Organopolysiloxane containing mercapto group and alkoxysilyl group and composition comprising same

Abstract

For example, an organopolysiloxane having a trialkoxysilyl group-containing organic group, a dialkoxymethylsilyl group-containing organic group or both, and a mercapto group-containing organic group, which is represented by the following average compositional formula (1), has low volatility, and has good adhesiveness and adhesion to an inorganic substrate. (A) a (B) b (C) c (D) dSiO (4-a-b-c-d) / 2 (1) (In the formula, A represents an organic group containing a mercapto group, B represents an organic group containing a trialkoxysilyl group or an organic group containing a dialkoxymethylsilyl group, C represents a hydrolyzable group, D represents an alkyl group having 1-12 carbon atoms, a haloalkyl group having 1-10 carbon atoms or an aryl group having 6-12 carbon atoms, and d represents an alkyl group having 1-12 carbon atoms; and a, b, c, and d represent numbers satisfying 0 < a < 1, 0 < b < 1, 0 < c < 3, 0 < = d < 1, and 0 < a + b + c + d < 4).

Description

Technical Field

[0001] The present invention relates to an organopolysiloxane containing a mercapto group and an alkoxysilyl group, and a composition containing the same, and more particularly to an organopolysiloxane having a hydrolysis condensate of an organosilicon compound containing a mercapto group as a main chain and containing a trialkoxysilyl group and / or a dialkoxysilyl group, and a composition containing the same. Background Art

[0002] Organic silicon compounds containing a mercapto group and a hydrolyzable silyl group are widely used as adhesion enhancers with inorganic substrates such as glass and metal (Patent Document 1), and 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane, and the like are already on the market.

[0003] On the other hand, 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyldimethoxymethylsilane are low molecular weight components and therefore have high volatility. As products whose volatility is reduced, oligomers formed by (co) hydrolysis and condensation of monomer components containing the above-mentioned alkoxysilane containing a mercapto group are known (Patent Documents 2 to 4), and as such products, KR-518 and KR-519 manufactured by Shin-Etsu Chemical Co., Ltd. are already on the market.

[0004] However, oligomers obtained by (co)hydrolyzing and condensing monomer components containing such mercapto group-containing alkoxysilanes do not contain highly active trialkoxysilyl groups or dialkoxyorganosilyl groups, and may have insufficient adhesiveness and adhesion to inorganic substrates such as glass and metals.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent No. 4692885

[0008] Patent Document 2: Japanese Patent Application Laid-Open No. 07-292108

[0009] Patent Document 3: Japanese Patent Application Laid-Open No. 09-111188

[0010] Patent Document 4: Japanese Patent Application Publication No. 2003-113243 Summary of the invention

[0011] Problems to be solved by the invention

[0012] The present invention has been made in view of the above-mentioned actual situation, and an object of the present invention is to provide an organic group organopolysiloxane containing a mercapto group which has low volatility and excellent adhesion and tightness to an inorganic substrate, a method for producing the same, and a composition containing the organopolysiloxane.

[0013] Means for solving problems

[0014] The present inventors have conducted intensive studies to achieve the above-mentioned purpose, and as a result, have discovered a method for producing an organopolysiloxane containing an organic group containing a mercapto group and a trialkoxysilyl group or a dialkoxymethylsilyl group and having low volatility. At the same time, they have learned that a resin composition such as an epoxy resin composition containing the organopolysiloxane exhibits excellent adhesion to an inorganic substrate, thereby completing the present invention.

[0015] That is, the present invention provides:

[0016] 1. An organopolysiloxane having:

[0017] an organic group containing a trialkoxysilyl group, an organic group containing a dialkoxymethylsilyl group, or both; and

[0018] An organic group containing a mercapto group.

[0019] 2. The organopolysiloxane according to 1, which is represented by the following average composition formula (1).

[0020] (A) a (B) b (C) c (D) d SiO (4-a-b-c-d) / 2 (1)

[0021] (In the formula, A represents an organic group containing a mercapto group, B represents an organic group containing a trialkoxysilyl group or an organic group containing a dialkoxymethylsilyl group, C represents a hydrolyzable group, D represents an alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and a, b, c, and d represent numbers satisfying 0<a<1, 0<b<1, 0<c<3, 0≤d<1, and 0<a+b+c+d<4.)

[0022] 3. The organopolysiloxane according to 2, wherein the mercapto group-containing organic group is represented by the following formula (2):

[0023] *-(CH2) m -SH (2)

[0024] (In the formula, m represents an integer of 1 to 10, and *- represents a bonding end.)

[0025] The trialkoxysilyl-containing organic group or dialkoxymethylsilyl-containing organic group is represented by the following formula (3):

[0026] *-(CH2) m -S-(CH2) n -Si(CH3)3-k (OR 1 ) k (3) (wherein, m represents an integer of 1 to 10, n represents an integer of 1 to 10, k represents 2 or 3, R 1 Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, and *- represents a bonding end. )

[0027] The hydrolyzable group is represented by the following formula (4):

[0028] *-OR 1 (4)

[0029] (Where R 1 It has the same meaning as above, and *- indicates a bonding end. ).

[0030] 4. The method for producing an organopolysiloxane according to any one of 1 to 3, wherein a hydrolysis condensate of a mercapto group-containing organosilicon compound represented by the following formula (5) is reacted with an alkenyl group-containing organosilicon compound represented by the following formula (7),

[0031] [Chemistry 1]

[0032]

[0033] (Where R 1 Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, y represents an integer of 1 to 3, m represents an integer of 1 to 10, and Me represents a methyl group.

[0034] [Chemistry 2]

[0035]

[0036] (Where R 1 represents the same meaning as above, k represents an integer of 0 to 8, z represents 2 or 3, and Me represents a methyl group. ).

[0037] 5. The method for producing an organopolysiloxane according to any one of 1 to 3, wherein a co-hydrolysis condensate of a mercapto group-containing organosilicon compound represented by the following formula (5) and an organosilicon compound represented by the following formula (6) is reacted with an alkenyl group-containing organosilicon compound represented by the following formula (7),

[0038] [Chemistry 3]

[0039]

[0040] (Where R1 Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, y represents an integer of 1 to 3, m represents an integer of 1 to 10, and Me represents a methyl group.

[0041] [Chemistry 4]

[0042] (R 1 O) z -Si-R 3 4-z (6)

[0043] (Where R 1 Means the same as above, R 3 represents an alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and z represents an integer of 1 to 4.

[0044] [Chemistry 5]

[0045]

[0046] (Where R 1 represents the same meaning as above, k represents an integer of 0 to 8, z represents 2 or 3, and Me represents a methyl group. ).

[0047] 6. A composition comprising the organopolysiloxane according to any one of 1 to 3.

[0048] Effects of the Invention

[0049] The organopolysiloxane of the present invention has low volatility and high adhesion and tackiness to inorganic substrates such as glass and metal, and can therefore be used as an adhesion improver. DETAILED DESCRIPTION

[0050] The present invention is described in detail below.

[0051] The organopolysiloxane of the present invention has an organic group containing a trialkoxysilyl group, an organic group containing a dialkoxymethylsilyl group, or both, and an organic group containing a mercapto group; specifically, an organopolysiloxane represented by the following average composition formula (1) is preferred.

[0052] (A) a (B) b (C) c (D) d S i (4-a-b-c-d) / 2 (1)

[0053] In formula (1), A represents an organic group containing a mercapto group, B represents an organic group containing a trialkoxysilyl group or an organic group containing a dialkoxymethylsilyl group, C represents a hydrolyzable group, D represents an alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and a, b, c, and d represent numbers satisfying 0<a<1, 0<b<1, 0<c<3, 0≤d<1, and 0<a+b+c+d<4.

[0054] In addition, a, b, c and d mean the average molar number of each organic group relative to 1 mole of silicon atoms.

[0055] More specifically, the following organopolysiloxane is more preferred: wherein in formula (1), the above-mentioned organic group containing a mercapto group is represented by the following formula (2):

[0056] *-(CH2) m -SH(2)

[0057] (In the formula, m represents an integer of 1 to 10, and *- represents a bonding end.)

[0058] The above-mentioned trialkoxysilyl-containing organic group or dialkoxymethylsilyl-containing organic group is represented by the following formula (3):

[0059] *-(CH2) m -S-(CH2) n -Si(CH3) 3-k (OR 1 ) k (3)

[0060] (wherein, m represents an integer of 1 to 10, n represents an integer of 1 to 10, k represents 2 or 3, R 1 Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, and *- represents a bonding end. ) represents, and the above-mentioned hydrolyzable group is represented by the following formula (4)

[0061] *-OR 1 (4)

[0062] (Where R 1 It has the same meaning as above, and *- indicates a bonding end. )

[0063] express.

[0064] In the above formula (3) and formula (4), R 1Specific examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-decyl, octadecyl, etc. Specific examples of the aryl group having 6 to 10 carbon atoms include phenyl, tolyl, naphthyl, etc. Specific examples of the aralkyl group having 7 to 10 carbon atoms include benzyl, etc. Specific examples of the alkenyl group having 2 to 10 carbon atoms include ethenyl, propenyl, pentenyl, etc.

[0065] In the above formula (1), specific examples of the alkyl group having 1 to 12 carbon atoms as D include methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-decyl and the like; specific examples of the halogenated alkyl group having 1 to 10 carbon atoms include 1-chloromethyl, 3-chloropropyl, 6-chlorohexyl, 8-chlorooctyl, 1-bromomethyl, 3-bromopropyl, 6-bromohexyl, 8-bromooctyl and the like; and specific examples of the aryl group having 6 to 12 carbon atoms include phenyl, tolyl, styryl, naphthyl, biphenyl and the like.

[0066] Specific examples of the mercapto group-containing organic group represented by the above formula (2) include the following groups.

[0067] *-CH2SH,

[0068] *-C2H4SH,

[0069] *-C3H6SH,

[0070] *-C4H8SH,

[0071] *-C5H 10 SH,

[0072] *-C6H 12 SH,

[0073] *-C7H 14 SH,

[0074] *-C8H 16 SH,

[0075] *-C9H 18 SH,

[0076] *-C 10 H 20 SH

[0077] (In the formula, *- represents the bonding end. The same applies below.)

[0078] Specific examples of the trialkoxysilyl group-containing organic group or the dialkoxymethylsilyl group-containing organic group represented by the above formula (3) include the following groups.

[0079] *-C3H6-S-C2H4-S i(OCH3)3、

[0080] *-C3H6-S-C2H4-S iCH3(OCH3)2、

[0081] *-C3H6-S-C2H4-S i(OC2H5)3、

[0082] *-C3H6-S-C2H4-S iCH3(OC2H5)2、

[0083] *-C3H6-S-C6H 12 -Si(OCH3)3,

[0084] *-C3H6-S-C6H 12 -SiCH3(OCH3)2,

[0085] *-C3H6-S-C6H 12 -Si(OC2H5)3,

[0086] *-C3H6-S-C6H 12 -SiCH3(OC2H5)2,

[0087] *-C3H6-S-C8H 16 -Si(OCH3)3,

[0088] *-C3H6-S-C8H 16 -SiCH3(OCH3)2,

[0089] *-C3H6-S-C8H 16 -Si(OC2H5)3,

[0090] *-C3H6-S-C8H 16 -SiCH3(OC2H5)2,

[0091] *-CH2-S-C2H4-S i(OCH3)3、

[0092] *-CH2-S-C2H4-S iCH3(OCH3)2、

[0093] *-CH2-S-C2H4-S i(OC2H5)3、

[0094] *-CH2-S-C2H4-S iCH3(OC2H5)2、

[0095] *-CH2-S-C6H 12 -Si(OCH3)3,

[0096] *-CH2-S-C6H 12 -SiCH3(OCH3)2,

[0097] *-CH2-S-C6H 12 -Si(OC2H5)3,

[0098] *-CH2-S-C6H 12 -SiCH3(OC2H5)2,

[0099] *-CH2-S-C8H 16 -Si(OCH3)3,

[0100] *-CH2-S-C8H 16 -SiCH3(OCH3)2,

[0101] *-CH2-S-C8H 16 -Si(OC2H5)3,

[0102] *-CH2-S-C8H 16 -SiCH3(OC2H5)2

[0103] Specific examples of the hydrolyzable group represented by the above formula (4) include the following groups.

[0104] *-OCH3,

[0105] *-OC2H5,

[0106] *-OC3H7,

[0107] *-OC4H9,

[0108] *-OC5H 11

[0109] The organopolysiloxane of the present invention can be produced by reacting a hydrolysis condensate of a mercapto group-containing organosilicon compound represented by the following formula (5) with an alkenyl group-containing organosilicon compound represented by the following formula (7), or by reacting a co-hydrolysis condensate of a mercapto group-containing organosilicon compound represented by the following formula (5) and an organosilicon compound represented by the following formula (6) with an alkenyl group-containing organosilicon compound represented by the following formula (7).

[0110] [Chemistry 6]

[0111]

[0112] (Where R 1 and m have the same meanings as above, y represents an integer of 1 to 3, and Me represents a methyl group.)

[0113] [Chemistry 7]

[0114]

[0115] (Where R 1 represents the same meaning as above, k represents an integer of 0 to 8, z is 2 or 3, and Me represents a methyl group. )

[0116] [Chemistry 8]

[0117] (R 1 O) z -Si-R 3 4-z (6)

[0118] (Where R 1 Means the same as above, R 3 represents an alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and z represents an integer of 1 to 4.

[0119] In the above formula (6), as R 3 Specific examples of the alkyl group having 1 to 12 carbon atoms represented by ' include methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-decyl and the like; specific examples of the haloalkyl group having 1 to 10 carbon atoms include 1-chloromethyl, 3-chloropropyl, 6-chlorohexyl, 8-chlorooctyl, 1-bromomethyl, 3-bromopropyl, 6-bromohexyl, 8-bromooctyl and the like; specific examples of the aryl group having 6 to 12 carbon atoms include phenyl, tolyl, styryl, naphthyl, biphenyl and the like.

[0120] Specific examples of the organic silicon compound represented by the above formula (5) include α-mercaptomethyltrimethoxysilane, α-mercaptomethylmethyldimethoxysilane, α-mercaptomethyltriethoxysilane, α-mercaptomethylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldiethoxysilane, etc.

[0121] Specific examples of the organosilicon compound represented by the formula (6) include methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, ethyltrimethoxysilane, ethylmethyldimethoxysilane, ethyltriethoxysilane, ethylmethyldiethoxysilane, butyltrimethoxysilane, butylmethyldimethoxysilane, butyltriethoxysilane, butylmethyldiethoxysilane, hexyltrimethoxysilane, hexylmethyldimethoxysilane, hexyltriethoxysilane, hexylmethyldiethoxysilane, octyltrimethoxysilane, octylmethyldimethoxysilane, octyltriethoxysilane, Organosilicon compounds containing alkyl groups, such as phenyltrimethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, p-phenylvinyltrimethoxysilane, p-phenylvinylmethyldimethoxysilane, p-phenylvinyltriethoxysilane, p-phenylvinylmethyldiethoxysilane; organosilicon compounds containing aromatic groups, such as 1-chloromethyltrimethoxysilane, 1-chloromethylmethyldimethoxysilane, 1-chloromethyltriethoxysilane , 1-chloromethylmethyldiethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropylmethyldiethoxysilane, 6-chlorohexyltrimethoxysilane, 6-chlorohexylmethyldimethoxysilane, 6-chlorohexyltriethoxysilane, 6-chlorohexylmethyldiethoxysilane, 8-chlorooctyltrimethoxysilane, 8-chlorooctylmethyldimethoxysilane, 8-chlorooctyltriethoxysilane, 8-chlorooctylmethyldiethoxysilane, 1-bromomethyltrimethoxysilane, 1-bromomethylmethyldimethoxysilane, 1-bromomethyltriethoxysilane, 1 - Organic silicon compounds containing a halogenated alkyl group such as bromomethylmethyldiethoxysilane, 3-bromopropyltrimethoxysilane, 3-bromopropylmethyldimethoxysilane, 3-bromopropyltriethoxysilane, 3-bromopropylmethyldiethoxysilane, 6-bromohexyltrimethoxysilane, 6-bromohexylmethyldimethoxysilane, 6-bromohexyltriethoxysilane, 6-bromohexylmethyldiethoxysilane, 8-bromooctyltrimethoxysilane, 8-bromooctylmethyldimethoxysilane, 8-bromooctyltriethoxysilane, 8-bromooctylmethyldiethoxysilane; tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane and tetrabutoxysilane.

[0122] Specific examples of the alkenyl-containing organosilicon compounds represented by the above formula (7) include vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, allyltrimethoxysilane, allylmethyldimethoxysilane, allyltriethoxysilane, allylmethyldiethoxysilane, hexenyltrimethoxysilane, hexenylmethyldimethoxysilane, hexenyltriethoxysilane, hexenylmethyldiethoxysilane, octenyltrimethoxysilane, octenylmethyldimethoxysilane, octenyltriethoxysilane, octenylmethyldiethoxysilane, and the like.

[0123] The hydrolysis condensate of the mercapto group-containing organosilicon compound represented by the above formula (5) or the co-hydrolysis condensate of the mercapto group-containing organosilicon compound represented by the above formula (5) and the organosilicon compound represented by the above formula (6) can be produced by a known method using a hydrolysis-condensation catalyst.

[0124] As the hydrolysis-condensation catalyst, various conventionally known hydrolysis-condensation catalysts can be used, and specific examples thereof include organic acids such as acetic acid, butyric acid, maleic acid, and citric acid; inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid, and sulfuric acid; basic compounds such as triethylamine; organic metal salts such as tetrabutyl titanate and dibutyltin dilaurate; F-containing compounds such as KF and NH4F, etc. These may be used alone or in combination.

[0125] The amount of the catalyst used is preferably in the range of 0.0001 to 1 mol % based on all reaction components.

[0126] The amount of water used in the hydrolysis-condensation reaction can be adjusted according to the desired degree of polymerization, and is usually preferably 0.5 to 0.99 mol, more preferably 0.66 to 0.90 mol, based on 1 mol of all hydrolyzable silyl groups.

[0127] In the hydrolysis-condensation reaction, a solvent may be used as necessary.

[0128] Examples of the solvent that can be used include alcohols such as methanol, ethanol, isopropanol, and tert-butyl alcohol; ketones such as acetone and methyl isobutyl ketone; ethers such as dibutyl ether; esters such as ethyl acetate; aromatics such as toluene, etc. Among these, alcohols such as methanol and ethanol are preferred.

[0129] The reaction of the hydrolysis condensate of the mercapto group-containing organosilicon compound represented by the above formula (5), or the co-hydrolysis condensate of the mercapto group-containing organosilicon compound represented by the above formula (5) and the organosilicon compound represented by the above formula (6) with the vinyl group-containing organosilicon compound represented by the above formula (7) can be carried out using the known ene-thiol reaction technology.

[0130] In the ene-thiol reaction, a catalyst such as an organic peroxide or an azo compound may be used as necessary.

[0131] Specific examples of the organic peroxide include benzoyl peroxide, cumene hydroperoxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, and dicumyl peroxide.

[0132] Specific examples of the azo compound include 2,2'-azobispropane, 2,2'-dichloro-2,2'-azobispropane, 1,1'-azo(methylethyl)diacetate, 2,2'-azobisisobutane, 2,2'-azobisisobutyramide, 2,2'-azobisisobutyronitrile (AIBN), methyl 2,2'-azobis-2-methylpropionate, 2,2'-dichloro-2,2'-azobisbutane, 2,2'-azobis-2-methylbutyronitrile, dimethyl 2,2'-azobisisobutyrate, 3,5-dihydroxymethylphenylazo-2-methylmalononitrile, 2,2'-azobis-2-methylvaleronitrile, dimethyl 4,4'-azobis-4-cyanovalerate, and 2,2'-azobis-2,4-dimethylvaleronitrile.

[0133] The amount of the catalyst used is preferably 0.00001 to 10 parts by mass relative to 100 parts by mass of the total amount of the hydrolysis condensate of the mercapto group-containing organosilicon compound represented by the above formula (5) or the co-hydrolysis condensate of the mercapto group-containing organosilicon compound represented by the above formula (5) and the organosilicon compound represented by the above formula (6), and the alkenyl group-containing organosilicon compound represented by the above formula (7).

[0134] In the ene-thiol reaction, a solvent may be used as necessary.

[0135] Examples of the solvent that can be used include alcohols such as methanol, ethanol, isopropanol, and tert-butanol; ketones such as acetone and methyl isobutyl ketone; ethers such as dibutyl ether; esters such as ethyl acetate; aromatics such as toluene; and hydrocarbons such as hexane and decane.

[0136] The reaction temperature of the ene-thiol reaction is preferably 0 to 200°C, more preferably 50 to 150°C, from the viewpoint of suppressing the volatilization of the vinyl group-containing organosilicon compound represented by the above formula (7).

[0137] The organopolysiloxane of the present invention is suitably used as an adhesion-improving agent for inorganic substrates such as glass and metal.

[0138] The organopolysiloxane of the present invention can be used as a composition added to various resins and the like.

[0139] The resin is not particularly limited, and examples thereof include polymethyl methacrylate resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, ABS resin, polycarbonate resin, polystyrene resin, epoxy resin, unsaturated polyester resin, melamine resin, diallyl phthalate resin, polyimide resin, polyurethane resin, nylon resin, polyethylene resin, polypropylene resin, polyvinyl chloride resin, fluororesin, etc., and it is particularly preferably used as an additive for epoxy resin.

[0140] The amount of the organopolysiloxane added is not limited as long as the adhesion-improving effect is exhibited, but it is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and further preferably 0.2 to 3% by mass in the composition.

[0141] Furthermore, in the composition of the present invention, other additives may be included as long as the performance of the composition is not impaired. As other additives, curing catalysts, release agents, flame retardants, ion trapping agents, antioxidants, adhesion imparting agents, stress reducing agents, coloring agents, etc. can be listed. As long as the performance of the composition is not impaired, the amount of other additives used is not particularly limited, and preferably accounts for 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and further preferably 0.5 to 5% by mass in the composition.

[0142] Example

[0143] The present invention is described in more detail below with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to these Examples. In the following examples, the average molecular weight represents the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography.

[0144] [Synthesis example 1]

[0145] In a 1L detachable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 786g (4.0 mol) of 3-mercaptopropyltrimethoxysilane (KBM-803 manufactured by Shin-Etsu Chemical Co., Ltd.) and 100g of methanol were placed, and then 63g of 0.5N hydrochloric acid water (3.5 mol of water) was dropped at room temperature. Then, the mixture was stirred at 80°C for 10 hours, and then cooled to room temperature. 3.0g of propylene oxide was dropped, and the mixture was stirred at room temperature for 1 hour. The reaction solution was distilled off under reduced pressure and filtered to obtain 620g of colorless transparent liquid silicone oligomer 1. The silicone oligomer 1 obtained by GPC measurement showed an average molecular weight of 1250 and a mercapto equivalent of 156g / mol, which is represented by the following average composition formula.

[0146] (-C3H6-SH) 1.00 (CH3O) 1.25 SiO 0.875

[0147] [Synthesis example 2]

[0148] In a 1L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 393g (2.0 mol) of 3-mercaptopropyltrimethoxysilane (KBM-803 manufactured by Shin-Etsu Chemical Co., Ltd.), 329g (2.0 mol) of propyltrimethoxysilane (KBM-3033 manufactured by Shin-Etsu Chemical Co., Ltd.), and 100g of methanol were placed, and 63g (3.5 mol of water) of 0.5N hydrochloric acid water was dropped at room temperature. Then, the mixture was stirred at 80°C for 10 hours, and then cooled to room temperature. 3.0g of propylene oxide was dropped, and the mixture was stirred at room temperature for 1 hour. The reaction solution was distilled off under reduced pressure and filtered to obtain 560g of colorless transparent liquid silicone oligomer 2. The silicone oligomer 2 obtained was measured by GPC, and the average molecular weight was 1100, and the mercapto equivalent was 275g / mol, which is represented by the following average composition formula.

[0149] (-C3H6-SH) 0.50 (-C3H7) 0.50 (CH3O) 1.25 S i 0.875

[0150] [Example 1-1]

[0151] In a 1L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 312g (2 moles in terms of mercapto groups) of the oligomer 1 obtained in Synthesis Example 1 and 148g (1.0 mole) of vinyl trimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-1003) were placed, and 0.1g of a peroxy ester compound (Perbutyl O manufactured by NOF Corporation) was added at 90°C, and stirred at 90°C for 3 hours. The reaction solution was distilled off under reduced pressure and filtered to obtain 450g of a colorless transparent liquid organopolysiloxane (i). The organopolysiloxane (i) obtained was measured by GPC, and the result showed that the average molecular weight was 1850, the mercapto equivalent was 463g / mole, and it was represented by the following average composition formula.

[0152] (-C3H6-SH) 0.50 (-C3H6-S-C2H4-Si(OCH3)3) 0.50 (CH3O) 1.25 S i 0.875

[0153] [Example 1-2]

[0154] In a 1L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 312g (2 moles in terms of mercapto groups) of the oligomer 1 obtained in Synthesis Example 1 and 74g (0.5 moles) of vinyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-1003) were placed, and then 0.1g of a peroxyester compound (Perbutyl O manufactured by NOF Corporation) was added at 90°C, and stirred at 90°C for 3 hours. The reaction solution was distilled off under reduced pressure and filtered to obtain 380g of a colorless transparent liquid organopolysiloxane (ii). The organopolysiloxane (ii) obtained was measured by GPC, and the result showed that the average molecular weight was 1550, the mercapto equivalent was 257g / mole, and it was represented by the following average composition formula.

[0155] (-C3H6-SH) 0.75 (-C3H6-S-C2H4-Si(OCH3)3) 0.25 (CH3O) 1.25 S i 0.875

[0156] [Examples 1-3]

[0157] In a 1L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 312 g (2 moles in terms of mercapto groups) of the oligomer 2 obtained in Synthesis Example 2 and 66 g (0.5 moles) of vinyl dimethoxymethylsilane (Shin-Etsu Chemical Co., Ltd., KBM-1012) were placed, and then 0.1 g of a peroxy ester compound (Perbutyl O manufactured by NOF Corporation) was added at 90°C, and stirred at 90°C for 3 hours. The reaction solution was distilled off under reduced pressure and filtered to obtain 370 g of a colorless transparent liquid organopolysiloxane (iii). The organopolysiloxane (iii) obtained was measured by GPC, and the average molecular weight was 1500, the mercapto equivalent was 252 g / mole, and it was represented by the following average composition formula.

[0158] (-C3H6-SH) 0.75 (-C3H6-S-C2H4-SiCH3(OCH3)2) 0.25 (CH3O) 1.25 S i 0.875

[0159] [Examples 1-4]

[0160] In a 1L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 312 g (2 moles in terms of mercapto groups) of the oligomer 1 obtained in Synthesis Example 1 and 116 g (0.5 moles) of octenyltrimethoxysilane (KBM-1083, Shin-Etsu Chemical Co., Ltd.) were placed, and 0.1 g of a peroxyester compound (Perbutyl O, manufactured by NOF Corporation) was added at 90°C, and stirred at 90°C for 3 hours. The reaction solution was distilled off under reduced pressure and filtered to obtain 420 g of a colorless transparent liquid organopolysiloxane (iv). The organopolysiloxane (iv) obtained was measured by GPC, and the average molecular weight was 1700, the mercapto equivalent was 285 g / mole, and it was represented by the following average composition formula.

[0161] (-C3H6-SH) 0.75 (-C3H6-S-C8H 16 -Si(OCH3)3) 0.25 (CH3O) 1.25 S i 0.875

[0162] [Examples 1-5]

[0163] In a 1L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 550 g (2 moles in terms of mercapto groups) of the oligomer 2 obtained in Synthesis Example 2 and 74 g (0.5 moles) of vinyl trimethoxysilane (KBM-1003 manufactured by Shin-Etsu Chemical Co., Ltd.) were placed, and 0.1 g of a peroxy ester compound (Perbutyl O manufactured by NOF Corporation) was added at 90°C, and stirred at 90°C for 3 hours. The reaction solution was distilled off under reduced pressure and filtered to obtain 615 g of a colorless transparent liquid organopolysiloxane (v). The organopolysiloxane (v) obtained was measured by GPC, and the average molecular weight was 1300, the mercapto equivalent was 416 g / mole, and it was represented by the following average composition formula.

[0164] (-C3H6-SH) 0.375 (-C3H6-S-C2H4-Si(OCH3)3) 0.125 (-C3H7) 0.50 (CH3O) 1.25 S i 0.875

[0165] [Evaluation of Volatility of Organopolysiloxane]

[0166] The volatility of the organopolysiloxanes (i) to (v) obtained in Examples 1-1 to 1-5, the organosilicon oligomers 1 and 2 obtained in Synthesis Examples 1 and 2, and 3-mercaptopropyltrimethoxysilane (KBM-803 manufactured by Shin-Etsu Chemical Co., Ltd.) was evaluated. As an evaluation method, the mass residual rate (%) of an aluminum dish into which 1 g of the compound was dropped and left to stand in an open system at a constant temperature of 105°C for 3 hours was evaluated as the non-volatile component. The larger the non-volatile component, the lower the volatility of the compound. The evaluation results are shown in Table 1.

[0167] [Table 1]

[0168]

[0169] [Examples 2-1 to 2-5, Comparative Examples 2-1 to 2-3]

[0170] The organopolysiloxanes (i) to (v) obtained in Examples 1-1 to 1-5, the organosilicon oligomers 1 and 2 obtained in Synthesis Examples 1 and 2, and 3-mercaptopropyltrimethoxysilane (KBM-803 manufactured by Shin-Etsu Chemical Co., Ltd.) were added to an epoxy resin (YDPN638 manufactured by Nippon Steel & Sumigin Chemical Co., Ltd., catalyst: 2-methylimidazole) in the amounts shown in Table 2 to prepare a composition.

[0171] Each composition obtained above was applied to a glass plate with a bar coater to a thickness of 10 μm, and cured at 150° C. for 1 hour to prepare a cured film. The obtained cured film was subjected to a cross-cut peel test according to JIS K 5400, and the adhesion was evaluated as (the number of cross-cuts remaining after the peel test) / 100.

[0172] [Table 2]

[0173]

[0174] As shown in Tables 1 and 2, it is understood that the organopolysiloxane of the present invention has low volatility and imparts excellent adhesion when added to a resin such as an epoxy resin.

Claims

1. An organopolysiloxane having: an organic group containing a trialkoxysilyl group, an organic group containing a dialkoxymethylsilyl group, or both; and An organic group containing a mercapto group.

2. The organopolysiloxane according to claim 1, which is represented by the following average composition formula (1): (A) a (B) b (C) c (D) d SiO (4-a-b-c-d) / 2 (1) In the formula, A represents an organic group containing a mercapto group, B represents an organic group containing a trialkoxysilyl group or an organic group containing a dialkoxymethylsilyl group, C represents a hydrolyzable group, D represents an alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and a, b, c, and d represent numbers satisfying 0<a<1, 0<b<1, 0<c<3, 0≤d<1, and 0<a+b+c+d<4.

3. The organopolysiloxane according to claim 2, wherein The organic group containing a mercapto group is represented by the following formula (2): *-(CH2) m -SH(2) In the formula, m represents an integer of 1 to 10, *- represents a bonding end, The trialkoxysilyl-containing organic group or dialkoxymethylsilyl-containing organic group is represented by the following formula (3): *-(CH2) m -S-(CH2) n -Si(CH3) 3-k (OR 1 ) k (3) In the formula, m represents an integer of 1 to 10, n represents an integer of 1 to 10, k represents 2 or 3, and R 1 Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, *- represents a bonding end, The hydrolyzable group is represented by the following formula (4): *-OR 1 (4) In the formula, R 1 It has the same meaning as above, and *- indicates a bonding end.

4. The method for producing an organopolysiloxane according to any one of claims 1 to 3, wherein A hydrolysis condensate of a mercapto group-containing organosilicon compound represented by the following formula (5) is reacted with an alkenyl group-containing organosilicon compound represented by the following formula (7), [Chemistry 1] In the formula, R 1 each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, y represents an integer of 1 to 3, m represents an integer of 1 to 10, Me represents a methyl group, [Chemistry 2] In the formula, R 1 represents the same meanings as above, k represents an integer of 0 to 8, z represents 2 or 3, and Me represents a methyl group.

5. The method for producing an organopolysiloxane according to any one of claims 1 to 3, wherein A co-hydrolysis condensate of a mercapto group-containing organosilicon compound represented by the following formula (5) and an organosilicon compound represented by the following formula (6) is reacted with an alkenyl group-containing organosilicon compound represented by the following formula (7), [Chemistry 3] In the formula, R 1 each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, Me represents a methyl group, [Chemistry 4] (R 1 About) z -Si-R 3 4-z (6) In the formula, R 1 Means the same as above, R 3 represents an alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and z represents an integer of 1 to 4, [Chemistry 5] In the formula, R 1 represents the same meanings as above, k represents an integer of 0 to 8, z represents 2 or 3, and Me represents a methyl group.

6. A composition comprising the organopolysiloxane according to any one of claims 1 to 3.

Images