JPH1095818A - Resin composition and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polysiloxane-vinyl polymer composite resin compsn. which is useful for coating materials, high-impact resins, etc., by utilizing the redistribution reaction of a polysiloxane. SOLUTION: This polysiloxane-vinyl polymer composite resin compsn. is obtd. by subjecting a monomer mixture comprising a vinyl monomer having a silyl group represented by the formula (wherein R<2> is 1-10C alkyl, aryl, or aralkyl ; X is halogen, alkoxy, hydroxy, acyloxy, phenoxy, thioalkoxy, or amino; and c is 0-2). and other copolymerizable vinyl monomers to free-radical emulsion polymn. in an aq. dispersion of a polyorganosiloxane compd. represented by the mean compsn. formula: R<1> a Si(OH)b O(4-a-b)/2 [wherein R<1> is 1-10C alkaryl or aralkyl; 0<a<4; and 0<b<4 provided 0<(a+b)<4] and subjecting the resultant product to redistribution reaction in an acidic state with a pH of 5.0 or lower.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a composite resin composition useful as a coating material, an impact-resistant resin, and the like, and a method for producing the same.

[0002]

2. Description of the Related Art Hitherto, as a method of compounding a polysiloxane and a vinyl polymer, a compound involved in vinyl polymerization has been introduced into the polysiloxane, followed by vinyl polymerization. For example, there has been proposed a method of copolymerizing another vinyl monomer in a polysiloxane having a vinyl group (Japanese Patent Publication No. 52-12231). A method using a methacrylo group instead of a vinyl group in the same manner (Japanese Patent Publication No. 6-29303) is also proposed. As another method, a method using a mercapto group-containing polysiloxane utilizing a chain transfer reaction of radical polymerization (US Pat. No. 407157)
No. 7) is also presented.

[0003]

According to the method described in Japanese Patent Publication No. 52-12231, since the copolymerization ratio of vinyl group and vinyl monomer in polysiloxane is low, there is not enough space between polysiloxane and vinyl monomer. No good bond has been obtained. Special fairness
No. 6-29303 describes a means for improving the copolymerizability, in which the copolymerization ratio is high, but the graft ratio is 80%.
%. U.S. Pat. No. 4,071,577 also fails to produce a sufficient bond between the polysiloxane and the vinyl monomer.

[0004] Further, when these compounds involved in vinyl polymerization are used, it is difficult to control the particle size in an emulsion polymerization system because it is necessary to simultaneously polymerize the polysiloxane and the vinyl monomer.

[0005]

Means for Solving the Problems The present inventors have made intensive studies on the above problems, and as a result, have found use of a redistribution reaction of polysiloxane. The redistribution reaction of polysiloxane is generally known in which the presence of a silanol-terminated polysiloxane in an acid causes an equilibrium reaction of cleavage and formation of SiOSi bonds. When a compound having an alkoxysilyl group or a siloxane bond is present during the redistribution reaction of the polysiloxane, the compound is incorporated into the polysiloxane. When the reaction is applied to a polymer, a redistribution reaction of the polysiloxane occurs during the formation of the vinyl polymer having a hydrolyzable silyl group or a siloxane bond, or after the formation, to form a hydropolymer having a bond already in the vinyl polymer. Degradable silyl or siloxane groups are homogeneously incorporated into the polysiloxane. It has been found that this method produces a more efficient bond between the polysiloxane and the vinyl polymer as compared to the prior art.
That is, the present invention provides an aqueous dispersion of a polyorganosiloxane compound represented by the average composition of the formula (I):
R ¹ _a Si (OH) _b O _{(4-ab) / 2} (I) (wherein, R ¹ is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group, and an aralkyl group) , A is 0 <a <4 and b is 0 <b <4, where 0 <a + b
<4. (A) a vinyl monomer having a silyl group represented by the following general formula (II): (Wherein, R ² is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group, and an aralkyl group, X is a halogen atom, or an alkoxy group, a hydroxy group, an acyloxy group, a phenoxy group, A group selected from a thioalkoxy group and an amino group, and c is an integer of 0 to ^{2. When} each of X and R ² bonded to Si is two or more, they may be the same group.) B) A polysiloxane-vinyl polymer composite resin composition obtained by radical emulsion polymerization of a mixture of other copolymerizable vinyl monomers and redistribution reaction in an acidic state of pH 5.0 or less. (Claim 1) A mixture of a polyorganosiloxane compound and a vinyl monomer ((A) + (B)) is in a weight ratio of 1:99 to 95: 5 in 100 parts by weight of a mixture of (A) and (B). 2. The polysiloxane-vinyl polymer composite resin composition according to claim 1, wherein (A) is 0.5 to 50 parts by weight.
(Claim 2) The polysiloxane-vinyl polymer composite resin composition according to any one of claims 1 to 2, which is obtained by performing a redistribution reaction in an acidic state of pH 2 to 4. (Claim 3) A mixture of vinyl monomers (A) and (B) is subjected to radical emulsion polymerization in an acidic aqueous dispersion of a polyorganosiloxane compound represented by the average composition of the formula (I). Claim 1 obtained
4. The polysiloxane-vinyl polymer composite resin composition according to any one of claims 1 to 3. (Claim 4) In a neutral aqueous dispersion of a polyorganosiloxane compound represented by the average composition of formula (I), a mixture of vinyl monomers (A) and (B) is subjected to radical emulsion polymerization, Then, the polysiloxane-vinyl polymer composite resin composition according to any one of claims 1 to 3, which is obtained by making the composition acidic. (Claim 5) In an aqueous dispersion of the polyorganosiloxane compound represented by the average composition of the formula (I), R ¹ _a Si (O
H) _b O _{(4-ab) / 2} (I) (wherein, R ¹ is a monovalent hydrocarbon group selected from an alkyl group, an aryl group and an aralkyl group having 1 to 10 carbon atoms, and a is 0 < a <4, b is 0 <b <4, where 0 <a + b
<4. (A) a vinyl monomer having a silyl group represented by the following general formula (II): (Wherein, R ² is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group, and an aralkyl group, X is a halogen atom, or an alkoxy group, a hydroxy group, an acyloxy group, a phenoxy group, A group selected from a thioalkoxy group and an amino group, and c is an integer of 0 to ^{2. When} each of X and R ² bonded to Si is two or more, they may be the same group.) B) Production of a polysiloxane-vinyl polymer composite resin composition, which comprises subjecting a mixture of other copolymerizable vinyl monomers to radical emulsion polymerization and redistribution reaction in an acidic state of pH 5.0 or less. Method. (Claim 6) A mixture of a polyorganosiloxane compound and a vinyl monomer ((A) + (B)) is in a weight ratio of 1:99 to 95: 5, and is in 100 parts by weight of a mixture of (A) and (B). The method for producing a polysiloxane-vinyl polymer composite resin composition according to claim 6, wherein (A) is 0.5 to 50 parts by weight. (Claim 7) The method for producing a polysiloxane-vinyl polymer composite resin composition according to any one of claims 6 to 7, which is obtained by performing a redistribution reaction in an acidic state of pH 2 to 4. (Claim 8) A radical emulsion polymerization of a mixture of monomers containing (A) and (B) in an acidic aqueous dispersion of a polyorganosiloxane compound represented by the average composition of the formula (I) A method for producing the polysiloxane-vinyl polymer composite resin composition according to any one of claims 6 to 8. (Claim 9) In a neutral aqueous dispersion of a polyorganosiloxane compound represented by the average composition of formula (I), a mixture of monomers containing (A) and (B) is subjected to radical emulsion polymerization, The method for producing a polysiloxane-vinyl polymer composite resin composition according to any one of claims 6 to 8, which is obtained by subsequently bringing the composition into an acidic state. (Claim 10)

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION [Aqueous Dispersion of Compound Having Siloxane Terminal Siloxane Unit] R ¹ _a Si (OH) _b O _{(4-ab) / 2} (I) wherein R ¹ is A monovalent hydrocarbon group selected from an alkyl group, an aryl group and an aralkyl group having 1 to 10 carbon atoms, a is 0 <a <4, b is 0 <b <4, and 0 <a + b
<4. The aqueous dispersion of the polyorganosiloxane compound represented by the average composition of the formula (I) can be prepared by mechanically stirring the existing polysiloxane compound with a surfactant or by emulsion polymerization of a cyclic low-molecular siloxane compound. can get.

The emulsification of the polysiloxane compound with a surfactant can be performed by a known method. Examples of the surfactant that can be used in the present invention include various nonionic and ionic surfactants. For example, the following can be used as the nonionic surfactant. Alkyl allyl ethers such as polyoxyethylene nonylphenyl ether and polyoxyethylene octyl phenyl ether; alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene oleyl ether and polyoxyethylene stearyl ether; polyoxyethylene laurate and poly Alkyl esters such as oxyethylene stearate; sorbitan derivatives such as sorbitan laurate, sorbitan palmitate and sorbitan stearate can be used.

The ionic surfactants include sodium oleate, sodium lauryl sulfonate,
Sulfonates such as sodium dodecylbenzenesulfonate and sodium isooctylbenzenesulfonate; Ne
wcol-560SN, Newcol-560SF (Nippon Emulsifier Co., Ltd.)
Made), Emar NC-35, Reveil WZ (or more, Kao Corporation)
Newcol-707SF, Newcol-707SN, Newcol-7
Polyoxyethylene allyl ether sulfate such as 23SF, Newcol-740SF; octylphenoxyethoxyethylsulfonate such as Newcol-861SE; Newcol-1305S
Anionic surfactants having a polyoxyethylene chain such as polyoxyethylene dodecyl ether sulfate (hereinafter, manufactured by Nippon Emulsifier Co., Ltd.) such as N are exemplified.

In the emulsion polymerization of a cyclic low-molecular siloxane compound, the ring is opened using a strong acid or strong alkali as a catalyst in an emulsified dispersion system to obtain an aqueous dispersion of a polysiloxane having a silanol group at the terminal end. This method is also known (Japanese Patent Publication No. 41-1)
3995, Japanese Patent Publication No. 44-20116), which is widely used. Examples of usable cyclic low molecular siloxane compounds include:
Hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and other 6-membered, 8-membered, and 10-membered ring compounds, and a large number of compounds having various organic groups other than methyl groups are commercially available. As a method for introducing the structure of SiO _1.5 (T) SiO ₂ (Q) units into polysiloxane, trialkoxysilanes such as methyltrimethoxysilane, phenyltrimethoxysilane, and ethyltrimethoxysilane, and tetramethoxysilane And can be easily synthesized by coexisting tetraalkoxysilanes such as tetraethoxysilane. These compounds are pre-emulsified by a homogenizer or the like and heated and stirred in an acidic state to easily obtain a stable aqueous dispersion of a polysiloxane having a silanol group at a terminal. [Silyl group-containing vinyl monomer (A)]
Vinyl monomer (A) having a silyl group represented by I)
Although not limited to, specific examples include CH ₂ CHCHSiCl ₃ , CH ₂ CHCHSi (CH ₃ ) Cl ₂ , CH ₂ CHCHCOO (CH ₂ ) ₃ SiCl ₃ , and CH ₂ CHCHCOO (CH ₂ ) ₃ Si _{(CH 3) Cl 2, CH} 2 = C (CH 3) COO (CH 2) 3 SiCl 3, CH 2 = C (CH 3) COO (CH 2) 3 Si (CH 3) Cl 2, CHCH 2 = CHSi _{(OCH 3) 3, CH 2} = CHSi (CH 3) (OCH 3) 2, CH 2 = CHSi (OC 2 H 5) 3, CH 2 = CHSi (CH 3) (OC 2 H 5) 2, CH 2 _{= CHSi (0C 3 H 7)} 3, CH 2 = CHSi (Oiso-C 3 H 7) 3, CH 2 = CHSi (OC 4 H 9) 3, CH 2 = CHSi (Oiso-C 4 H 9) 3, _{CH 2 = CHSi (Osec-C} 4 H 9) 3, CH 2 = CHSi (OC 6 H 13) 3, CH 2 = CHSi (OC 8 H 17) 3, CH 2 = CHSi (OC 10 H 21) 3, _{CH 2 = CHSi (OC 12 H} 25) 3, CH 2 = CHCOO (CH 2) 3 Si (OCH 3) 3, CH 2 = CHCOO (CH 2) 3 Si (CH 3) (OCH 3) 2, CH 2 _{= C (CH 3) COO (} CH 2) 3 Si (OCH 3) 3, CH 2 = C (CH 3) COO (CH 2) 3 Si (CH 3) (OCH 3) 2, CH 2 = CHCH 2 OCO (ort-C ₆ H ₄ ) COO (CH ₂ ) ₃ Si (CH ₃ ) ₃ , CH ₂ = CHCH ₂ OCO (ort-C ₆ H ₄ ) COO (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) _2, CH _{2 C (CH 3) COO (CH} 2) 3 Si (OC 2 H 5) 3, CH 2 = C (CH 3) COO (CH 2) 3 Si (CH 3) (OC 2 H 5) 2, CH 2 = _{CH (CH 2) 4 Si (} OCH 3) 3, CH 2 = CH (CH 2) 8 Si (OCH 3) 3, CH 2 = CHO (CH 2) 3 Si (OCH 3) 3, CH 2 = CHOCO ( _{CH 2) 10 Si (OCH 3} ) 3, CH 2 = CH (pC 6 H 4) 4 Si (OCH 3) 3, CH 2 = C (CH 3) COO (CH 2) 2 O (CH 2) 3 Si (CH ₃ ) (OCH ₃ ) ₂ and CH ₂ CC (CH ₃ ) COO (CH ₂ ) ₁₁ Si (OCH ₃ ) ₃ .

[0010] These silyl group-containing vinyl monomers are
One type may be used alone, or two or more types may be used in combination. Silyl group-containing vinyl monomer (A) is 0.5 to 5 parts by weight of the mixture of vinyl monomers (A) and (B) used.
0 parts by weight, preferably 0.5 to 30 parts by weight are copolymerized. 0.5
If the amount is less than 5 parts by weight, it is difficult to obtain a sufficient bond between the polysiloxane portion and the vinyl polymer portion. If the amount exceeds 50 parts by weight, the emulsion becomes unstable and gels during polymerization, which is not preferable. Hereinafter, the number of parts indicates parts by weight. [Vinyl monomer (B) copolymerizable with vinyl monomer having silyl group] There is no limitation on vinyl monomer (B) copolymerizable with vinyl monomer having silyl group. But methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, t-butyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth)
(Meth) acrylate monomers such as acrylate, 2-ethylhexyl (meth) acrylate, isodecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, and isobonyl methacrylate; styrene, α-methylstyrene, chlorostyrene, 4- Aromatic hydrocarbon vinyl monomers such as hydroxystyrene and vinyl toluene; nitrile group-containing vinyl monomers such as (meth) acrylonitrile; epoxy group-containing vinyl monomers such as glycidyl (meth) acrylate; butadiene; Conjugated diene compounds such as isoprene and chloroprene; polyfunctional alkenyl compounds such as allyl methacrylate, divinylbenzene and ethylene glycol dimethacrylate; olefins such as ethylene and propylene; (meth) acrylic Α, β-ethylenically unsaturated carboxylic acids such as luic acid, maleic acid, itaconic acid, crotonic acid, fumaric acid, citraconic acid; 2-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- Hydroxyethyl vinyl ether, hydroxystyrene, ARONIX 5700 (manufactured by Toa Gosei Chemical Co., Ltd.), p
laccelFA-1, placcelFA-4, placcelFM-1, placcelFM-4
(Daicel Chemical Co., Ltd.), HE-10, HE-20, HP-1
0, HP-20 (Nippon Shokubai Chemical Co., Ltd.), Plemmer PEP Series, Plemmer NKH-5050, Plemmer GLM (Nippon Yushi Co., Ltd.)
), Hydroxyl-containing vinyl-based monomers such as hydroxyl-containing vinyl-modified hydroxyalkylvinyl-based monomers; dialkylaminoalkyl methacrylates and dialkylaminoalkyls such as dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl methacrylate and its hydrochloride Methacrylate hydrochloride; Fullermer PE-90, PE-200, PE-350, PME-100, PME-
200, PME-400, AE-350 (manufactured by NOF Corporation), MA-3
0, MA-50, MA-100, MA-150, RA-1120, RA-2614, RMA-56
4, RMA-568, RMA-1114, MPG130-MA (all manufactured by Nippon Emulsifier Co., Ltd.), Fullermer PP-1000, PP-500, PP-800, AP-400
Vinyl monomers having a polyoxyethylene chain or a polyoxypropylene chain, such as (Nippon Yushi Co., Ltd.) and RS-30 (manufactured by Sanyo Chemical Industries, Ltd.); hexafluoropropylene, chlorotrifluoroethylene, Vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, pentafluoropropylene, trifluoro (meth) acrylate, pentafluoro (meth) acrylate, perfluorocyclohexyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl methacrylate ,
Fluorine-containing vinyl monomers such as β- (perfluorooctyl) ethyl (meth) acrylate; hydroxyalkyl esters of α, β-ethylenically unsaturated carboxylic acids such as hydroxyalkyl esters of (meth) acrylic acid; Vinyl compounds as condensation products with phosphoric acid or phosphoric esters or vinyl monomers such as (meth) acrylates containing urethane or siloxane bonds;
AS-6 and AN, macromonomers manufactured by Toa Gosei Chemical Co., Ltd.
-6, AA-6, AB-6, AK-5, etc., vinyl methyl ether, vinyl chloride, vinylidene chloride, chloroprene, polymerized light stabilizer such as LA87, LA82, LA22 manufactured by Asahi Denka Kogyo Co., Ltd. , Polymerization type UV absorbers, other vinyl monomers,
And the like.

The weight ratio of the mixture of the polysiloxane component and the vinyl monomer ((A) + (B)) or the vinyl polymer component is preferably 1:99 to 95: 5, but is preferably 5: 5 to 5: 5.
95-75: 25 is more preferred. As the emulsion polymerization method, for example, a vinyl monomer (A) in an aqueous dispersion of polysiloxane,
It can be obtained by subjecting the mixture of (B) to radical emulsion polymerization. As a method for supplying the monomer, any of the commonly used emulsion polymerization methods such as batch addition of a monomer, timely addition, and timely addition of a monomer emulsion can be used.
Considering the control of the particle size and the timing of the redistribution reaction, the timely addition of the monomer is preferable. In the case of timely addition, the site of polymerization of the added monomer is considered to be in the polysiloxane particles due to the absence of the emulsifier required for micelle formation.
Polymerization proceeds, and the obtained particles are considered to have polysiloxane and vinyl polymer in the same particles.
It is believed that this allows for the creation of a uniform bond of polysiloxane and vinyl polymer in the subsequent redistribution reaction.

In addition, in addition to the surfactant emulsifying the polysiloxanes during polymerization, other ionic systems such as new particles are not generated to further stabilize the emulsion polymerization of vinyl monomers. It is also possible to add a nonionic surfactant. Specific examples of the ionic surfactant include sulfonate salts such as sodium oleate, sodium lauryl sulfonate, sodium decylbenzenesulfonate, and sodium isooctylbenzenesulfonate;
Newcol-560SN, Newcol-560SF or higher, Nippon Emulsifier Co., Ltd.
Newcol-707SF, Newcol-707SN, Newcol-723SF, Ne) Polyoxyethylene nonyl phenyl ether sulfates such as Emar NC-35 and Rezell WZ (all manufactured by Kao Corporation)
Polyoxyethylene allyl ether sulfate such as wcol-740SF; octylphenoxyethoxyethylsulfonate such as Newcol-861SE; polyoxyethylene tridecyl ether sulfate such as Newcol-1305SN (all manufactured by Nippon Emulsifier Co., Ltd.) And an anionic surfactant having a polyoxyethylene chain.

Examples of the nonionic surfactant include polyoxyethylenes such as polyoxyethylene nonylphenyl ether and polyoxyethylene lauryl ether;
Non-ionic surfactants containing silicon, such as 7, L-720, L-5410, L-7602, and L-7607 (all manufactured by Union Carbite Corp.) are typical examples. As the polymerization initiator, organic peroxides, hydrogen peroxide, persulfates, inorganic peroxides, organic azo compounds such as azobisvaleronitrile or V-50, V-59 manufactured by Wako Pure Chemical, redox-based A general radical polymerization initiator such as a catalyst can be used.

Examples of the redox catalyst include potassium persulfate, ammonium persulfate and sodium acid sulfite, a combination of Rongalite, a combination of hydrogen peroxide and ascorbic acid, t-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide, p -A combination of an organic peroxide such as menthane hydroperoxide and sodium acid sulfite, Rongalite, or the like is used. In particular, a combination of an organic peroxide and a reducing agent is preferable in that polymerization can be stably performed. In order to stably obtain a catalytic activity, a compound containing a divalent iron ion such as iron sulfate and a chelating agent such as a sodium salt of ethylenediaminetetraacetic acid, for example, disodium ethylenediaminetetraacetate may be appropriately used.

The amount of the initiator used is preferably from 0.01 to 10%, more preferably from 0.05 to 10%, based on the weight of all monomers.
5%. It is also possible to add a chain transfer agent to adjust the molecular weight of the polymer obtained by polymerization. Examples of the chain transfer agent include mercaptan, sulfidebenzene, isopropylbenzene, chloroform, carbon tetrachloride, and ferric chloride. Among mercaptans, n-dodecyl mercaptan, t-dodecyl mercaptan, n-butyl mercaptan, in terms of price, odor and efficiency
γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, and γ-mercaptopropylmethyldiethoxysilane are preferred.

It is also possible to cause a redistribution reaction of the polysiloxane chains in the obtained polysiloxane-vinyl polymer composite by maintaining the system in an acidic state after completion of the polymerization. By the redistribution reaction, the polysiloxane compound existing before the vinyl polymerization and the hydrolyzable silyl group connected to the vinyl polymer chain after the vinyl polymerization, or the siloxane bond of the hydrolysis condensate is homogenized, so that the polysiloxane and the vinyl polymer A reliable covalent bond is formed. When the system is not acidified, self-condensation of the hydrolyzable silyl group in the vinyl polymer mainly occurs, resulting in a crosslinked product of substantially only the vinyl polymer. In addition, the condensation reaction between the terminal silanol group of the existing polysiloxane and the hydrolyzable silyl group of the vinyl polymer side chain is disadvantageous in terms of stericity due to the small amount of the polysiloxane terminal, so that the polysiloxane as described in the present invention is used. Almost no bond between the polymer and the vinyl polymer is seen.

The terminal of the polysiloxane can be blocked by the presence of a trimethylsiloxy derivative such as hexamethyldisiloxane or methoxytrimethylsilane in the acidic state. It is possible to control the molecular weight of the polysiloxane by this end blocking,
It is also possible to arbitrarily set the crosslinking density of the siloxane-vinyl polymer composite.

The acidic state is preferably a pH of 2 to 5. If the pH is less than 2, the decomposition of the vinyl polymer and the stability of the protective layer are liable to cause coagulation of the composite emulsion, and if the pH is 5 or more, the efficiency of the redistribution reaction of the polysiloxane tends to be extremely low. Not preferred. Examples of the compound to be in an acidic state include sulfonic acids such as fatty acid sulfonic acid and fatty acid-substituted benzenesulfonic acid;
Inorganic acids such as sulfuric acid, hydrochloric acid, and nitric acid; One of these compounds may be used alone, or two or more of them may be used in combination.

[0019]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited by these examples. (Synthesis Example 1) (Synthesis of Polysiloxane Aqueous Dispersion 1) Octamethylcyclotetrasiloxane (100 parts), dodecylbenzenesulfonic acid (2 parts), and deionized water (300 parts) were pre-emulsified with a homogenizer to obtain an octamethylcyclotetrasiloxane emulsion. A liquid was obtained. An emulsion of octamethylcyclotetrasiloxane was charged into a 1 L reactor equipped with a stirrer, a reflux condenser, and a nitrogen gas inlet tube, and reacted at 80 ° C. for 6 hours. The polymerization rate of the obtained polysiloxane was 90%, and the average particle size of the aqueous polysiloxane dispersion was 0.10 μm.

(Synthesis Example 2) (Polysiloxane aqueous dispersion 2)
Synthesis of 100 parts of octamethylcyclotetrasiloxane, 2.5 parts of dodecylbenzenesulfonic acid and 300 parts of deionized water were pre-emulsified with a homogenizer to obtain an octamethylcyclotetrasiloxane emulsion. An emulsion of octamethylcyclotetrasiloxane was charged into a 1 L reactor equipped with a stirrer, a reflux condenser, and a nitrogen gas inlet tube, and reacted at 80 ° C. for 6 hours. The polymerization rate of the obtained polysiloxane was 89%, and the average particle size of the aqueous polysiloxane dispersion was 0.08 μm.

(Synthesis Example 3) (Polysiloxane aqueous dispersion 3)
Synthesis of 100 parts of octamethylcyclotetrasiloxane, 1.8 parts of dodecylbenzenesulfonic acid and 300 parts of deionized water were pre-emulsified with a homogenizer to obtain an octamethylcyclotetrasiloxane emulsion. An emulsion of octamethylcyclotetrasiloxane was charged into a 1 L reactor equipped with a stirrer, a reflux condenser, and a nitrogen gas inlet tube, and reacted at 80 ° C. for 6 hours. The polymerization rate of the obtained polysiloxane was 87%, and the average particle size of the aqueous polysiloxane dispersion was 0.12 μm. (Synthesis Example 4) (Synthesis of Polysiloxane Aqueous Dispersion 4) Octamethylcyclotetrasiloxane 95 parts, methyltrimethoxysilane 5 parts, dodecylbenzenesulfonic acid 2
Parts, 300 parts of deionized water are pre-emulsified with a homogenizer,
An emulsion of octamethylcyclotetrasiloxane was obtained.
1L equipped with a stirrer, reflux condenser and nitrogen gas inlet
Was charged with an emulsion of octamethylcyclotetrasiloxane and reacted at 80 ° C. for 6 hours. The polymerization rate of the obtained polysiloxane was 88%, and the average particle size of the aqueous polysiloxane dispersion was 0.10 μm. (Synthesis Example 5) (Synthesis of Polysiloxane Aqueous Dispersion 5) 100 parts of silanol-terminated polysiloxane (PS341 manufactured by Chisso Corporation), 10 parts of nonionic surfactant (NP720 manufactured by Nippon Emulsifier Co., Ltd.), 10 parts 100 parts of ionic water were mixed and treated three times with a high-pressure homogenizer to obtain a stable emulsion. Further, 200 parts of deionized water was added to obtain a 25% solid polysiloxane emulsion. The average particle diameter of the aqueous polysiloxane dispersion was 0.20 μm. (Synthesis Example 6) (Synthesis of Polysiloxane Aqueous Dispersion 6) 95 parts of octamethylcyclotetrasiloxane, 5 parts of γ-methacryloxypropylmethyldimethoxysilane, 2 parts of dodecylbenzenesulfonic acid, and 300 parts of deionized water were mixed with a homogenizer. The emulsion was emulsified to obtain an emulsion of octamethylcyclotetrasiloxane. An emulsion of octamethylcyclotetrasiloxane was charged into a 1 L reactor equipped with a stirrer, a reflux condenser, and a nitrogen gas inlet tube, and reacted at 80 ° C. for 6 hours. The polymerization rate of the obtained polysiloxane is 85%,
The average particle diameter of the aqueous polysiloxane dispersion was 0.12 μm.

Table 1 shows the synthesis example 1 of the aqueous polysiloxane dispersion.
6 shows the results of polymerization.

[0023]

[Table 1]

(Production Example 1 of Polysiloxane-Vinyl Polymer Composite Resin) Examples 1 to 11 and Comparative Examples 1 to 2 Synthesized in a 1 L reactor equipped with a stirrer, a reflux condenser, a nitrogen gas inlet tube and a dropping funnel The polysiloxane aqueous dispersion, deionized water, Rongalit, and Fe / EDTA aqueous solution in the number of parts shown in Table 2 were charged and heated to 50 ° C. with stirring. After the temperature was raised, a mixed solution in which cumene hydroperoxide was dissolved in the number of monomers shown in Table 2 was continuously added from a dropping funnel over 4 hours. After the completion of the addition, polymerization was carried out for 2 hours, followed by cooling to room temperature. After cooling, the pH was measured.
Was ~ 4.6. In addition, dodecylbenzenesulfonic acid
A 0% aqueous solution was added to pH 2.5, and the mixture was further stirred for 2 hours. (Production Example 2 of Polysiloxane-Vinyl Polymer Composite Resin) Example 12 An aqueous dispersion of 400 parts of a polysiloxane synthesized in a 1 L reactor equipped with a stirrer, a reflux condenser, a nitrogen gas inlet tube and a dropping funnel was removed. 60 parts of ionic water, Rongalite, Fe
/ EDTA aqueous solution was charged, and the temperature was raised to 50 ° C. while stirring.
After the temperature was raised, 200 parts of a mixed solution in which cumene hydroperoxide was dissolved in the monomers shown in Table 2 was continuously added from a dropping funnel over 4 hours. After the completion of the addition, polymerization was carried out for 2 hours, followed by cooling to room temperature. After cooling, the pH was measured to be 6.3. Further, a 10% aqueous solution of dodecylbenzenesulfonic acid was added.
It was added to pH 2.5 and stirred for another 2 hours. (Production Example 3 of Polysiloxane-Vinyl Polymer Composite Resin) Example 13 Water of polysiloxane neutralized to pH 7.5 in advance in a 1 L reactor equipped with a stirrer, a reflux condenser, a nitrogen gas introduction pipe, and a dropping funnel. Charge 400 parts of dispersion, 60 parts of deionized water, Rongalit, Fe / EDTA aqueous solution, and stir at 50 ° C
The temperature rose. After the temperature was raised, 200 parts of a mixed solution in which cumene hydroperoxide was dissolved in the monomers shown in Table 2 was continuously added from a dropping funnel over 4 hours. After the completion of the addition, polymerization was carried out for 2 hours, followed by cooling to room temperature. After cooling, the pH was measured to be 6.0. In addition, 10% of dodecylbensulfonic acid
An aqueous solution was added so as to have a pH of 2.5, and the mixture was further stirred for 2 hours. (Production Example 4 of Polysiloxane-Vinyl Polymer Composite Resin) Comparative Example 3 400 parts of an aqueous dispersion of polysiloxane synthesized in a 1 L reactor equipped with a stirrer, a reflux condenser, a nitrogen gas introduction pipe and a dropping funnel, 60 parts of ionic water, Rongalite, Fe
/ EDTA aqueous solution was charged, and the temperature was raised to 50 ° C. while stirring.
After the temperature was raised, 200 parts of a mixed solution in which cumene hydroperoxide was dissolved in the monomers shown in Table 2 was continuously added from a dropping funnel over 4 hours. After the completion of the addition, polymerization was carried out for 2 hours, followed by cooling to room temperature. The pH after cooling was as in Examples 1 to 11, Comparative Example 1,
As in 2, it was between 4.1 and 4.6. (Production Example 5 of Polysiloxane-Vinyl Polymer Composite Resin) Comparative Example 4 1 L equipped with a stirrer, a reflux condenser, and a nitrogen gas inlet pipe
Aqueous dispersion of polysiloxane 400
, 60 parts of deionized water, and 200 parts of a mixture obtained by dissolving cumene hydroperoxide in a monomer, and stirred for 30 minutes. Thereafter, the temperature was raised to 50 ° C., Rongalit and an aqueous Fe / EDTA solution were added, and the mixture was stirred for 4 hours. The pH after cooling was as in Examples 1-1.
1, as in Comparative Examples 1 and 2, it was between 4.1 and 4.6. (Production Example 6 of Polysiloxane-Vinyl Polymer Composite Resin) Comparative Example 5 Water of polysiloxane previously neutralized to pH 7.5 in a 1 L reactor equipped with a stirrer, a reflux condenser, a nitrogen gas introduction pipe, and a dropping funnel. Charge 400 parts of dispersion, 60 parts of deionized water, Rongalit, Fe / EDTA aqueous solution, and stir at 50 ° C
The temperature rose. After the temperature was raised, 200 parts of a mixed solution in which cumene hydroperoxide was dissolved in the monomers shown in Table 2 was continuously added from a dropping funnel over 4 hours. After the completion of the addition, polymerization was carried out for 2 hours, followed by cooling to room temperature. After cooling, the pH was measured.6.
It was 0. (Evaluation of Toluene Insoluble Content) Examples 1 to 13 and Comparative Examples 1 to
The emulsion obtained in 5 was directly applied onto a polyethylene sheet, and the obtained solid was immersed in toluene for 24 hours, dried at 70 ° C. for 6 hours, and the rate of weight change before and after immersion was calculated. (Measurement of Particle Size) Synthesis Example 1 of Polysiloxane Aqueous Dispersion
6. The particle diameters of the emulsions obtained in Examples 1 to 13 and Comparative Examples 1 to 5 were measured with a Nicomp 370 submicron analyzer. Tables 2 and 3 show Examples 1 to 13 and Table 4 show the monomers used, Comparative Example 1 to 5, the particle diameter after polymerization, and the toluene insoluble content.

[0025]

[Table 2]

[0026]

[Table 3]

[0027]

[Table 4]

(Examples 1 to 13) Aqueous dispersion of polysiloxane, change in type and amount of monomer (A) having silyl group,
Sufficient toluene-insoluble fractions were also obtained by changing various monomer compositions and changing the ratio of polysiloxane to vinyl monomer. (Comparative Example 1) When the amount of the monomer having a silyl group was less than 0.5 part, a sufficient toluene-insoluble content could not be obtained. (Comparative Example 2) When the amount of the monomer having a silyl group exceeded 50 parts, gelation occurred during polymerization, and a stable emulsion could not be obtained. (Comparative Example 3) When a vinyl monomer was polymerized in an aqueous dispersion of a polysiloxane into which a methacryl group was introduced, only the initially added monomer and polysiloxane became toluene-insoluble. (Comparative Example 4) When a vinyl monomer was subjected to batch polymerization in an aqueous dispersion of a polysiloxane into which a methacryl group was introduced, a toluene-insoluble fraction of about 80% was obtained. The particles did not enlarge, and it was considered that new particles were formed only by the vinyl monomer. The formation of the new particles reduced the toluene insoluble content. (Comparative Example 5) When the acidic state was not obtained after the polymerization, the silane portion bonded to the vinyl polymer chain was not sufficiently incorporated into the polysiloxane chain, and the toluene insoluble content was 75%.

[0029]

According to the present invention, there is provided a composition in which a covalent bond is formed between polysiloxane and vinyl polymer with high efficiency and a method for producing the same. It is possible.

Claims (10)

[Claims] In an aqueous dispersion of a polyorganosiloxane compound represented by the average composition of the formula (I), R ¹ _a Si (OH) _b O _{(4-ab) / 2} (I) R ¹ is a monovalent hydrocarbon group selected from an alkyl group, an aryl group and an aralkyl group having 1 to 10 carbon atoms, a is 0 <a <4, b is 0 <b <4, and 0 <a + b
<4. (A) A vinyl monomer having a silyl group represented by the following general formula (II) (Wherein, R ² is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group, and an aralkyl group, X is a halogen atom, or an alkoxy group, a hydroxy group, an acyloxy group, a phenoxy group, A group selected from a thioalkoxy group and an amino group, and c is an integer of 0 to ^{2. When} each of X and R ² bonded to Si is two or more, they may be the same group.) B) A polysiloxane obtained by radical emulsion polymerization of a mixture of other copolymerizable vinyl monomers, and redistribution reaction in an acidic state having a pH of 5.0 or less.
-A vinyl polymer composite resin composition. 2. The weight ratio of the mixture of the polyorganosiloxane compound and the vinyl monomer ((A) + (B)) is 1:99 to 95: 5,
The polysiloxane-vinyl polymer composite resin composition according to claim 1, wherein (A) is 0.5 to 50 parts by weight based on 100 parts by weight of the mixture of (A) and (B). 3. The polysiloxane-vinyl polymer composite resin composition according to claim 1, which is obtained by performing a redistribution reaction in an acidic state of pH 2 to 4. 4. A polyorganosiloxane compound represented by the average composition of the formula (I) in an acidic aqueous dispersion of:
The polysiloxane-vinyl polymer composite resin composition according to any one of claims 1 to 3, which is obtained by radical emulsion polymerization of a mixture of monomers containing (B). 5. In a neutral aqueous dispersion of a polyorganosiloxane compound represented by the average composition of the formula (I), (A)
The polysiloxane-vinyl polymer composite resin composition according to any one of claims 1 to 3, which is obtained by subjecting a mixture of monomers containing (B) to radical emulsion polymerization and then to an acidic state. 6. In a water dispersion of a polyorganosiloxane compound represented by the average composition of the formula (I), R ¹ _a Si (OH) _b O _{(4-ab) / 2} (I) ¹ is a monovalent hydrocarbon group selected from an alkyl group, an aryl group, and an aralkyl group having 1 to 10 carbon atoms, a is 0 <a <4, b is 0 <b <4, and 0 <a + b
<4. (A) A vinyl monomer having a silyl group represented by the following general formula (II) (Wherein, R ² is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group, and an aralkyl group, X is a halogen atom, or an alkoxy group, a hydroxy group, an acyloxy group, a phenoxy group, A group selected from a thioalkoxy group and an amino group, and c is an integer of 0 to ^{2. When} each of X and R ² bonded to Si is two or more, they may be the same group.) B) A method for producing a polysiloxane-vinyl polymer composite resin composition, which comprises subjecting a mixture of other copolymerizable vinyl monomers to radical emulsion polymerization and redistributing the mixture in an acidic state at a pH of 5.0 or less. . 7. The weight ratio of the mixture of the polyorganosiloxane compound and the vinyl monomer ((A) + (B)) is 1:99 to 95: 5,
The method for producing a polysiloxane-vinyl polymer composite resin composition according to claim 6, wherein (A) is 0.5 to 50 parts by weight in 100 parts by weight of the mixture of (A) and (B). 8. The method for producing a polysiloxane-vinyl polymer composite resin composition according to claim 6, which is obtained by performing a redistribution reaction in an acidic state of pH 2 to 4. 9. An aqueous dispersion of a polyorganosiloxane compound represented by the average composition of the formula (I) in an acidic state, wherein (A) and (B)
The polysiloxane according to any one of claims 6 to 8, which is obtained by radical emulsion polymerization of a mixture of monomers containing:
-A method for producing a vinyl polymer composite resin composition. 10. A polyorganosiloxane compound represented by the average composition represented by the formula (I) in a neutral aqueous dispersion: (A)
The method for producing a polysiloxane-vinyl polymer composite resin composition according to any one of claims 6 to 8, wherein the mixture is obtained by subjecting a mixture of monomers containing (B) to radical emulsion polymerization and then to an acidic state.