WO2009104569A1 - Copolymère siliconé greffé et son procédé de production - Google Patents

Copolymère siliconé greffé et son procédé de production Download PDF

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WO2009104569A1
WO2009104569A1 PCT/JP2009/052617 JP2009052617W WO2009104569A1 WO 2009104569 A1 WO2009104569 A1 WO 2009104569A1 JP 2009052617 W JP2009052617 W JP 2009052617W WO 2009104569 A1 WO2009104569 A1 WO 2009104569A1
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silicone
graft copolymer
meth
group
based graft
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PCT/JP2009/052617
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English (en)
Japanese (ja)
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慎哉 神戸
哲也 杉浦
隆之 牧
嘉男 森
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東亞合成株式会社
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Publication of WO2009104569A1 publication Critical patent/WO2009104569A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C08L51/085—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/068—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D151/085—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds on to polysiloxanes

Definitions

  • the present invention relates to a silicone-based graft copolymer and a method for producing the same.
  • a structurally controlled graft copolymer obtained by copolymerizing a macromonomer having a polymerizable group at the end of a molecule with another polymerizable monomer has attracted attention as a high-performance polymer material, It is used for adhesives, polymer additives, molding materials, sealants, etc.
  • the graft copolymer is a silicone polymer that forms branches, and has properties such as water repellency, lubricity, mold release, weather resistance, and stain resistance. It is suitably used as a material coating agent, paint additive, sealing agent, molding material and the like (see Patent Documents 1 and 2).
  • these silicone-based graft copolymers are used as coating agents, they are generally used in the form of organic solvent solutions.
  • organic solvents has problems in terms of safety and environmental pollution. Therefore, an aqueous silicone graft copolymer that can be used in the form of an aqueous solution that is safe and environmentally friendly is desired.
  • a silicone graft copolymer is produced by copolymerizing a silicone-based macromonomer with a polymerizable monomer such as an ethylenically unsaturated carboxylic acid or (meth) acrylic acid ester in an organic solvent.
  • a polymerizable monomer such as an ethylenically unsaturated carboxylic acid or (meth) acrylic acid ester in an organic solvent.
  • a method has been proposed in which a graft copolymer is reacted with a base to make it water-soluble, and then an organic solvent is removed to obtain a silicone-based graft copolymer (see Patent Documents 3 and 4). Yes.
  • a polymer composition containing an aqueous silicone graft copolymer by a combination of a silicone graft copolymer and an amino resin is used to improve the transport speed in the transport of the can manufacturing process, It is known that it can be suitably used as a coating agent that satisfies the required performance such as reduction of scratches on the can surface and is excellent in lubricity, scratch resistance, and adhesion (see Patent Document 5).
  • an aqueous silicone polymer composition containing an organic amine neutralized product of a silicone graft copolymer having a carboxyl group has water resistance, printability, and running property during recording. It is known that it can be suitably used as an excellent coating agent (see Patent Document 6).
  • a graft copolymer having a hydrophilic polymer segment and a hydrophobic polymer segment derived from a silicone-based macromonomer, a block copolymer having a vinyl polymer segment and a silicone polymer segment, or a graft copolymer may be used for inkjet, etc. It has been proposed to improve the water resistance and printing characteristics of printed matter by using it as an additive / dispersant for ink (see Patent Documents 7 and 8).
  • the silicone-based graft copolymer and the aqueous silicone-based block copolymer described in these documents are still insufficient in stability, oil resistance, weather resistance and the like when made into an aqueous solution.
  • the lubricity, scratch resistance, gloss, etc. of the film deteriorated and the required performance may not be satisfied.
  • the object of the present invention is to provide a hydrophobic property derived from a silicone-based polymer that is stably present in a polymerization system during polymerization, and forms a stable aqueous solution by adding a base after the polymerization to neutralize and dissolve in water.
  • a silicone-based graft copolymer having, as a trunk, a polymer having a structural unit derived from a branching unit and a hydrophilic polymerizable monomer, and using this as an additive, a paint / ink containing a pigment For example, a film having sufficient lubricity, scratch resistance and gloss is formed.
  • the objective of this invention is providing the method of manufacturing the said silicone type graft copolymer smoothly with a high polymerization rate and a high yield.
  • a specific (meth) acrylic acid ester, an ethylenically unsaturated carboxylic acid, and a silicone-based macromonomer having a predetermined molecular weight, and optionally other polymerizable monomers such as (meth) acrylic acid alkyl ester A new silicone-based graft copolymer having a specific structure, which is copolymerized with a base, forms a stable aqueous solution when neutralized with a base to make it water-soluble.
  • a polymer composition for aqueous coating is prepared using a copolymer
  • water repellency, lubricity, scratch resistance, mold release, weather resistance, stain resistance, gloss, etc. are obtained from the aqueous coating polymer composition. It is found that a film with excellent properties is formed, and even when the composition is added to a paint or ink containing a pigment such as a coloring material, the performance is maintained at a high rate. It was found to be.
  • the present inventors perform copolymerization in a mixed solvent obtained by mixing two or more kinds of specific organic solvents, thereby producing monomer components and polymerization.
  • a mixed solvent obtained by mixing two or more kinds of specific organic solvents, thereby producing monomer components and polymerization.
  • the monomers used for the polymerization are copolymerized to form hydrophobic branches and hydrophilicity derived from the silicone polymer.
  • a novel silicone-based graft copolymer with a copolymer composition and a narrow molecular weight distribution, which is based on a polymer having a structural unit derived from a polymerizable monomer, can be obtained smoothly with a high polymerization rate and high yield. I found out.
  • the present inventors changed the mixed composition of the mixed solvent during the polymerization step for producing the silicone-based graft copolymer, and maintained the solubility in the mixed solvent of the components present in the polymerization system. It has been found that a silicone-based graft copolymer having a narrower molecular weight distribution can be produced in a higher yield by polymerization, and the present invention has been completed based on these findings.
  • the silicone-based graft copolymer of (1) further having a structural unit derived from a (meth) acrylic acid ester other than the (meth) acrylic acid ester (I); (3) Based on the total mass of all structural units constituting the silicone-based graft copolymer, the content of structural units derived from (meth) acrylic acid ester (I) is 10 to 70% by mass, ethylenically unsaturated The content of the structural unit derived from the carboxylic acid (II) and / or its salt is 5 to 30% by mass, the content of the structural unit derived from the silicone macromonomer (III) is 10 to 50% by mass, and (meth) The silicone-based graft copolymer of (1) or (2) above, wherein the content of structural units derived from (meth) acrylic acid esters other than acrylic acid ester (I) is 0 to 70% by mass; (4) The silicone graft copolymer according to any one of (1) to (3), having a weight average molecular weight of
  • the silicone graft copolymer of the present invention has a silicone polymer portion derived from a silicone macromonomer as a hydrophobic branch, and a polymer having a structural unit derived from a hydrophilic polymerizable monomer as a trunk. Because of its graft structure, it exhibits excellent lubrication performance, mold release performance, water repellency performance, scratch resistance performance, contamination resistance performance, weather resistance performance, and gloss performance by the silicone polymer forming the branches. . These performances are not greatly impaired even in paints and inks containing pigments.
  • the silicone-based graft copolymer of the present invention has a hydrophilic structural unit, particularly a structural unit in which a part or all of the carboxyl group is neutralized with a base to form a salt at the trunk. Therefore, it has excellent solubility in water, and the structural unit derived from (meth) acrylic acid ester (I) generates insoluble components even in an aqueous solution in which many low pH or hydrophilic organic solvents are mixed. It is difficult to add to water-based paints and water-based inks mixed with a large amount of low pH or hydrophilic organic solvents. Further, because of the hydrophilic structural unit, the aqueous polymer solution obtained by dissolving the silicone-based graft copolymer of the present invention in water is excellent in storage stability and does not aggregate or precipitate during storage.
  • the silicone-based graft copolymer of the present invention in which a part or all of the carboxyl groups in the silicone-based graft copolymer is neutralized with a base to be water-solubilized, is a polymer composition for aqueous coating, a sealing agent It can be effectively used for various applications such as molding materials.
  • an aqueous coating polymer composition in which the water-soluble silicone-based graft copolymer of the present invention is dissolved in an aqueous medium has various bases as a coating material excellent in safety and environmentally friendly using water as a medium.
  • structural unit (II) and a structural unit derived from the silicone-based macromonomer (III) [hereinafter sometimes referred to as “structural unit (III)”] are included as essential units. In some cases, it further has structural units derived from other polymerizable monomers.
  • the trunk has structural units (I), structural units (II) and units derived from a polymerizable unsaturated group at one end of the silicone-based macromonomer. Furthermore, it has a structural unit derived from another polymerizable monomer, and a silicone-based polymer that forms the main body of the silicone-based macromonomer is bonded to the trunk as a branch.
  • the branching silicone polymer is bonded to the trunk in a branching manner at the site of copolymerization of the silicone macromonomer (that is, the portion of the silicone macromonomer copolymerized by the polymerizable unsaturated group at one end). Yes.
  • R 1 is a hydrogen atom or a methyl group It is.
  • R 1 is preferably a methyl group, that is, a methacrylic terminal, from the viewpoint of high scratch resistance and good weather resistance.
  • R 2 is an ethylene group or a propylene group.
  • R 2 is preferably an ethylene group from the viewpoint of excellent oil resistance and gloss of the coating.
  • R 3 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms.
  • R 3 is an alkyl group having 1 to 6 carbon atoms, particularly a methyl group or an ethyl group, so that the solubility of the (meth) acrylic acid ester (I) in the mixed solvent during polymerization is improved.
  • the copolymerization with the silicone-based macromonomer is more smoothly performed, and the viscosity of the resulting aqueous solution of the silicone-based graft copolymer is preferably reduced.
  • n is a number from 1 to 25. Among these, n is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 2 to 5.
  • n When n is small, the stability of the aqueous polymer solution tends to be inferior when the aqueous polymer solution has a low pH or a large amount of hydrophilic organic solvent is mixed. When n is larger than 25, The copolymerizability of the polymer deteriorates, and a uniform copolymer cannot be obtained.
  • (meth) acrylic acid ester (I) examples include methoxy (poly) ethylene glycol (meth) acrylate and ethoxy (poly) ethylene, wherein n is any number from 1 to 10 in general formula (I) Glycol (meth) acrylate, propoxy (poly) ethylene glycol (meth) acrylate, butoxy (poly) ethylene glycol (meth) acrylate, pentoxy (poly) ethylene glycol (meth) acrylate, hexoxy (poly) ethylene glycol (meth) acrylate, Methoxy (poly) propylene glycol (meth) acrylate, ethoxy (poly) propylene glycol (meth) acrylate, propoxy (poly) propylene glycol (meth) acrylate, butoxy (poly) propylene glycol (meth) Acrylate, pentoxy (poly) propylene glycol (meth) acrylate, and the like can be illustrated he
  • Commercial products of (meth) acrylic acid ester (I) include “NK Ester M Series” and “NK Ester AM Series” (trade name) manufactured by Shin-Nakamura Chemical Co., Ltd., “Blemmer PME Series” manufactured by Nippon Oil & Fats Co., Ltd.
  • the ethylenically unsaturated carboxylic acid forming the structural unit (II) in the trunk portion of the silicone-based graft copolymer of the present invention can be copolymerized with (meth) acrylic acid ester (I) and a silicone-based macromonomer. Any ethylenically unsaturated carboxylic acid having one or more carboxyl groups can be used.
  • ethylenically unsaturated carboxylic acid examples include (meth) acrylic acid, ethacrylic acid, propylacrylic acid, isopropylacrylic acid, crotonic acid, itaconic acid, fumaric acid, citraconic acid, maleic acid, Maleic anhydride, ⁇ -carboxypolycaprolactone mono (meth) acrylate, ⁇ -carboxypolyalkylene glycol mono (meth) acrylate, various acid anhydride adducts of ⁇ -hydroxymono (meth) acrylate, etc. These 1 type (s) or 2 or more types can be used.
  • the ethylenically unsaturated carboxylic acid is preferably acrylic acid and / or methacrylic acid from the viewpoints of availability, copolymerization with a silicone-based macromonomer, efficiency of introduction of carboxylic acid, and the like.
  • methacrylic acid is particularly preferably used.
  • the silicone-based macromonomer (III) for introducing a branch made of a silicone-based polymer into the silicone-based graft copolymer of the present invention has a polymerizable unsaturated group at one end and has a weight average molecular weight of 5000-35000. This is a silicone polymer.
  • Silicone macromonomer (III) is a linear silicone polymer with lubricity, releasability, water repellency, scratch resistance, stain resistance, weather resistance, and gloss, and is polymerized at one end. Any silicone-based macromonomer having a polymerizable unsaturated group (particularly a polymerizable double bond) may be used.
  • silicone-based macromonomer (III) the following general formula (IIIa): D—O— [Si (R 4 ) (R 5 ) —O] p —X (IIIa)
  • D is a group having a polymerizable unsaturated bond at the terminal (polymerizable unsaturated group)
  • R 4 and R 5 are each independently a monovalent aliphatic hydrocarbon group or a monovalent aromatic hydrocarbon.
  • X represents a substituent having no radical polymerizability
  • p represents the degree of polymerization.
  • a silicone macromonomer represented by the formula is preferably used.
  • the silicone-based macromonomer represented by the above general formula (IIIa), that is, the silicone-based macromonomer having a polymerizable unsaturated group at one end of the silicone-based polymer composed of diorganopolysiloxane is lubricity and releasability. Excellent in terms of chemical stability.
  • R 4 and R 5 are preferably an alkyl group having 1 to 3 carbon atoms and a phenyl group, and particularly preferably a methyl group from the viewpoint of lubricity.
  • the silicone macromonomer (III) is a dimethylpolysiloxane macromonomer in which R 4 and R 5 are both methyl groups and a polymerizable unsaturated group is bonded to one end in the above general formula (IIIa).
  • a diorganopolysiloxane macromonomer in which a part of R 4 and / or R 5 in the dimethylpolysiloxane macromonomer is replaced with an ethyl group, another alkyl group and / or a phenyl group is more preferably used.
  • a dimethylpolysiloxane-based macromonomer in which all of R 4 and R 5 are methyl groups is more preferably used.
  • the polymerizable unsaturated group at one end of the silicone-based macromonomer (III) represents (meth) acrylic acid ester (I), ethylenically unsaturated carboxylic acid (II), Any polymerizable unsaturated group copolymerizable with other polymerizable monomers may be used, but (meth) acrylic acid ester (I), ethylenically unsaturated carboxylic acid (II), other polymerizable monomers
  • a polymerizable unsaturated group having a (meth) acryloyl group at the end is preferable from the viewpoint of copolymerization with a monomer and ease of production of a silicone-based macromonomer.
  • Preferable examples of the polymerizable unsaturated group D at one end of the silicone macromonomer include, for example, those represented by the following general formula (IIId). CH 2 ⁇ C (R 6 ) —COO— (CH 2 ) q — (O) r — (CH 2 ) 3 —Si (R 7 ) (R 8 ) — (IIId) (Wherein R 6 is a hydrogen atom or a methyl group, R 7 and R 8 are alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, acetoxy group, and q is 0 to 0 when r is 0) 2. When r is 1, it is 2, and r is 0 or 1.)
  • the other end of the silicone-based macromonomer (III) [X in the general formula (IIIa)] is a chemical group such as a trialkylsilyl group (for example, trimethylsilyl group, dimethylethylsilyl group, dimethylbutylsilyl group). It is preferable that a stable group is bonded from the viewpoint of the chemical stability of the silicone macromonomer and the graft copolymer. If an active group such as a silanol group, hydroxyl group, epoxy group, amino group, or alkoxy group is bonded to the other end of the silicone-based macromonomer (III), the chemical stability of the silicone-based macromonomer is reduced. It tends to decrease.
  • a trialkylsilyl group for example, trimethylsilyl group, dimethylethylsilyl group, dimethylbutylsilyl group. It is preferable that a stable group is bonded from the viewpoint of the chemical stability of the silicone macromonomer and the graft cop
  • the silicone-based macromonomer (III) constituting the silicone-based graft copolymer of the present invention has a weight average molecular weight of 5,000 to 35,000, preferably 8,000 to 30,000, and particularly preferably 10,000 to 20,000.
  • weight average molecular weight of the silicone-based macromonomer is smaller than the above range, when the silicone-based graft copolymer produced using the silicone-based macromonomer is used as a coating agent, lubricity, releasability, water repellency, A film excellent in scratch resistance, stain resistance and weather resistance is not formed.
  • the weight average molecular weight of the silicone macromonomer is larger than the above range, the copolymerizability with other monomers deteriorates and unreacted monomers (silicone macromonomer and / or other monomers). The polymer) remains, or it is difficult to make the resulting silicone-based graft copolymer water-soluble.
  • the silicone-based graft copolymer is used as a coating agent or the like, the adhesion to the substrate is lowered, and problems such as repellency occur.
  • the weight average molecular weight in this specification refers to the weight average molecular weight determined by gel permeation chromatography using polystyrene as a reference substance.
  • silicone macromonomer (III) only one silicone macromonomer may be used, or two or more silicone macromonomers may be used.
  • Silicone macromonomers that can be used in the present invention include, for example, “AK-5”, “AK-30” and “AK-32” (trade name) manufactured by Toagosei Co., Ltd., “Shin-Etsu Chemical Co., Ltd.” X-22-174DK ",” X-24-8201 ",” X-22-2426 “(trade name), etc., and these commercial products may be used.
  • the method for producing the silicone macromonomer is not particularly limited.
  • the silicone-based macromonomer can be produced by a known method.
  • a living polymer is produced by anionic polymerization of cyclic siloxane using lithium trialkylsilanolate as an initiator, and ⁇ -methacryloxypropyldimethylmono It can be produced by a method in which chlorosilane is reacted (see Patent Document 6), a method in which a terminal silanol group-containing silicone and an organic silicon compound such as ⁇ -methacryloxypropyldimethylmonochlorosilane are subjected to a condensation reaction (Patent Document 1).
  • the silicone-based graft copolymer of the present invention uses only the above-mentioned (meth) acrylic acid ester (I), ethylenically unsaturated carboxylic acid (salt) (II), and silicone-based macromonomer (III). It may be formed, or (meth) acrylic acid ester (I), ethylenically unsaturated carboxylic acid (II) and silicone-based macromonomer (III) together with other polymerizable monomers [hereinafter “others” It may be formed using a polymerizable monomer (IV) ”.
  • the structural unit derived from the other polymerizable monomer (IV) is generally It constitutes the structural unit of the polymer constituting the trunk.
  • silicone-based graft copolymer of the present invention has a structural unit derived from another polymerizable monomer (IV)
  • examples of the other polymerizable monomer (IV) include (meta ) Alkyl ester of acrylic acid, alicyclic hydrocarbon ester of (meth) acrylic acid, hydroxyalkyl ester of (meth) acrylic acid, (meth) acrylamide vinyl, (meth) acrylonitrile, aromatic vinyl compound, sulfonic acid group-containing Monomer, vinyl acetate, N-vinylpyrrolidone and the like can be mentioned.
  • the silicone-based graft copolymer of the present invention can have a structural unit derived from one or more of these other polymerizable monomers.
  • alkyl esters of (meth) acrylic acid that can be used as other polymerizable monomers (IV) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth Butyl acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and the like.
  • alicyclic hydrocarbon esters of (meth) acrylic acid that can be used as other polymerizable monomer (IV) include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and (meth) acrylic acid.
  • Examples thereof include pentenyloxyalkyl and adamantyl (meth) acrylate.
  • sulfonic acid group-containing monomer that can be used as the other polymerizable monomer (IV) include (meth) acrylic acid 2-ethyl sulfonate, styrene sulfonic acid, ⁇ -methyl styrene sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, (meth) allylsulfonic acid, isoprenesulfonic acid, vinyltoluenesulfonic acid, (meth) allyloxybenzenesulfonic acid, (meth) allyloxy-2-hydroxypropylsulfonic acid And (meth) acrylic acid 3-sulfopropyl, itaconate bis (3-sulfopropyl), and the like.
  • the silicone-based graft copolymer of the present invention is a small amount (generally 2 mol% or less, particularly 0.5 mol% or less based on the total number of moles of all monomers constituting the silicone-based graft copolymer). If present, a structural unit derived from a monomer having two or more vinyl groups in one molecule may be included as a structural unit derived from another polymerizable monomer (IV).
  • the monomer having two or more vinyl groups at that time include methylene bisacrylamide, methylene bismethacrylamide, butanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di ( (Meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, di (meth) acryloxyethylene phosphate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, diallyl maleate, poly Examples thereof include crosslinkable monomers such as allyl saccharose.
  • the silicone-based graft copolymer of the present invention has a structural unit derived from another polymerizable monomer (IV), among the polymerizable monomers described above, an alkyl ester of (meth) acrylic acid Particularly, having a structural unit derived from an alkyl ester of methacrylic acid has good copolymerizability with (meth) acrylic acid ester (I), ethylenically unsaturated carboxylic acid and silicone-based macromonomer, and is obtained.
  • the silicone-based graft copolymer film is preferable from the viewpoint that the scratch resistance and weather resistance of the film are more excellent.
  • alkyl ester of (meth) acrylic acid in that case include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate.
  • methyl methacrylate is preferable from the viewpoint of excellent scratch resistance of the coating film.
  • the silicone-based graft copolymer of the invention is excellent in molecular weight distribution, stability of aqueous polymer solution, lubricity of film, release property, water repellency, scratch resistance, stain resistance, weather resistance, etc. It is.
  • the silicone-based graft copolymer of the present invention comprises 10 to 10 structural units (I) derived from (meth) acrylic acid ester (I) based on the total mass of all structural units constituting the silicone-based graft copolymer. 70% by mass, 10-30% by mass of structural unit (II) derived from ethylenically unsaturated carboxylic acid (II) and / or a salt thereof, and 10% of structural unit (III) derived from silicone-based macromonomer (III)
  • the structural unit derived from (meth) acrylic acid ester (I) preferably has a structural unit derived from ⁇ 50% by mass and other polymerizable monomer (IV) in a proportion of 0 to 70% by mass.
  • the silicone-based graft copolymer When the ethylenically unsaturated carboxylic acid (II) is less than 5% by mass, it is difficult to make the silicone-based graft copolymer water-soluble, and when it is more than 35% by mass, the water resistance of the coating is inferior.
  • the silicone-based macromonomer (III) When the silicone-based macromonomer (III) is less than 10% by mass, the film has poor lubricity, releasability, water repellency, scratch resistance, stain resistance, and weather resistance. Stable production of the graft copolymer becomes difficult.
  • the amount of the other polymerizable monomer (IV) When the amount of the other polymerizable monomer (IV) is small, there is a tendency that the scratch resistance of the film is insufficient, and when it exceeds 70% by mass, it is difficult to balance various physical properties.
  • the stability of the silicone-based graft copolymer in the aqueous medium after polymerization during the production of the silicone-based graft copolymer is improved.
  • the lubricity, releasability, water repellency, scratch resistance, stain resistance, weather resistance, and gloss of the coating film of the graft copolymer are further improved.
  • the acid value of the silicone-based graft copolymer (the acid value before neutralizing the carboxyl group in the silicone-based graft copolymer with a base) is in the range of 40 to 200 mgKOH / g. Further, it is preferable to adjust the content ratio of the structural unit (II) derived from the ethylenically unsaturated carboxylic acid so as to be in the range of 60 to 150 mgKOH / g, particularly 80 to 120 mgKOH / g.
  • the acid value of the silicone-based graft copolymer before neutralization with the base is too low, it will be difficult to water-solubilize the silicone-based graft copolymer even if neutralized with a base. If the acid value of the coalescence is too high, the water resistance of the silicone-based graft copolymer film is lowered.
  • Tg glass transition temperature
  • the glass transition temperature of the homopolymer is a value described in POLYMER HANDBOOK (John WILLY & SONNS, INC) It was adopted.
  • the weight average molecular weight of the silicone-based graft copolymer of the present invention is preferably 6000 to 40,000, more preferably 8000 to 30000, and particularly preferably 10,000 to 20000. If the weight average molecular weight of the silicone graft copolymer is too low, the characteristics of the silicone polymer will not be sufficiently exerted, and the film lubricity, releasability, water repellency, scratch resistance, stain resistance, weather resistance Gets worse. Moreover, when the weight average molecular weight of a silicone type graft copolymer is too high, water-solubilization will become difficult, or the viscosity of aqueous solution will become high and handling will become difficult.
  • the molecular weight distribution (Mw / Mn) of the silicone-based graft copolymer is preferably 4.0 or less, more preferably 3.0 or less, and particularly preferably 2.5 or less.
  • the deterioration of physical properties when the molecular weight distribution is large varies depending on the composition, but the stability of the aqueous polymer solution and the scratch resistance of the coating are often reduced.
  • the polymerization is unstable (progresses in a state where it is not uniformly dissolved), the molecular weight distribution tends to be high.
  • the number average molecular weight and the weight average molecular weight of the silicone-based graft copolymer in the present specification are the weight average molecular weight determined by gel permeation chromatography using polystyrene as a reference substance, like the silicone-based macromonomer.
  • the present invention provides a silicone-based graft copolymer in which all of the carboxyl groups are not neutralized, and a silicone-based graft copolymer in which a part or all of the carboxyl groups are neutralized with a base to form a salt. Include.
  • the silicone-based graft copolymer of the present invention in which some or all of the carboxyl groups are neutralized with a base is excellent in solubility in water.
  • the carboxyl groups of the silicone-based graft copolymer are neutralized with a base to form a salt
  • the base used for neutralization inorganic alkali agents such as alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, and organic amines such as diethanolamine and triethanolamine can be used.
  • a method for producing a silicone-based graft copolymer As a method for producing a silicone-based graft copolymer, a macromonomer method, an ionic polymerization method, a method by introducing a side chain by a polymer reaction, and the like are known.
  • the silicone-based graft copolymer of the present invention is produced by adopting a macromonomer method because adjustment is easy and branch portions can be easily connected (bonded) to the trunk portion. That is, (meth) acrylic acid ester (I), ethylenically unsaturated carboxylic acid (II), silicone-based macromonomer (III) having a weight average molecular weight of 5000 to 35000 and optionally other polymerizable monomer (IV).
  • the silicone-based graft copolymer of the present invention is produced by copolymerization in an organic solvent.
  • one or more organic solvents selected from the following group (A) and the following group (B) are used as the organic solvent.
  • Solution polymerization using a mixed solvent obtained by mixing one or two or more organic solvents selected can stabilize both the monomer component used for polymerization and the polymer component generated by the polymerization in the mixed solvent.
  • a silicone graft copolymer having a narrow molecular weight distribution and narrow composition distribution in a dissolved state is preferable because it can be smoothly produced in a high yield.
  • organic solvents ketones, ethers, esters, aromatic hydrocarbons, chlorinated aromatic hydrocarbons, aliphatic hydrocarbons, chlorinated aliphatic hydrocarbons, alicyclic hydrocarbons.
  • organic solvents monohydric alcohols, polyhydric alcohols, glycol ethers.
  • the boiling point of the mixed solvent of the group (A) organic solvent and the group (B) organic solvent used for the polymerization is 100 from the viewpoint of handling at the time of copolymerization, easiness of separation and removal of the solvent after polymerization, and the like.
  • the temperature is preferably not higher than ° C, more preferably 60 to 95 ° C.
  • the monomer component may be dissolved in a single organic solvent selected from the group (A) organic solvent or the group (B) organic solvent. It is preferable to use a mixed solvent composed of at least one kind of the organic solvent of group (A) and at least one kind of the organic solvent of group (B).
  • ketones used as the organic solvent of the group (A) include acetone and methyl ethyl ketone.
  • Specific examples of the ethers include diethyl ether and tetrahydrofuran.
  • Specific examples of the esters Examples include methyl acetate, ethyl acetate, propyl acetate, cellosolve acetate, etc.
  • Specific examples of aromatic hydrocarbons include benzene, toluene, etc.
  • chlorinated aromatic hydrocarbons examples include hexane, heptane, and various paraffin oils.
  • chlorinated aliphatic hydrocarbons include methylene chloride, dichloroethane, and chloroform. , Carbon tetrachloride and the like, and alicyclic carbonization
  • Motorui can include cyclohexane, etc. cycloheptane.
  • one or two of methyl ethyl ketone and tetrahydrofuran are preferably used as the organic solvent of the group (A) from the viewpoint of the solubility and ease of handling of the silicone-based macromonomer and the generated silicone-based graft copolymer. .
  • Specific examples of the above-described monohydric alcohol used as the organic solvent of group (B) include methanol, ethanol, propanol, butanol, isopropyl alcohol and the like.
  • Specific examples of the polyhydric alcohol include ethylene glycol and propylene.
  • Examples of the glycol ether include methyl cellosolve, ethyl cellosolve, diethylene glycol monomethyl ether, and diethylene glycol dimethyl ether.
  • one or two kinds of ethanol and isopropyl alcohol are preferably used as the organic solvent of the group (B) from the viewpoint of the dissolving power and ease of handling of the silicone-based macromonomer and the generated silicone-based graft copolymer. .
  • each monomer component used for the polymerization and the polymer component produced by the polymerization are more stably dissolved in the mixed solvent, and each monomer.
  • Polymerization is preferably carried out using a solvent, a mixed solvent of methyl ethyl ketone and ethanol, a mixed solvent of tetrahydrane and isopropyl alcohol, or a mixed solvent of tetrahydrfuran and ethanol.
  • a solvent a mixed solvent of methyl ethyl ketone and ethanol
  • a mixed solvent of tetrahydrane and isopropyl alcohol or a mixed solvent of tetrahydrfuran and ethanol.
  • Alcohol mixed solvent or methyl ethyl ketone and ethanol It is more preferable to carry out the polymerization using a mixed solvent.
  • the content ratio of the organic solvent of group (A) and the organic solvent of group (B) in the mixed solvent during the polymerization reaction is more preferably continuously changed as the polymerization proceeds.
  • the organic solvent that is most suitable for dissolving the monomer components before polymerization and the organic solvent that is most suitable for dissolving the silicone-based graft copolymer produced by polymerization are generally different.
  • [the organic of the group (A) Solvent]: [Organic solvent of group (B)] is preferably continuously changed by mass ratio within a range of 1: 5 to 5: 1, and within a range of 1: 3 to 3: 1. It is more preferable to change continuously.
  • the mixing ratio of [(A) group organic solvent]: [(B) group organic solvent] exceeds the above range, the productivity of the silicone-based graft copolymer may be lowered.
  • the mass ratio of methyl ethyl ketone to isopropyl alcohol at the start of the polymerization is in the range of 2: 1 to 1: 2
  • the mass ratio of methyl ethyl ketone: isopropyl alcohol or the mass ratio of methyl ethyl ketone to ethanol at the end of the polymerization is in the range of 1: 1 to 1: 3.
  • radical polymerization using a radical polymerization initiator is preferably employed because it can be applied to a wide variety of monomers and the adjustment of the polymerization operation and molecular weight is easy.
  • the type of radical polymerization initiator is not particularly limited, but it is easy to control the molecular weight of the silicone-based graft copolymer, has a low decomposition temperature, and is easy to handle.
  • a polymerization initiator is preferably used, and an azo polymerization initiator is particularly preferably used.
  • azo polymerization initiator preferably used in the present invention include cyano azobisisobutyronitrile, azobis (2-methylbutyronitrile), and non-cyano dimethyl-2,2′-azobis. Examples include isobutyrate.
  • organic peroxide polymerization initiator preferably used in the present invention include peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, peroxyesters, and the like. Can do.
  • the amount of the radical polymerization initiator used is preferably 0.1 to 15% by mass, more preferably 0.3 to 10% by mass, based on the total mass of all monomers used for the polymerization. .
  • azo macroazo initiators having a polymer skeleton of polyethylene oxide and / or polydimethylsiloxane examples include VPE-0201, VPE-0401, and VPE-0601 (manufactured by Wako Pure Chemical Industries, Ltd.), and a macroazo initiator having a polydimethylsiloxane unit. Examples thereof include VPS-0501 and VPS-1001 (manufactured by Wako Pure Chemical Industries, Ltd.). When these initiators are used, block copolymers having polyethylene oxide and polydimethylsiloxane skeleton can be obtained, respectively.
  • an appropriate amount of a chain transfer agent may be added as necessary for polymerization.
  • the chain transfer agent that can be used in the present invention include mercaptoacetic acid, mercaptopropionic acid, 2-propanethiol, 2-mercaptanethanol, thiophenol, dodecyl mercaptan, and thioglycerol. Species or two or more can be used.
  • the polymerization temperature for producing the silicone-based graft copolymer is preferably 40 to 180 ° C, more preferably 50 to 150 ° C. If the polymerization temperature is too low, the copolymerization rate is decreased and the polymerization initiator is likely to remain. On the other hand, if the polymerization temperature is too high, the thermal decomposition of the (meth) acrylate (I) and the generated silicone graft copolymer There is a risk of thermal decomposition of the coalescence.
  • the polymerization time is generally preferably about 3 to 25 hours, more preferably about 3 to 12 hours.
  • the silicone-based graft copolymer of the present invention having a weight average molecular weight generally in the range of 6000 to 40,000 can be obtained.
  • the carboxyl group present in the silicone-based graft copolymer is in a state of being not neutralized.
  • Water-solubilization can be achieved by neutralizing a part or all of the carboxyl groups present in the silicone-based graft copolymer obtained above with a base.
  • the degree of neutralization when the silicone graft copolymer is water-solubilized by neutralizing the carboxyl group in the silicone graft copolymer with a base is as follows. By setting the degree of neutralization so that 50 mol% or more, particularly 70 mol% or more of the salt becomes a salt form, the silicone-based graft copolymer can be stably water-solubilized.
  • Examples of the base used for neutralization include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide, and organic amines such as aqueous ammonia, diethanolamine, and triethanolamine.
  • alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide
  • organic amines such as aqueous ammonia, diethanolamine, and triethanolamine.
  • sodium hydroxide and / or potassium hydroxide is used, the stability of the aqueous polymer solution is excellent, and when ammonia or an organic amine having a low boiling point is used, the water resistance of the film after drying is excellent.
  • Neutralization and water-solubilization of the silicone-based graft copolymer with a base may be performed while the produced silicone-based graft copolymer is present in the organic solvent used for the polymerization, or from the polymerization system. After the silicone-based graft copolymer is separated and recovered, the recovered silicone-based graft copolymer may be placed in water, and a base may be added thereto for neutralization and water solubilization. In general, all or part of the organic solvent is distilled, vacuum distilled, dried, etc.
  • the method of distilling off by an appropriate method is preferably employed because an aqueous solution in which a water-soluble silicone-based graft copolymer is dissolved can be easily obtained, and a uniform and stable aqueous polymer solution can be obtained.
  • the aqueous polymer solution obtained by dissolving the water-soluble silicone graft copolymer obtained by converting a part or all of the carboxyl groups of the silicone graft copolymer into a salt form with a base to be water-solubilized is obtained as described above. It is particularly useful as a combined composition (including use as an additive in water-based paints and water-based inks). Accordingly, the present invention includes the aqueous coating polymer composition. From the aqueous coating polymer composition containing the silicone-based graft copolymer of the present invention, a coating excellent in properties such as lubricity, mold release, water repellency, scratch resistance, stain resistance, weather resistance, and gloss Is formed.
  • the water forming the medium is deionized water or distilled water from which ionic components have been removed by ion exchange or other treatments.
  • the aqueous coating polymer composition containing the water-solubilized silicone-based graft copolymer dissolved therein may contain a water-soluble organic solvent together with water, if necessary. By containing a water-soluble organic solvent, it is possible to prevent drying during storage of the aqueous coating polymer composition and to improve adhesion to the substrate.
  • One or two or more of these can be contained in the aqueous coating polymer composition.
  • lower alkyl ethers of polyhydric alcohols such as diethylene glycol, other polyhydric alcohols, and triethylene glycol monomethyl ether are preferably used.
  • the obtained water-soluble polymer can be used as it is as various paints, coatings, inks, or additives thereof.
  • high weather resistance and precision material applications such as inkjet, In order to remove the adverse effects of trace impurities, those purified by liquid-liquid separation washing, reprecipitation purification method, etc. can be applied.
  • aqueous coating polymer composition containing a water-soluble silicone-based graft copolymer dissolved therein has been conventionally used in various known and commonly used additives added to aqueous pigment inks and silicone-based aqueous coating polymer compositions.
  • Various additives can be contained as required. Examples of such additives include surfactants, antifoaming agents, preservatives, antisettling agents, chelating agents, thickeners, antioxidants, dyes and pigments, and one or more of these Two or more kinds can be contained.
  • the aqueous coating polymer composition containing the silicone-based graft copolymer of the present invention is an aqueous coating from the viewpoint of the stability of the aqueous coating polymer composition, the handleability during coating, the leveling properties of the liquid, and the like.
  • the water-soluble silicone-based graft copolymer of the present invention is contained in a proportion of 0.1 to 50% by mass, based on the total mass of the polymer composition for use, and a proportion of 0.5 to 30% by mass It is more preferable to contain.
  • the water-soluble silicone-based graft copolymer content in the aqueous coating polymer composition is too low, the water repellency, lubricity, releasability, weather resistance, scratch resistance, stain resistance, and strength are excellent. It is difficult to form a coating film having excellent durability, and on the other hand, if the content ratio of the water-soluble silicone-based graft copolymer is too high, the viscosity of the aqueous coating polymer composition becomes too high and the coating composition is Handling properties and leveling properties (uniform coating properties) are likely to deteriorate.
  • the content of water is in the range of 10 to 97% by mass based on the total mass of the aqueous coating polymer composition. It is preferably in the range of 25 to 90% by mass, and more preferably in the range of 40 to 80% by mass.
  • the water-soluble polymer composition containing the silicone-based graft copolymer of the present invention contains a water-soluble organic solvent together with water, the content ratio of the water-soluble organic solvent is determined based on the weight of the water-based coating weight. Based on the total mass of the combined composition, the range is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less.
  • the pH of the aqueous coating polymer composition containing the silicone-based graft copolymer of the present invention is preferably in the range of 4 to 11, more preferably in the range of 5 to 10. If the pH of the aqueous coating polymer composition is 5 or less, the ionization rate of the carboxyl group in the polymer (ratio of being a salt) is insufficient to maintain water solubility, and if the pH exceeds 10, the polymer Alkaline hydrolysis is promoted.
  • the pH of the aqueous coating polymer composition is adjusted by alkali metal hydroxides such as sodium hydroxide and potassium hydroxide and other inorganic alkali agents, organic amines such as dimethylethanolamine, diethanolamine and triethanolamine,
  • alkali metal hydroxides such as sodium hydroxide and potassium hydroxide and other inorganic alkali agents
  • organic amines such as dimethylethanolamine, diethanolamine and triethanolamine
  • the reaction can be performed using an organic acid such as acid or tartaric acid, or an inorganic acid such as hydrochloric acid or phosphoric acid.
  • the aqueous coating polymer composition containing the silicone-based graft copolymer of the present invention can be used in combination with various water-based crosslinking agents. Although it does not restrict
  • the aqueous coating polymer composition containing the silicone-based graft copolymer of the present invention has excellent film lubricity, releasability, water repellency, scratch resistance, stain resistance, weather resistance, gloss, etc.
  • Various products and semi-finished products made of various materials, such as fabrics, papers, synthetic resins, rubber, wood, metals, ceramics, or one or two of the above-described materials, using the characteristics For example, it can be effectively used as a coating composition for coating clothing, coated paper, and the like.
  • the coating method and the coating apparatus in performing the coating treatment using the aqueous coating polymer composition containing the silicone-based graft copolymer of the present invention are not particularly limited, and the coating technique using the aqueous coating polymer composition Can be carried out by using a coating method and a coating apparatus conventionally employed.
  • a coating method such as roller coating, spray coating, cast coating, blade coating, brush coating, dipping, or inkjet coating using the aqueous coating polymer composition containing the silicone-based graft copolymer of the present invention. (Coating method) can be used for coating.
  • the aqueous coating polymer composition containing the silicone-based graft copolymer of the present invention exhibits sufficient characteristics even when it is dried at room temperature after coating various materials, products, semi-finished products, etc.
  • lubricity, releasability, water repellency, scratch resistance, scratch resistance, A film excellent in properties such as contamination, weather resistance, and gloss can be formed.
  • the thickness of the coating is not particularly limited and can be adjusted according to the type, use, shape, etc. of the material for coating the aqueous coating polymer composition.
  • Example 1 Production of silicone graft copolymer: In a glass flask equipped with a stirrer, dropping funnel, reflux condenser, nitrogen gas inlet tube and thermometer, methoxydiethylene glycol methacrylate [“NK Ester M-20G” manufactured by Shin-Nakamura Chemical Co., Ltd.
  • the concentration is adjusted by adding ion-exchanged water, and a silicone-based graft copolymer aqueous solution having a silicone graft copolymer content of 25% by mass Manufactured.
  • This aqueous solution filtered with a membrane filter having a pore size of 5.0 ⁇ m was used as an aqueous coating polymer composition (potassium hydroxide neutralized product) containing a silicone-based graft copolymer, and the performance was as follows. Evaluation was performed (general performance evaluation of a polymer composition for aqueous coating and performance evaluation of an ink jet type coating agent).
  • Example 1 dimethylethanolamine (4.3 g in Example 1) was used instead of potassium hydroxide, and an aqueous coating polymer composition (dimethylethanolamine neutralized product) was prepared in the same manner as described above.
  • the performance was evaluated by the following method (performance evaluation of the coating agent for metal cans).
  • Example 1 except that in the polymerization step of the silicone-based graft copolymer of Example 1 (1), the monomers listed in Table 1 below were used in the proportions described in Table 1.
  • an organic solvent solution of the silicone-based graft copolymer was produced.
  • the appearance of the organic graft solution of the silicone graft copolymer thus obtained was evaluated by the following method, and the acid of the silicone graft copolymer contained in the organic solvent solution of the silicone graft copolymer was evaluated.
  • molecular weight weight average molecular weight and number average molecular weight
  • molecular weight distribution were determined by the method, they were as shown in Table 1 below.
  • Example 6 (1) In the polymerization step of the silicone-based graft copolymer of (1) of Example 1, azobis-2-methylobutylnitrile (ABN-E) was added to a mixed solvent of 40 g of methyl ethyl ketone and 40 g of isopropyl alcohol as a polymerization initiator solution. An organic solvent solution of the silicone-based graft copolymer was produced in the same manner as (1) of Example 1 except that 1.5 g dissolved was used. The appearance of the organic graft solution of the silicone graft copolymer thus obtained was evaluated by the following method, and the acid of the silicone graft copolymer contained in the organic solvent solution of the silicone graft copolymer was evaluated.
  • ABS-E azobis-2-methylobutylnitrile
  • Example 7 In the polymerization step of the silicone graft copolymer of Example 1 (1), 1.5 g of azobis-2-methylobutylnitrile (ABN-E) was dissolved in 80 g of methyl ethyl ketone as a polymerization initiator solution. An organic solvent solution of a silicone-based graft copolymer was produced in the same manner as (1) of Example 1 except that the above was used. The appearance of the organic graft solution of the silicone graft copolymer thus obtained was evaluated by the following method, and the acid of the silicone graft copolymer contained in the organic solvent solution of the silicone graft copolymer was evaluated.
  • ABS-E azobis-2-methylobutylnitrile
  • Example 8-14 In the polymerization step of the silicone-based graft copolymer of (1) of Example 1, Example 1 was used except that the monomers listed in Table 2 below were used as monomers in the proportions described in Table 2. In the same manner as in (1), an organic solvent solution of the silicone-based graft copolymer was produced. The appearance of the organic graft solution of the silicone graft copolymer thus obtained was evaluated by the following method, and the acid of the silicone graft copolymer contained in the organic solvent solution of the silicone graft copolymer was evaluated. When the value, molecular weight (weight average molecular weight and number average molecular weight) and molecular weight distribution were determined by the method, they were as shown in Table 2 below.
  • Example 1 except that in the polymerization step of the silicone-based graft copolymer of Example 1 (1), the monomers listed in Table 3 below were used in the proportions described in Table 3.
  • an organic solvent solution of the silicone-based graft copolymer was produced.
  • the appearance of the organic graft solution of the silicone graft copolymer thus obtained was evaluated by the following method, and the acid of the silicone graft copolymer contained in the organic solvent solution of the silicone graft copolymer was evaluated.
  • molecular weight weight average molecular weight and number average molecular weight
  • molecular weight distribution were determined by the method, they were as shown in Table 3 below.
  • Examples 21-23 (1) In the polymerization step of the silicone-based graft copolymer of (1) of Example 1, 0.2 g of dodecyl mercaptan (Example 21), dodecyl mercaptan 3 instead of 1.8 g of dodecyl mercaptan as a chain transfer agent Preparation of an organic solvent solution of a silicone-based graft copolymer in the same manner as (1) of Example 1 except that 0.0 g (Example 22) or 0.9 g of 3-mercaptopropionic acid (Example 23) was used. did.
  • Example 24 In the polymerization step of the silicone graft copolymer of Example 1 (1), the silicone graft copolymer was used in the same manner as in Example 1 (1) except that 160 g of isopropyl alcohol was used alone as a polymerization solvent. An organic solvent solution of the polymer was prepared. The appearance of the organic graft solution of the silicone graft copolymer thus obtained was evaluated by the following method, and the acid of the silicone graft copolymer contained in the organic solvent solution of the silicone graft copolymer was evaluated. When the value, molecular weight (weight average molecular weight and number average molecular weight) and molecular weight distribution were determined by the method, they were as shown in Table 4 below.
  • Example 25 (1) In the polymerization step of the silicone-based graft copolymer of (1) of Example 1, 160 g of methyl ethyl ketone was used alone as a polymerization solvent, and 80 g of methyl ethyl ketone as a polymerization initiator solution was added to azobis-2-methylobutylnitrile ( An organic solvent solution of a silicone-based graft copolymer was produced in the same manner as (1) of Example 1 except that 1.5 g of ABN-E was used.
  • Example 26 In the preparation process of the aqueous coating polymer composition of Example 1 (2), 33 g (33 g) of the organic solvent used in the polymerization was added before adding the neutralizing base to the organic solvent solution of the silicone-based graft copolymer. 47% by mass of the total amount of the solvent was distilled off under reduced pressure, and then a neutralized base was added (solid content concentration at the time of neutralization 45% by mass) in the same manner as (2) of Example 1 except that silicone An aqueous coating polymer composition (solid content 25% by mass, pH 8.0) containing a system graft copolymer was produced, and its performance was evaluated by the following method. The results are shown in Table 4 below.
  • Example 1 except that the monomers described in Table 5 below were used as monomers in the polymerization step of the silicone-based graft copolymer of Example 1 (1) in the proportions described in Table 5.
  • an organic solvent solution of the silicone-based graft copolymer was produced.
  • the appearance of the organic graft solution of the silicone graft copolymer thus obtained was evaluated by the following method, and the acid of the silicone graft copolymer contained in the organic solvent solution of the silicone graft copolymer was evaluated.
  • molecular weight weight average molecular weight and number average molecular weight
  • molecular weight distribution were determined by the method, they were as shown in Table 5 below.
  • Comparative Examples 7-10 (1) In the polymerization step of the silicone-based graft copolymer of (1) of Example 1, the monomers and chain transfer agents described in Table 6 below are described in Table 6 without using a silicone-based macromonomer. In this case, 160 g of isopropyl alcohol is used alone as a polymerization solvent, and 1.5 g of azobis-2-methylobutylnitrile (ABN-E) is dissolved in 80 g of isopropyl alcohol as a polymerization initiator solution. Then, an organic solvent solution of a non-silicone copolymer was produced in the same manner as in Example 1 (1).
  • ABSN-E azobis-2-methylobutylnitrile
  • the appearance of the organic solvent solution of the silicone-based graft copolymer obtained in Examples 1 to 26 and Comparative Examples 1 to 6 and the organic solvent solution of the non-silicone copolymer obtained in Comparative Examples 7 to 10 were as follows. Evaluation, measurement of acid value and molecular weight of silicone-based graft copolymer or non-silicone-based copolymer contained in the organic solvent solution, aqueous solutions obtained in Examples 1 to 26 and Comparative Examples 1 to 10 above The appearance and stability of the coating polymer composition and the performance when the aqueous coating composition was used as a coating agent were evaluated by the following methods.
  • a gel permeation chromatograph (GPC) method was employed in which the components adsorbed on the column were eluted by passing through the column at 0.0 mL / min.
  • the number average molecular weight (Mn) and the weight average molecular weight (Mw) were calculated from a calibration curve prepared in advance using polystyrene having a known molecular weight as a reference substance.
  • the molecular weight distribution (Mw / Mn) was determined by dividing the weight average molecular weight (Mw) obtained above by the number average molecular weight (Mn).
  • aqueous coating composition neutralized potassium hydroxide (silicone graft copolymer or non-silicone copolymer aqueous solution): The appearance of the aqueous coating composition (silicone graft copolymer or non-silicone copolymer aqueous solution) was visually determined according to the following criteria. Transparent: The aqueous coating composition (aqueous solution) is transparent. White: The aqueous coating composition (aqueous solution) has a transparent white color. -White turbidity: The aqueous coating composition (aqueous solution) has a white color with no transparency (white turbidity). Precipitate generation: Precipitates are confirmed in the aqueous coating composition (aqueous solution).
  • aqueous coating composition (potassium hydroxide neutralized product) (aqueous solution of silicone-based graft copolymer or non-silicone copolymer):
  • the aqueous coating compositions (silicone graft copolymer or non-silicone copolymer aqueous solution) prepared in the following examples and comparative examples were stored at a temperature of 60 ° C. for 3 months, and then visually in a liquid state.
  • the storage stability was evaluated according to the following evaluation criteria.
  • A Transparency and color of the aqueous coating composition (aqueous solution) are almost unchanged before and after the test, and no two-layer separation or agglomeration of the liquid occurs, and the storage stability is very good.
  • ⁇ Transparency and / or coloration of the aqueous coating composition (aqueous solution) was slightly confirmed before and after the test, but the liquid was not separated into two layers or aggregated, and the storage stability was quite good. is there.
  • ⁇ In the aqueous coating composition (aqueous solution), generation of fine aggregates or two-layer separation of the liquid was slightly confirmed, and the storage stability was slightly inferior.
  • X Generation
  • a coating polymer composition neutralized dimethylethanolamine
  • silicone graft copolymer or non-silicone copolymer aqueous solution, solid content 25% by mass, pH 8.0 was added, and further dimethyl 20 parts by weight of an imino-type benzoguanamine resin [“My Coat 106” manufactured by Mitsui Cytec Co., Ltd.] is added, and ion-exchanged water is further added to adjust the solid content to 30% by weight.
  • Got. (C) Apply the aqueous coating agent for metal cans obtained in (b) above onto an aluminum plate with a bar coater so that the film pressure is 5-6 ⁇ m, and heat cure at a temperature of 200 ° C. for 10 minutes.
  • An aluminum plate (test piece) was prepared, and various performances of the coating film were evaluated by the following methods using the test piece.
  • (Ii) Leveling properties of the coating film The coating film surface of the test piece (painted aluminum plate) prepared in (c) of (i) above was visually observed, and the leveling property of the coating film was evaluated according to the following criteria. ⁇ : No coating lines on the bar coater were confirmed, and the leveling property was excellent. ⁇ : A slight coating line of the bar coater is confirmed, and the leveling property is slightly inferior. X: The coating line of the bar coater is clearly confirmed, and the leveling property is inferior.
  • (V) Oil resistance of coating film A drop of soybean oil is dropped on a coating surface on the test piece (painted aluminum plate) prepared in (i) (c) above, and left for 1 hour with a dropper, and then wiped off. The uneven gloss of the film was visually observed and evaluated according to the following criteria. ⁇ : Uneven gloss is not confirmed. ⁇ : Gloss unevenness is confirmed to some extent. X: Uneven gloss is clearly confirmed.
  • inkjet discharge type coating agent (I) Inkjet discharge type coating agent and printing on paper: (A) Polymer compositions for aqueous coating obtained in Examples 1 to 26 and Comparative Examples 1 to 10 with respect to 100 parts by mass of commercially available pigment ink for inkjet [BCI-9BK manufactured by Canon Inc.] 20 parts by weight of a product (neutralized potassium hydroxide) (silicone graft copolymer or non-silicone copolymer aqueous solution, solid content 25% by mass, pH 8.0), It filtered using the membrane filter and prepared the inkjet discharge type coating agent (ink for printing).
  • a product neutralized potassium hydroxide
  • the inkjet discharge type coating agent (printing ink) obtained in the above (a) is filled in an ink cartridge of a commercially available printer [“PIXUS iP4200” manufactured by Canon Inc.], and commercially available glossy paper [Canon "Photo Glossy Paper GP-301” manufactured by Co., Ltd.] was printed solidly to evaluate the ink jetting suitability at the time of printing, and the printed matter was dried at room temperature for 24 hours. Evaluation was performed.
  • Inkjet ejection suitability Using the inkjet discharge coating agent (printing ink) prepared in (a) of (i) above, 10 sheets of solid paper are continuously printed on glossy paper by the method of (i) (b) above. The print defects were visually observed and evaluated according to the following criteria.
  • Double-circle There is no blur of printing in all 10 printed matter, and it is excellent in the discharge property of an inkjet.
  • ⁇ Less than 3 out of 10 printed materials, there is a slight blur of printing, which is slightly inferior in ink jet discharge.
  • delta All the 10 printed matter has a printing blur considerably, and it is inferior to the discharge property of an inkjet.
  • X Inkjet ejection is not possible.
  • (V) Gloss of printed matter Using as a control a printed matter printed using the same printer as described above using a normal pigment ink [Canon, Inc. “BCI-9BK”] to which no aqueous coating polymer composition was added, the following: The gloss was evaluated according to the following criteria. ⁇ : The same or higher gloss is maintained as compared with the control. (Triangle
  • (Vii) Weather resistance of printed matter The printed matter obtained in (b) of (i) above was measured using a metering weather meter (“DAIPLA METAL WEATHER KU-R5NCI-A” manufactured by Daipura Wintes Co., Ltd.) without using water. After conducting a weather resistance test for 100 hours, the printed material was subjected to a scratch resistance test in the same manner as in (iv) above. The weather resistance was evaluated according to the following criteria, compared with the results of the scratch resistance test before exposure). ⁇ : There is almost no difference in scratch resistance after the weather resistance test, and the weather resistance is excellent. ⁇ : Scratch resistance is slightly deteriorated after the weather resistance test, and weather resistance is slightly inferior. X: Scratch resistance is greatly deteriorated after the weather resistance test, and the weather resistance is poor.
  • MMA Methyl methacrylate
  • BMA Butyl methacrylate M-5300: “Aronix M-5300” ( ⁇ -carboxypolycaprolactone monoacrylate) manufactured by Toagosei Co., Ltd.
  • HEMA 2-hydroxymethyl methacrylate
  • St Styrene
  • the silicone graft copolymer of the present invention has a silicone polymer portion derived from a silicone macromonomer as a hydrophobic branch, and a polymer having a structural unit derived from a hydrophilic polymerizable monomer as a trunk. Therefore, the silicone-based polymer forming the branches exhibits excellent water repellency performance, lubrication performance, mold release performance, weather resistance performance, and contamination resistance performance.
  • the water-soluble polymer composition for dissolution containing the water-soluble silicone-based graft copolymer is excellent in storage stability, water repellency, lubricity, release properties, weather resistance, stain resistance, Since the film having excellent gloss is formed, the silicone-based graft copolymer of the present invention and the aqueous coating polymer composition containing the same should be effectively used as an aqueous coating polymer composition for other applications. Can do. Furthermore, the above-described silicone-based graft copolymer can be produced smoothly with good productivity by the production method of the present invention using a mixed solvent of a specific group (A) organic solvent and group (B) organic solvent. Therefore, the method of the present invention is also useful as a method for producing a silicone-based graft copolymer.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne un copolymère siliconé greffé comportant une fraction constituée d'un polymère siliconé en tant que chaîne hydrophobe et un polymère issu d'un monomère hydrophile polymérisable en tant que tige, ainsi qu'un procédé de production dudit copolymère siliconé greffé. L'invention concerne, plus précisément, un copolymère siliconé greffé produit par copolymérisation d'un ester d'acide (méth)acrylique de formule suivante : CH2=C(R1)-COO-(R2-O)n-R3 [où R1 représente H ou un groupe méthyle ; R2 représente un groupe éthylène ou propylène ; R3 représente H ou un groupe hydrocarbure en C1-C6 ; et n représente un nombre de 1 à 25, sous réserve que R3 représente un groupe hydrocarbure monovalent en C1-C6 lorsque n est égal à 1], un (sel d') acide carboxylique éthyléniquement insaturé, un macromonomère de silicone d'une masse moléculaire de 5 000 à 35 000, et éventuellement un autre monomère ; une composition polymère aqueuse de revêtement comprenant le copolymère greffé ; et un procédé de production du copolymère greffé par copolymérisation dans un solvant mixte constitué d'un solvant organique choisi parmi les éléments du groupe (A), à savoir une cétone, un éther, un ester, un hydrocarbure aromatique et autres, et d'un solvant organique choisi parmi les éléments du groupe (B), à savoir un alcool monovalent ou polyvalent et un ester de glycol.
PCT/JP2009/052617 2008-02-19 2009-02-17 Copolymère siliconé greffé et son procédé de production WO2009104569A1 (fr)

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CN115023449A (zh) * 2020-02-06 2022-09-06 哈利玛化成株式会社 脱模剂、和树脂成形物的制造方法
CN113402681A (zh) * 2021-06-24 2021-09-17 中科院广州化学有限公司 一种含巯基有机硅改性苯丙乳液及其制备方法与应用
CN114276502A (zh) * 2021-11-10 2022-04-05 佛山金戈新材料股份有限公司 一种用于导热有机硅灌封胶的防沉降剂的制备与应用
CN114276502B (zh) * 2021-11-10 2023-09-26 广东金戈新材料股份有限公司 一种用于导热有机硅灌封胶的防沉降剂的制备与应用

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