirred for 2 hours. A solution containing 0.3 parts by weight of 2,2-azobisisobutyronitrile dissolved in 10 parts by weight of toluene was further added thereto, and the mixture was stirred for 2 hours to provide a toluene solution (solid content: 60%) of a reactive silyl group-containing (meth)acrylic polymer (C-5) having 2.0 silyl groups on average per molecule and having a number average molecular weight of 3,000 (calculated in the same way as in Synthesis Example 1).

Synthesis Example 25

(35) To 40 parts by weight of toluene heated to 105 C. was added dropwise over 5 hours a solution prepared by dissolving in 15 parts by weight of toluene 66 parts by weight of methyl methacrylate, 5 parts by weight of butyl acrylate, 15 parts by weight of stearyl methacrylate, 5 parts by weight of 3-methacryloxypropyltrimethoxysilane, 9 parts by weight of -mercaptopropyltrimethoxysilane, and 3 parts by weight of 2,2-azobisisobutyronitrile as a polymerization initiator, and the mixture was then stirred for 2 hours. A solution containing 0.3 parts by weight of 2,2-azobisisobutyronitrile dissolved in 10 parts by weight of toluene was further added thereto, and the mixture was stirred for 2 hours to provide a toluene solution (solid content: 60%) of a reactive silyl group-containing (meth)acrylic polymer (C-6) having 2.0 silyl groups on average per molecule and having a number average molecular weight of 3,000 (calculated in the same way as in Synthesis Example 1).

Synthesis Example 26

(36) To 40 parts by weight of toluene heated to 105 C. was added dropwise over 5 hours a solution prepared by dissolving in 15 parts by weight of toluene 66 parts by weight of methyl methacrylate, 10 parts by weight of butyl acrylate, 15 parts by weight of stearyl methacrylate, 9 parts by weight of n-dodecyl mercaptan, and 3 parts by weight of 2,2-azobisisobutyronitrile as a polymerization initiator, and the mixture was then stirred for 2 hours. A solution containing 0.3 parts by weight of 2,2-azobisisobutyronitrile dissolved in 10 parts by weight of toluene was further added thereto, and the mixture was stirred for 2 hours to provide a toluene solution (solid content: 60%) of a (meth)acrylic polymer (C-7) having a number average molecular weight of 3,000 (calculated in the same way as in Synthesis Example 1).

Example 1

(37) With 100 parts by weight in total of the polymer (A-1) (70 parts by weight) and the polymer (B-1) (30 parts by weight) were mixed 50 parts by weight of fatty acid-treated calcium carbonate (product name: Hakuenka CCR, product of Shiraishi Kogyo Kaisha, Ltd.) and 50 parts by weight of heavy calcium carbonate (product name: Whiton SB Red, a product of Shiraishi Calcium Kaisha, Ltd.). The mixture was sufficiently kneaded and then dispersed by passing through triple paint rolls three times. Thereafter, the mixture was dehydrated under reduced pressure at 120 C. for 2 hours and cooled to 50 C. or lower. To the mixture were then added 4 parts by weight of vinyltrimethoxysilane (product name: A-171, a product of Momentive Performance Materials Inc.) as a dehydrating agent, 3 parts by weight of -aminopropyltrimethoxysilane (product name: A-1110, a product of Momentive Performance Materials Inc.) as an adhesion-imparting agent, and 0.3 parts by weight of DBU (1,8-diazabicyclo[5,4,0]undecene-7, product of Wako Pure Chemical Industries, Ltd.) as a condensation catalyst, and the mixture was kneaded under dehydrated conditions with substantially no water. Thereafter, the mixture was charged into a moisture-proof container (cartridge) and then hermetically packed therein to provide a one-pack curable composition.

(38) (Evaluation)

(39) The skin formation time and tensile properties of the prepared composition were determined by the following methods.

(40) (Skin Formation Time)

(41) In an atmosphere of 23 C. and 50% RH, each curable composition was squeezed out of the cartridge and charged into a mold having a thickness of about 5 mm with a spatula, and the time point at which the surface of the charged composition was flattened was defined as the start time of curing. The curing time was measured by touching the surface of the composition by a spatula from time to time, and determining the time period required for the mixture to no longer stick to the spatula (regarded as skin formation time). Table 1 shows the results.

(42) (Tensile Properties)

(43) In an atmosphere of 23 C. and 50% RH, each curable composition was squeezed out of the cartridge, and the mixture was charged into a polyethylene mold having a thickness of 3 mm so that no air bubble was trapped. The charged composition was cured at 23 C. and 50% RH for 3 days and then at 50 C. for 4 days to give a cured product. No. 3 dumbbell-shaped specimens were punched out from the obtained cured product according to JIS K6251 and subjected to a tensile test (tensile rate: 200 mm/min., 23 C., 50% RH) to determine the tensile strength at break (TB) and the elongation at break (EB). Table 1 shows the results.

Examples 2 to 12 and 16 and Comparative Examples 1 to 12

(44) Each curable composition was prepared in the same way as in Example 1 except that the polymers (A), (B), and (C), plasticizer, filler, thixotropy-imparting agent, ultraviolet absorber, light stabilizer, dehydrating agent, adhesion-imparting agent, and catalyst were mixed at the ratios of Examples 2 to 12 and 16 and Comparative Examples 1 to 12 shown in Tables 1 to 3. The prepared compositions were evaluated. Tables 1 and 3 show their respective results.

Example 13

(45) A polymer mixture having a polymer weight ratio of (A-1)/(C-1)=60/40 was prepared by mixing 60 parts by weight of the reactive silyl group-containing polyoxypropylene polymer (A-1) obtained in Synthesis Example 1 with 66.7 parts by weight of the isobutanol solution of the reactive silyl group-containing (meth)acrylic polymer (C-1) obtained in Synthesis Example 20, and distilling off the isobutanol under reduced pressure. To 100 parts by weight of this polymer mixture were added 50 parts by weight of fatty acid-treated calcium carbonate (product name: Hakuenka CCR, product of Shiraishi Kogyo Kaisha, Ltd.) and 50 parts by weight of heavy calcium carbonate (product name: Whiton SB Red, a product of Shiraishi Calcium Kaisha, Ltd.). The mixture was sufficiently kneaded and then dispersed by passing through triple paint rolls three times. Thereafter, the mixture was dehydrated under reduced pressure at 120 C. for 2 hours and cooled to 50 C. or lower. To the mixture were then added 4 parts by weight of vinyltrimethoxysilane (product name: A-171, a product of Momentive Performance Materials Inc.) as a dehydrating agent, 3 parts by weight of -aminopropyltrimethoxysilane (product name: A-1110, a product of Momentive Performance Materials Inc.) as an adhesion-imparting agent, and 0.3 parts by weight of DBU (1,8-diazabicyclo[5,4,0]undecene-7, product of Wako Pure Chemical Industries, Ltd.) as a condensation catalyst, and the mixture was kneaded under dehydrated conditions with substantially no water. Thereafter, the mixture was charged into a moisture-proof container (cartridge) and then hermetically packed therein to provide a one-pack curable composition. Evaluation was performed in the same way as in Example 1.

Examples 14 to 15 and Comparative Examples 13 to 14

(46) Each curable composition was prepared in the same way as in Example 13 except that the polymers (A), (B), and (C), plasticizer, filler, thixotropy-imparting agent, ultraviolet absorber, light stabilizer, dehydrating agent, adhesion-imparting agent, and catalyst were mixed at the ratios of Examples 14 to 15 and Comparative Examples 13 to 14 shown in Tables 2 and 3. The prepared compositions were evaluated. Tables 2 and 3 show their respective results.

(47) TABLE-US-00001 TABLE 1 Composition (parts by weight) Mole- Back- Silyl cular bone group Comparative weight structure structure.sup.(1) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 1 Polyether (A-1) 21,100 Linear CMDMS 70 50 30 30 100 polymer (A) (A-2) 28,500 Linear CMDMS (A-3) 26,200 Branched CMDMS 50 (A-4) 14,600 Linear CMDMS (A-5) 14,600 Linear MMDMS (A-6) 14,600 Linear -type DMS 50 (A-7) 28,500 Linear CMDMS (A-8) 7,000 Linear CMDMS Polyether (B-1) 21,100 Linear DMS 30 50 50 polymer (B) (B-2) 28,500 Linear DMS (B-3) 26,200 Branched DMS 70 50 (B-4) 28,500 Linear DMS (B-5) 28,500 Linear TMS 70 (B-6) 7,000 Linear DMS Filler Hakuenka CCR.sup.(2) 50 50 50 50 50 50 50 Whiton SB Red.sup.(3) 50 50 50 50 50 50 50 Plasticizer DIDP.sup.(4) Hexamoll DINCH.sup.(5) Thixotropy- DISPARLON #6500.sup.(6) imparting agent Ultraviolet SUMISORB 400.sup.(7) absorber Light SANOL LS-770.sup.(8) stabilizer Dehydrating A-171.sup.(9) 4 4 4 4 4 4 4 agent Adhesion- A-1110.sup.(10) 3 3 3 3 3 3 3 imparting agent Catalyst DBU.sup.(11) 0.3 0.3 0.3 0.3 0.3 1-Phenylguanidine NEOSTANN S-1.sup.(12) 0.2 TIB223.sup.(13) U-220H.sup.(14) Curability Skin formation time (minutes) 20 20 35 35 15 20 15 Tensile test TB (MPa) 1.6 1.8 2.0 1.7 2.0 2.2 1.4 (No. 3 EB (%) 280 260 250 280 220 170 190 dumbbell) Composition (parts by weight) Mole- Back- Silyl cular bone group Comparative Comparative Comparative Comparative Comparative weight structure structure.sup.(1) Example 2 Example 3 Example 4 Example 5 Example 6 Polyether (A-1) 21,100 Linear CMDMS polymer (A) (A-2) 28,500 Linear CMDMS (A-3) 26,200 Branched CMDMS 100 (A-4) 14,600 Linear CMDMS (A-5) 14,600 Linear MMDMS (A-6) 14,600 Linear -type DMS 100 (A-7) 28,500 Linear CMDMS (A-8) 7,000 Linear CMDMS Polyether (B-1) 21,100 Linear DMS 100 polymer (B) (B-2) 28,500 Linear DMS (B-3) 26,200 Branched DMS 100 (B-4) 28,500 Linear DMS (B-5) 28,500 Linear TMS 100 (B-6) 7,000 Linear DMS Filler Hakuenka CCR.sup.(2) 50 50 50 50 50 Whiton SB Red.sup.(3) 50 50 50 50 50 Plasticizer DIDP.sup.(4) Hexamoll DINCH.sup.(5) Thixotropy- DISPARLON #6500.sup.(6) imparting agent Ultraviolet SUMISORB 400.sup.(7) absorber Light SANOL LS-770.sup.(8) stabilizer Dehydrating A-171.sup.(9) 4 4 4 4 4 agent Adhesion- A-1110.sup.(10) 3 3 3 3 3 imparting agent Catalyst DBU.sup.(11) 0.3 0.3 0.3 0.3 1-Phenylguanidine NEOSTANN S-1.sup.(12) TIB223.sup.(13) U-220H.sup.(14) Curability Skin formation time (minutes) 10 10 250 150 200 Tensile test TB (MPa) 1.8 2.2 1.7 2.0 1.5 (No. 3 EB (%) 110 110 470 200 250 dumbbell) .sup.(1)CMDMS: chloromethyldimethoxysilyl group, MMDMS: methoxymethyldimethoxysilyl group, DMS: dimethoxymethylsilyl group, TMS: trimethoxysilyl group .sup.(2)Fatty acid-treated precipitated calcium carbonate (Shiraishi Kogyo Kaisha, Ltd.) .sup.(3)Heavy calcium carbonate (SHIRAISHI CALCIUM KAISHA, LTD.) .sup.(4)Diisodecyl phthalate (J-PLUS Co., Ltd.) .sup.(5)1,2-Cyclohexanedicarboxylic acid diisononyl ester (BASF) .sup.(6)Fatty acid amide wax (Kusumoto Chemicals, Ltd.) .sup.(7)2,4-Di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate (Sumitomo Chemical Company, Limited) .sup.(8)Bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate (Sankyo Lifetech Co., Ltd.) .sup.(9)Vinyltrimethoxysilane (Momentive) .sup.(10)3-Aminopropyltrimethoxysilane (Momentive) .sup.(11)1,8-Diazabicyclo[5.4.0]undecene-7 (Wako Pure Chemical Industries, Ltd.) .sup.(12)Dioctyltin(bistriethoxysilicate) (Nitto Kasei Co., Ltd.) .sup.(13)Dioctyltin diacetylacetonate (TIB Chemicals AG) .sup.(14)Dibutyltin diacetylacetonate (Nitto Kasei Co., Ltd.)

(48) TABLE-US-00002 TABLE 2 Composition (parts by weight) Mole- Back- Silyl cular bone group Comparative weight structure structure.sup.(1) Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 7 Polyether (A-1) 21,100 Linear CMDMS polymer (A) (A-2) 28,500 Linear CMDMS 70 100 (A-3) 26,200 Branched CMDMS (A-4) 14,600 Linear CMDMS 50 50 (A-5) 14,600 Linear MMDMS 50 (A-6) 14,600 Linear -type DMS 50 (A-7) 28,500 Linear CMDMS 50 (A-8) 7,000 Linear CMDMS 30 Polyether (B-1) 21,100 Linear DMS 50 polymer (B) (B-2) 28,500 Linear DMS 50 70 (B-3) 26,200 Branched DMS (B-4) 28,500 Linear DMS 50 (B-5) 28,500 Linear TMS (B-6) 7,000 Linear DMS 30 Filler Hakuenka CCR.sup.(2) 50 50 50 50 50 50 50 Whiton SB Red.sup.(3) 160 160 160 160 160 160 160 Plasticizer DIDP.sup.(4) Hexamoll DINCH.sup.(5) 30 30 30 30 30 30 30 Thixotropy- DISPARLON #6500.sup.(6) 3 3 3 3 3 3 3 imparting agent Ultraviolet SUMISORB 400.sup.(7) 1 1 1 1 1 1 1 absorber Light SANOL LS-770.sup.(8) 1 1 1 1 1 1 1 stabilizer Dehydrating A-171.sup.(9) 4 4 4 4 4 4 4 agent Adhesion- A-1110.sup.(10) 3 3 3 3 3 3 3 imparting agent Catalyst DBU.sup.(11) 1-Phenylguanidine 0.3 0.3 0.3 0.3 0.3 NEOSTANN S-1.sup.(12) TIB223.sup.(13) 0.3 U-220H.sup.(14) 1 Curability Skin formation time (minutes) 15 20 50 50 30 10 15 Tensile test TB (MPa) 1.5 2.0 1.5 1.8 1.3 2 1.5 (No. 3 EB (%) 350 200 250 220 380 150 200 dumbbell) Composition (parts by weight) Mole- Back- Silyl cular bone group Comparative Comparative Comparative Comparative Comparative weight structure structure.sup.(1) Example 8 Example 9 Example 10 Example 11 Example 12 Polyether (A-1) 21,100 Linear CMDMS polymer (A) (A-2) 28,500 Linear CMDMS (A-3) 26,200 Branched CMDMS (A-4) 14,600 Linear CMDMS 100 (A-5) 14,600 Linear MMDMS 100 (A-6) 14,600 Linear -type DMS (A-7) 28,500 Linear CMDMS 100 (A-8) 7,000 Linear CMDMS Polyether (B-1) 21,100 Linear DMS polymer (B) (B-2) 28,500 Linear DMS 100 (B-3) 26,200 Branched DMS (B-4) 28,500 Linear DMS 100 (B-5) 28,500 Linear TMS (B-6) 7,000 Linear DMS Filler Hakuenka CCR.sup.(2) 50 50 50 50 50 Whiton SB Red.sup.(3) 160 160 160 160 160 Plasticizer DIDP.sup.(4) Hexamoll DINCH.sup.(5) 30 30 30 30 30 Thixotropy- DISPARLON #6500.sup.(6) 3 3 3 3 3 imparting agent Ultraviolet SUMISORB 400.sup.(7) 1 1 1 1 1 absorber Light SANOL LS-770.sup.(8) 1 1 1 1 1 stabilizer Dehydrating A-171.sup.(9) 4 4 4 4 4 agent Adhesion- A-1110.sup.(10) 3 3 3 3 3 imparting agent Catalyst DBU.sup.(11) 1-Phenylguanidine 0.3 0.3 0.3 NEOSTANN S-1.sup.(12) TIB223.sup.(13) 0.3 U-220H.sup.(14) 1 Curability Skin formation time (minutes) 20 30 20 50 150 Tensile test TB (MPa) 1.5 1.3 1.8 1.7 1.4 (No. 3 EB (%) 110 200 250 350 110 dumbbell) .sup.(1)CMDMS: chloromethyldimethoxysilyl group, MMDMS: methoxymethyldimethoxysilyl group, DMS: dimethoxymethylsilyl group, TMS: trimethoxysilyl group .sup.(2)Fatty acid-treated precipitated calcium carbonate (Shiraishi Kogyo Kaisha, Ltd.) .sup.(3)Heavy calcium carbonate (SHIRAISHI CALCIUM KAISHA, LTD.) .sup.(4)Diisodecyl phthalate (J-PLUS Co., Ltd.) .sup.(5)1,2-Cyclohexanedicarboxylic acid diisononyl ester (BASF) .sup.(6)Fatty acid amide wax (Kusumoto Chemicals, Ltd.) .sup.(7)2,4-Di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate (Sumitomo Chemical Company, Limited) .sup.(8)Bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate (Sankyo Lifetech Co., Ltd.) .sup.(9)Vinyltrimethoxysilane (Momentive) .sup.(10)3-Aminopropyltrimethoxysilane (Momentive) .sup.(11)1,8-Diazabicyclo[5.4.0]undecene-7 (Wako Pure Chemical Industries, Ltd.) .sup.(12)Dioctyltin(bistriethoxysilicate) (Nitto Kasei Co., Ltd.) .sup.(13)Dioctyltin diacetylacetonate (TIB Chemicals AG) .sup.(14)Dibutyltin diacetylacetonate (Nitto Kasei Co., Ltd.)

(49) TABLE-US-00003 TABLE 3 Composition (parts by weight) Mole- Back- Silyl cular bone group Example Example Example Example Comparative Comparative weight structure structure.sup.(1) 13 14 15 16 Example 13 Example 14 Polyether polymer (A) (A-1) 21,100 Linear CMDMS 60 60 (A-2) 28,500 Linear CMDMS (A-3) 26,200 Branched CMDMS 60 (A-4) 14,600 Linear CMDMS 50 (A-5) 14,600 Linear MMDMS (A-6) 14,600 Linear -type DMS (A-7) 28,500 Linear CMDMS (A-8) 7,000 Linear CMDMS Polyether polymer (B) (B-1) 21,100 Linear DMS 60 60 (B-2) 28,500 Linear DMS (B-3) 26,200 Branched DMS (B-4) 28,500 Linear DMS (B-5) 28,500 Linear TMS (B-6) 7,000 Linear DMS Acrylic polymer (C) (C-1) 2,000 Linear DMS 40 40 (C-2) 2,000 Linear TMS 40 40 (C-3) 2,000 Linear -type TMS 40 (C-4) 27,000 Linear DMS 50 Filler Hakuenka CCR.sup.(2) 50 50 50 50 50 50 Whiton SB Red.sup.(3) 50 50 160 160 50 50 Plasticizer DIDP.sup.(4) 20 20 20 20 Hexamoll DINCH.sup.(5) 30 30 Thixotropy-imparting agent DISPARLON #6500.sup.(6) 3 3 Ultraviolet absorber SUMISORB 400.sup.(7) 1 1 Light stabilizer SANOL LS-770.sup.(8) 1 1 Dehydrating agent A-171.sup.(9) 4 4 4 4 4 4 Adhesion-imparting agent A-1110.sup.(10) 3 3 3 3 3 3 Catalyst DBU.sup.(11) 0.3 0.3 0.3 1-Phenylguanidine 1 0.3 NEOSTANN S-1.sup.(12) 0.2 TIB223.sup.(13) U-220H.sup.(14) Curability Skin formation time (minutes) 15 35 3 20 270 60 Tensile test TB (MPa) 2.0 2.3 2.0 1.7 2.0 2.3 (No. 3 dumbbell) EB (%) 360 200 150 150 390 200 .sup.(1)CMDMS: chloromethyldimethoxysilyl group, MMDMS: methoxymethyldimethoxysilyl group, DMS: dimethoxymethylsilyl group, TMS: trimethoxysilyl group .sup.(2)Fatty acid-treated precipitated calcium carbonate (Shiraishi Kogyo Kaisha, Ltd.) .sup.(3)Heavy calcium carbonate (SHIRAISHI CALCIUM KAISHA, LTD.) .sup.(4)Diisodecyl phthalate (J-PLUS Co., Ltd.) .sup.(5)1,2-Cyclohexanedicarboxylic acid diisononyl ester (BASF) .sup.(6)Fatty acid amide wax (Kusumoto Chemicals, Ltd.) .sup.(7)2,4-Di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate (Sumitomo Chemical Company, Limited) .sup.(8)Bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate (Sankyo Lifetech Co., Ltd.) .sup.(9)Vinyltrimethoxysilane (Momentive) .sup.(10)3-Aminopropyltrimethoxysilane (Momentive) .sup.(11)1,8-Diazabicyclo[5.4.0]undecene-7 (Wako Pure Chemical Industries, Ltd.) .sup.(12)Dioctyltin(bistriethoxysilicate) (Nitto Kasei Co., Ltd.) .sup.(13)Dioctyltin diacetylacetonate (TIB Chemicals AG) .sup.(14)Dibutyltin diacetylacetonate (Nitto Kasei Co., Ltd.)

(50) Comparing the results of Examples and Comparative Examples in Tables 1 to 3, it is found that the mixture of the polymer (A) containing a reactive silyl group having a specific structure with the dimethoxymethylsilyl- or trimethoxysilyl-terminated polymer (B) and/or the acrylic polymer (C) exhibits favorable skin formation time and excellent tensile properties of the cured product even when an amine catalyst or a small amount of a dioctyltin compound was used. As demonstrated, however, the polymer (A) alone offers insufficient elongation of the cured product, while the polymer (B) alone slows the skin formation time.

Example 17

(51) With 100 parts by weight in total of the polymer (A-2) (20 parts by weight) and the polymer (B-7) (80 parts by weight) were mixed 100 parts by weight of heavy calcium carbonate (product name: Whiton SB Red, a product of Shiraishi Calcium Kaisha, Ltd.) and 2 parts by weight of hydrophilic fumed silica (product name: Aerosil 200, a product of Nippon Aerosil Co., Ltd.). The mixture was sufficiently kneaded and then dispersed by passing through triple paint rolls once. Subsequently, the mixture was kneaded for 2 hours while dehydrated under reduced pressure conditions of 0.2 mmHg at 120 C. using a planetary mixer. After cooling to room temperature, 2 parts by weight of vinyltrimethoxysilane as a dehydrating agent, 2 parts by weight of -aminopropyltrimethoxysilane as an adhesion-imparting agent, 5 parts by weight of 1-o-tolylbiguanide as a condensation catalyst, and 0.3 parts by weight of dibutyltin dilaurate (product name: NEOSTANN U-100, produced by Nitto Kasei Co., Ltd.) were added to the mixture and the mixture was kneaded under dehydrated conditions with substantially no water. Thereafter, the mixture was charged into a moisture-proof container (cartridge) and then hermetically packed therein to provide a one-pack curable composition.

(52) (Evaluation)

(53) The initial tack properties and adhesion of the prepared compositions were determined by the following methods.

(54) (Initial Tack)

(55) Tack Development Time and Tack Time

(56) Each prepared composition was applied to a slate plate by combing. Thereafter, the state of the applied composition was observed by a finger touch. The time point at which the finger felt a resistance when it was released from the composition was regarded as the tack development time. The time period during which this resistance continued was regarded as the tack time.

(57) Initial Holding Power (Tack Strength)

(58) Each prepared composition was applied to a slate plate by combing. A vinyl floor sheet (PERMALEUM, a product of Tajima, Inc.) having a length of 200 mm and a width of 25 mm was laminated thereto. The vinyl floor sheet used was in advance wrapped, with its backside facing inward, around a PVC pipe having a radius of 25 mm and thereby deformed. After the lamination of this vinyl floor sheet, the laminate was left for a while. The tack strength was assessed as being poor (x) when the vinyl floor sheet arched up and separated. The tack strength was assessed as being good () when the vinyl floor sheet stayed laminated without arching up.

(59) (Adhesion Strength)

(60) Each prepared composition was applied to a slate plate by combing according to JIS A5536, and an open time was taken until tack was developed. Thereafter, a vinyl floor sheet (PERMALEUM, a product of Tajima, Inc.) having a length of 200 mm and a width of 25 mm was laminated thereto. The laminate was left at 23 C. for 1 week and then subjected to a tensile test (tensile rate: 200 mm/min) in a peeling direction at 90 to determine the adhesion strength.

Examples 18 to 23 and Comparative Examples 15 to 20

(61) Each curable composition was prepared in the same way as in Example 18 except that the polymers (A), (B), and (C), filler, dehydrating agent, adhesion-imparting agent, and catalyst were mixed at the ratios of Examples 18 to 23 and Comparative Examples 15 to 20 shown in Tables 4 and 5. The prepared compositions were evaluated. Tables 4 and 5 show their respective results.

(62) TABLE-US-00004 TABLE 4 Composition (parts by weight) Mole- Back- Silyl cular bone group Example Example Comparative Comparative weight structure structure.sup.(1) 17 18 Example 15 Example 16 Polyether polymer (A) (A-2) 28,500 Linear CMDMS 20 20 100 100 Polyether polymer (B) (B-2) 28,500 Linear DMS 50 (B-7) 14,500 Linear DMS 80 (B-8) 4,200 Linear DMS 30 Filler Aerosil 200.sup.(2) 2 2 2 2 Whiton SB Red.sup.(3) 100 100 100 100 Dehydrating agent A-171.sup.(4) 2 2 2 2 Adhesion-imparting agent A-1110.sup.(5) 2 2 2 2 Catalyst 1-o-Tolylbiguanide 5 5 5 5 NEOSTANN U-100.sup.(6) 0.3 0.3 0.3 Viscosity (Pa .Math. S) 410 190 490 480 Tack development time (minutes) 15 15 10 10 Initial holding power (Tack strength) Tack time (minutes) 15-110 15-100 10-20 10-20 Peel adhesion strength (N/25 mm) 27 24 20 21 .sup.(1)CMDMS: chloromethyldimethoxysilyl group, DMS: dimethoxymethylsilyl group, TMS: trimethoxysilyl group .sup.(2)Hydrophilic fumed silica (Nippon Aerosil Co., Ltd.) .sup.(3)Heavy calcium carbonate (SHIRAISHI CALCIUM KAISHA, LTD.) .sup.(4)Vinyltrimethoxysilane (Momentive) .sup.(5)N-(-aminoethyl)--aminopropyltrimethoxysilane (Momentive) .sup.(6)Dibutyltin dilaurate (Nitto Kasei Co., Ltd.)

(63) TABLE-US-00005 TABLE 5 Composition (parts by weight) Compar- Compar- Compar- Compar- Molec- Back- Silyl ative ative ative ative ular bone group Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- weight structure structure.sup.(1) ple 19 ple 20 ple 21 ple 22 ple 23 ple 17 ple 18 ple 19 ple 20 Polyether (A-2) 28,500 Linear CMDMS 30 30 30 100 20 polymer (A) Polyether (B-1) 21,100 Linear DMS 70 70 70 70 70 70 polymer (B-5) 28,500 Linear TMS 30 20 20 (B) (B-7) 14,500 Linear DMS 80 80 80 Acrylic (C-5) 3,000 Linear DMS 30 30 30 30 30 polymer (C-6) 3,000 Linear TMS 30 30 (C) (C-7) 3,000 Linear 30 30 Filler Aerosil 200.sup.(2) 2 2 2 2 2 2 2 2 2 Whiton SB Red.sup.(3) 100 100 100 100 100 100 100 100 100 Dehy- A-171.sup.(4) 2 2 2 2 2 2 2 2 2 drating agent Adhesion- A-1110.sup.(5) 2 2 2 2 2 2 2 2 2 imparting agent Catalyst 1-o-Tolylbiguanide 5 5 5 5 5 5 5 5 NEOSTANN U-100.sup.(6) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Tack development time (minutes) 15 10 10 5 20 150 50 60 60 Initial holding power (tack strength) Tack time (minutes) 15-220 10-190 10-310 5-100 20-220 150-170 50-80 60-80 60-80 Peel adhesion strength (N/25 mm) 34 32 38 30 35 31 29 24 26 .sup.(1)CMDMS: chloromethyldimethoxysilyl group, DMS: dimethoxymethylsilyl group, TMS: trimethoxysilyl group .sup.(2)Hydrophilic fumed silica (Nippon Aerosil Co., Ltd.) .sup.(3)Heavy calcium carbonate (SHIRAISHI CALCIUM KAISHA, LTD.) .sup.(4)Vinyltrimethoxysilane (Momentive) .sup.(5)N-(-aminoethyl)--aminopropyltrimethoxysilane (Momentive) .sup.(6)Dibutyltin dilaurate (Nitto Kasei Co., Ltd.)

(64) Comparing the results of Examples and Comparative Examples in Tables 4 and 5, it is found that the mixture of the polymer (A) containing a reactive silyl group having a specific structure and the polymer (B) (and the polymer (C)) develops tack rapidly and keeps it for a very long period of time and is thus excellent as contact adhesive. In addition, the tack strength thus developed is sufficiently high for practical use. On the other hand, compositions containing components other than the combinations of the polymers according to the present invention fail to have tack strength suitable for practical use, or have a tack time shorter than that of the compositions of the present invention.

INDUSTRIAL APPLICABILITY

(65) The curable composition of the present invention comprising the reactive silyl group-containing polyether polymer (A), and the reactive silyl group-containing polyether polymer (B) and/or the reactive silyl group-containing (meth)acrylic polymer has excellent elongation properties and rapid curability and is also excellent in initial tack properties.