Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
  • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
• • 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
  • C08G77/04—Polysiloxanes
  • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
• • 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
  • C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
• • 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
  • C08F290/08—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 side groups
  • C08F290/14—Polymers provided for in subclass C08G
  • C08F290/148—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
  • C08G77/04—Polysiloxanes
  • C08G77/06—Preparatory processes
• • 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
  • C08G77/04—Polysiloxanes
  • C08G77/38—Polysiloxanes modified by chemical after-treatment
  • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
  • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
• • 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
  • C08G77/04—Polysiloxanes
  • C08G77/38—Polysiloxanes modified by chemical after-treatment
  • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
  • C08G77/392—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing sulfur
• • 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
  • C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester 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
• • 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
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
  • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
• • 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
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
  • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
• • 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
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/10—Block or graft copolymers containing polysiloxane sequences
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/52—Aqueous emulsion or latex, e.g. containing polymers of a glass transition temperature (Tg) below 20°C
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another

Definitions

• the present invention relates to polysiloxane resins and their uses.
• Patent Document 1 discloses a curable resin composition containing a resin obtained by condensation reaction of a polymer having a hydrolyzable silyl group and a polysiloxane having a hydroxyl group bonded to a silicon atom, and a curing catalyst.
• a product (a paint) is disclosed.
• Patent Document 1 is a paint using an organic solvent.
• attempts have been made to convert from the use of organic solvents to water-soluble or water-dispersible resins from the viewpoint of pollution control and resource conservation.
• polysiloxane resins are hydrophobic, it is difficult to make them water-based, and when used as a paint, it is necessary to keep the viscosity of the water-based resin within a range suitable for practical use.
• an object of the present invention is to provide a polysiloxane resin that can be stably dispersed or dissolved (water-based) in an aqueous medium and has an appropriate viscosity when water-based.
• a poly that can be stably dispersed or dissolved in an aqueous medium water-based
• the inventors have found for the first time that a siloxane-based resin can be obtained, and (2) that a solution or dispersion having an appropriate viscosity can be obtained when the polysiloxane-based resin is made water-based, thereby completing the present invention.
• one aspect of the present invention has, as a structural unit, a polymer containing a structural unit derived from a monomer having a radically polymerizable group, wherein the monomer is (i) soluble in water, It is also a polysiloxane resin containing a monomer that does not form micelles in water and (ii) a monomer that can form micelles in water.
• a polysiloxane-based resin that can be stably dispersed or dissolved (water-based) in an aqueous medium and has an appropriate viscosity when water-based.
• a water-soluble polysiloxane resin can be obtained by adding a salt structure composed of an acid and a base to a polysiloxane resin. Therefore, the inventors of the present invention have found the following problems while further studying the above technology: ⁇ When a salt structure consisting of an acid and a base is added to a polysiloxane-based resin, the polysiloxane-based resin becomes soluble in water, but the viscosity of the solution in which the polysiloxane-based resin is dissolved increases significantly, resulting in water-based paint. It cannot be used for other purposes.
• the present inventors have made intensive studies on a method that can simultaneously achieve the above problems of solubility and viscosity, and as a result, have succeeded in obtaining the following knowledge: -
• a monomer that is soluble in water and does not form micelles in water and (ii) a unit that can form micelles in water
• a polysiloxane resin that can be stably dispersed or dissolved in an aqueous medium (water-based) can be obtained by adding a structural unit derived from a polymer.
• a solution or dispersion having a suitable viscosity as a water-based paint can be obtained.
• the polysiloxane-based resin is extremely useful as a material for paints, especially water-based paints.
• a polysiloxane resin according to one embodiment of the present invention has, as a structural unit, a polymer containing a structural unit derived from a monomer having a radically polymerizable group, and the monomer is (i) water and (ii) monomers capable of forming micelles in water.
• the polysiloxane-based resin according to one embodiment of the present invention may be referred to as “the present polysiloxane-based resin”.
• the present polysiloxane-based resin has the above-described structure, so that it can be stably dispersed or dissolved in an aqueous medium (water-based), and provides a polysiloxane-based resin that has an appropriate viscosity when water-based. can do.
• polysiloxane-based resin means a resin containing a polysiloxane structure as a main component.
• the polysiloxane-based resin is not particularly limited as long as it satisfies the above definition.
• dehydration condensation with a single compound represented by the following general formula (I), or multiple Examples include resins mainly composed of polysiloxane structures obtained by cocondensation of compounds of: R 1 a R 2 b —Si—(OR 3 ) 4-ab (I)
• R 1 has a substituted alkyl group having 1 to 10 carbon atoms, an alkenyl group, or a polymerizable unsaturated group having a polymerizable unsaturated group, and may optionally have other substituents.
• the polysiloxane resin is a single compound represented by the general formula (I), or a plurality of compounds, and a single compound represented by the following general formula (II), or a plurality of It may be a resin mainly composed of a polysiloxane structure obtained by co-condensing a compound of: R 4 n —Si—(OR 5 ) 4-n (II) (In the formula, each R 4 is independently an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms or an unsubstituted or substituted aryl group, and each R 3 is independently a hydrogen atom or 1 to 10 carbon atoms; is an alkyl group, a is an integer of 1 to 3, b is an integer of 0 to 2, and a+b is an integer of 1 to 3.)
• the polysiloxane resin is a single compound represented by the general formula (I), or a plurality of compounds, and a single compound represented by the following general formula (II
• the polysiloxane structure which is the main component of the polysiloxane resin, that is, the structural unit formed by condensing a monomer having a hydrolyzable silyl group may be referred to as a "main chain”.
• a structural unit composed of a monomer having a radically polymerizable group and bonded to the main chain by radical polymerization may be referred to as a "side chain”.
• the side chains of this polysiloxane resin are composed of a polymer containing structural units derived from a monomer having a radically polymerizable group.
• the monomers constituting the side chains of the present polysiloxane-based resin are (i) monomers that are soluble in water and do not form micelles in water, and (ii) capable of forming micelles in water. It is not particularly limited as long as it contains possible monomers.
• the side chains of the present polysiloxane-based resin may be composed only of the monomers (i) and (ii) above, or may contain other monomers.
• the monomer other than (i) and (ii) above is preferably a monomer having no hydrolyzable silyl group, and optionally , may contain a monomer having a hydrolyzable silyl group.
• the present polysiloxane-based resin can also be expressed as follows as a preferred example: a side chain made of a polymer containing, as a structural unit, a structural unit derived from a monomer having a radically polymerizable group; having, as a constituent unit of the side chain, a salt structure consisting of an acid and a base and a radically polymerizable group (not having a polyoxyalkylene structure), and having no hydrolyzable silyl group; A structural unit (b) derived from a monomer (B) that is soluble in water and does not form micelles in water, and a structure (having a polyoxyalkylene structure) capable of forming micelles in water and a structural unit (c) derived from a monomer (C) having a radically polymerizable group and not having a hydrolyzable silyl group.
• the polysiloxane-based resin comprises a structural unit (a) derived from a silane compound (A) having a radically polymerizable unsaturated group and a hydrolyzable silyl group, and a salt composed of an acid and a base.
• the polysiloxane-based resin has the structural unit (a) forming the main chain and the structural units (b) and (c) forming side chains.
• the polysiloxane-based resin in addition to the above (A) to (C), optionally has the following general formula (II) as a constituent unit of the main chain: R 4 n —Si—(OR 5 ) 4-n (II) (In the formula, each R 4 is independently an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms or an unsubstituted or substituted aryl group, and when there are multiple R 4 s, they may be the same or different, Each R 5 is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and n is an integer of 0 to 3.) It is more preferable to further contain a structural unit (d) derived from the silane compound (D) represented by.
• structural unit (a) derived from the silane compound (A) having a radically polymerizable unsaturated group and a hydrolyzable silyl group is simply referred to as “structural unit (a)”, and “acid and A structure derived from a monomer (B) that has a salt structure consisting of a base and a radically polymerizable group, does not have a hydrolyzable silyl group, is soluble in water, and does not form micelles in water
• the unit (b) is simply referred to as the “structural unit (b)” and “has a polyoxyalkylene structure and a radically polymerizable group, does not have a hydrolyzable silyl group, and forms micelles in water.
• structural unit (c) derived from the monomer (C) that can Unit (d)” is simply referred to as “structural unit (d)”
• structural unit (e) structure derived from monomer (E) having a radically polymerizable group other than the above (A), (B) and (C) Unit (e)” is simply referred to as “structural unit (e)”.
• silane compound (A) having a radically polymerizable unsaturated group and a hydrolyzable silyl group is simply referred to as “silane compound (A)” or “monomer (A)", and “acid and a base having a salt structure and a radically polymerizable group, and having no hydrolyzable silyl group, being soluble in water and not forming micelles in water (B) Simply referred to as “monomer (B)", "a monomer having a polyoxyalkylene structure and a radically polymerizable group, and having no hydrolyzable silyl group and capable of forming micelles in water "Compound (C)” is simply referred to as “monomer (C)", and “silane compound (D) represented by general formula (II)” is simply referred to as “silane compound (D)” or “monomer ( D)”, and “monomer (E) having a radically polymerizable group other than
• the structural unit (a) is derived from the silane compound (A) having a radically polymerizable unsaturated group and a hydrolyzable silyl group.
• the silane compound (A) having a radically polymerizable unsaturated group and a hydrolyzable silyl group has the following general formula (I): R 1 a R 2 b —Si—(OR 3 ) 4-ab (I) (In the formula, R 1 has a substituted alkyl group having 1 to 10 carbon atoms, an alkenyl group, or a polymerizable unsaturated group having a polymerizable unsaturated group, and may optionally have other substituents.
• each R 2 is independently an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms or an unsubstituted or substituted aryl group
• each R 3 is independently a hydrogen atom or 1 to 10 carbon atoms; is an alkyl group, a is an integer of 1 to 3, b is an integer of 0 to 2, and a+b is an integer of 1 to 3.
• R 1 in general formula (I) is a substituted alkyl group or alkenyl group having 1 to 10 carbon atoms having a radically polymerizable unsaturated group, or an unsubstituted or substituted aryl group having a radically polymerizable unsaturated group.
• radically polymerizable unsaturated groups include (meth)acryloyl groups.
• Examples of the silane compound (A) in which R 1 is an alkyl group having a radically polymerizable unsaturated group include (meth)acryloxymethyltrimethoxysilane, (meth)acryloxymethylmethyldimethoxysilane, (meth)acryloxy methyldimethylmethoxysilane, (meth)acryloxymethyltriethoxysilane, (meth)acryloxymethylmethyldiethoxysilane, (meth)acryloxymethyldimethylethoxysilane, 2-(meth)acryloxyethyltrimethoxysilane, 2- (Meth) acryloxyethylmethyldimethoxysilane, 2-(meth)acryloxyethyldimethylmethoxysilane, 2-(meth)acryloxyethyltriethoxysilane, 2-(meth)acryloxyethylmethyldiethoxysilane, 2-( meth)acryloxyethyldimethylethoxysilane, ⁇ -(me
• silane compound (A) in which R 1 is an alkenyl group examples include vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, vinyldimethylethoxysilane, and the like. be done.
• Examples of the silane compound (A) in which R 1 is an aryl group having a polymerizable unsaturated group and optionally having other substituents include p-styryltrimethoxysilane, p-styrylmethyl dimethoxysilane, p-styryldimethylmethoxysilane, p-styryltriethoxysilane, p-styrylmethyldiethoxysilane, p-styryldimethylethoxysilane and the like.
• a (meth)acryloyl group-substituted alkyl group is preferable as R 1 from the viewpoint of thermal radical polymerization reactivity.
• Each R 2 in general formula (I) is independently an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms or an unsubstituted or substituted aryl group.
• alkyl group for R 2 in general formula (I) examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, amyl group, isoamyl group, hexyl group, cyclohexyl group and cyclohexyl.
• Examples include methyl group, cyclohexylethyl group, heptyl group, isoheptyl group, n-octyl group, isooctyl group, 2-ethylhexyl group and the like.
• aryl group for R 2 in general formula (I) examples include a phenyl group, a naphthyl group, a benzyl group and the like.
• R 2 in general formula (I) is preferably a methyl group.
• R 3 in general formula (I) is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl and amyl. group, isoamyl group, hexyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylethyl group, heptyl group, isoheptyl group, octyl group, n-octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, decyl group and the like. .
• the alkyl of R 2 and R 3 in the general formula (I) is preferably 1-3, most preferably 1.
• the content of the structural unit (a) is, for example, 1% by weight or more, preferably 2% by weight or more, with respect to 100% by weight of the total amount of the polysiloxane resin. is.
• the structural unit (b) and/or the structural unit (c) can be sufficiently graft-polymerized directly or indirectly, resulting in stability in an aqueous medium. It is possible to obtain a polysiloxane resin that can be dispersed or dissolved in (water-based).
• the upper limit of the content of the structural unit (a) is not particularly limited as long as the effect of the present invention is exhibited, but is, for example, 10% by weight or less, preferably 8% by weight or less, more preferably 5% by weight or less. % by weight or less.
• the structural unit (b) has a salt structure consisting of an acid and a base and a radically polymerizable group, does not have a hydrolyzable silyl group, is soluble in water, and does not form micelles in water. Derived from mer (B).
• salt structure means the structure of a neutral salt obtained by neutralizing an acid and a base.
• the acid used for neutralization may be a strong acid or a weak acid.
• the base used for neutralization may be a strong base or a weak base.
• the salt structure is, for example, a structure of a neutral salt of a strong acid and a strong base, a structure of a neutral salt of a strong acid and a weak base, a structure of a neutral salt of a weak acid and a strong base, Or it can be the structure of a neutral salt of a weak acid and a weak base.
• More specific salt structures include, for example, sodium sulfonate, potassium sulfonate, calcium sulfonate, sodium nitrate, potassium nitrate, calcium nitrate (structure of neutral salt of strong acid and strong base), ammonium sulfonate, ammonium nitrate. etc.
• the salt structure is preferably sodium sulfonate.
• water-soluble means that an aqueous solution of 1 g of the target monomer in 10 g of water at 25° C. is sufficiently stirred, allowed to stand at 25° C. for 1 week, and visually When the appearance is observed in the aqueous solution, it means that the aqueous solution is transparent without any precipitate, dispersion, layer separation, or the like.
• the content of the structural unit (b) is, for example, 1% by weight or more, preferably 2% by weight or more, with respect to 100% by weight of the total amount of the polysiloxane resin. and more preferably 4% by weight or more.
• the content of the structural unit (b) is within the above range, the effect of uniformly dispersing or being soluble in water is exhibited.
• the upper limit of the content of the structural unit (b) is not particularly limited as long as the effect of the present invention is exhibited, but is, for example, 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less. % by weight or less.
• stably dispersed or dissolved in an aqueous medium means that no "precipitate” occurs when a solution containing a polysiloxane resin is evaluated by the following method: An aqueous solution of a polysiloxane-based resin produced by the method described in Examples is allowed to stand at 25° C. for 1 week, and the appearance of the aqueous solution is evaluated by visual observation.
• stably dispersed or dissolved in an aqueous medium means that the solution containing the polysiloxane resin is uniformly “colorless and transparent” when the solution containing the polysiloxane resin is evaluated by the above method. , "Pale transparent” or “white dispersion”, and if “precipitate” is observed, it does not correspond to "stably dispersed or dissolved in an aqueous medium”.
• Monomer (B) has a salt structure consisting of an acid and a base and a radically polymerizable group, does not have a hydrolyzable silyl group, is soluble in water, and does not form micelles in water. It is a monomer.
• the radically polymerizable group in the monomer (B) undergoes radical polymerization with the radically polymerizable group in the monomer (A), and the monomer (B) is attached to the polysiloxane main chain. form the derived graft chain. Since the monomer (B) has a salt structure consisting of an acid and a base and is soluble in water, the present polysiloxane resin can be stably dispersed or dissolved in an aqueous medium.
• the radically polymerizable unsaturated group in the monomer (B) is not particularly limited as long as it can contribute to radical polymerization with the monomer (A).
• examples of radically polymerizable unsaturated groups in the monomer (B) include (meth)acryloyl groups, (meth)acrylamide groups, and vinyl groups. From the viewpoint of high reactivity and versatility, a (meth)acryloyl group or a (meth)acrylamide group is preferred.
• the monomer (B) is not particularly limited as long as it has a salt structure consisting of an acid and a base and has a radically polymerizable group.
• Examples include sodium sulfoethyl methacrylate and acrylamide-t. Sodium butylsulfonate, Sodium 2-(methacryloyloxy)ethanesulfonate, Sodium acrylamide-tbutylsulfonate, Potassium 2-(methacryloyloxy)ethanesulfonate, Potassium acrylamide-tbutylsulfonate, 2-(Methacryloyloxy)ethane Calcium sulfonate, calcium acrylamide-t-butylsulfonate, ammonium sulfoethyl methacrylate, ammonium acrylamide-t-butylsulfonate, ammonium 2-(methacryloyloxy)ethanesulfonate, ammonium acrylamide-t
• the monomer (B) can be obtained as a commercial product.
• commercial products include "Antox MS-2N-D” manufactured by Nippon Nyukazai Co., Ltd., “ATBS-Na” manufactured by Toagosei Co., Ltd., and "Acrylic sodium acid”, “potassium acrylate”, and the like.
• the structural unit (c) is derived from the monomer (C) which has a radically polymerizable group, does not have a hydrolyzable silyl group, and is capable of forming micelles in water.
• the radically polymerizable group in the monomer (C) undergoes direct or indirect radical polymerization with the radically polymerizable group in the monomer (A) to form the monomer on the polysiloxane main chain.
• a graft chain derived from body (C) is formed.
• the present polysiloxane-based resin can have an appropriate viscosity by forming micelles when water-based, and can be applied to water-based paints and the like. .
• micelle means an assembly formed by association of amphiphilic molecules through hydrophobic interactions.
• an amphipathic molecule intends a molecule having a hydrophobic group and a hydrophilic group in the molecule. Therefore, "a structure capable of forming micelles in water” means a structure having a hydrophobic group and a hydrophilic group in the molecule.
• the monomer (C) can be an amphiphilic molecule that does not have a hydrolyzable silyl group.
• Whether or not "micelles can be formed in water” is determined by the following method: 1 g of the target monomer is added to a two-layer liquid containing 10 g of water and 2 g of butyl acetate. After sufficient stirring and standing for 12 hours, if uniform white turbidity is observed, it is determined that the monomer of interest is capable of forming micelles in water. If a transparent layer of water and butyl acetate can be seen to be separated after standing for 12 hours, it is determined that the target monomer does not form micelles in water (impossible to form micelles).
• the term "having an appropriate viscosity” means that the viscosity of the solution containing the polysiloxane resin is 7000 mPa S or less when the viscosity of the solution is measured, and 6000 mPa S. It is preferably 5000 mPa ⁇ S or less, more preferably 4000 mPa ⁇ S or less.
• the viscosity of the solution containing the polysiloxane resin is measured by the method described in Examples.
• the monomer (C) has a radically polymerizable group, has a structure that forms micelles in water (that is, a structure having a hydrophobic group and a hydrophilic group in the molecule), and There are no particular limitations as long as it is a monomer that does not have a decomposable silyl group.
• the hydrophobic group in the monomer (C) is not particularly limited, but examples thereof include an alkyl group having 3 or more carbon atoms and an aryl group having a radically polymerizable group.
• the hydrophilic group in the monomer (C) is not particularly limited. cationic hydrophilic groups, amphoteric hydrophilic groups such as betaine, and nonionic hydrophilic groups such as polyoxyalkylene.
• the monomer (C) preferably has a polyoxyalkylene structure from the viewpoint of versatility.
• examples of such monomers include polyoxyethylene and polyoxypropylene.
• the monomer (C) preferably has a polyoxyalkylene structure having 1 to 100 repeating units of oxyalkylene, more preferably has a polyoxyalkylene structure having 2 to 50, and has 5 to 20. It is more preferable to have a polyoxyalkylene structure.
• the monomer (C) is not particularly limited as long as it is included in the above definition. -2025, SR-3025, SR-10S, NE-10, NE-20, NE-30, NE-40, SE-10, SE-20, ER-10, ER-20, ER-30, ER-40 , Nippon Emulsifier Co., Ltd. Antox-MS-60, RMA-1120, RMA-564, RMA-568, RMA-506, MA-30, MA-50, MA-100, MA-150, RMA-1120, MPG130 -MA, MPG-130MA, RMA-150M, RMA-300M, RMA-450M, RA-1020, RA-1820, Daiichi Kogyo Seiyaku Co., Ltd.
• Adekaria Soap SR-10 is preferred from the viewpoint of versatility and micelle stability.
• the monomer (C) may have a salt structure consisting of an acid and a base.
• the salt structure is, for example, a neutral salt structure of a strong acid and a strong base, a neutral salt structure of a strong acid and a weak base, a neutral salt structure of a weak acid and a strong base, or a neutral salt structure of a weak acid and a weak base.
• the salt structure is preferably sodium sulfonate or ammonium sulfonate.
• the content of the structural unit (c) is, for example, 0.5% by weight or more, preferably 1% by weight, with respect to 100% by weight of the total amount of the polysiloxane resin. % or more, more preferably 2% by weight or more.
• the content of the structural unit (c) is within the above range, there is an effect that a solution having an appropriate viscosity can be obtained when the polysiloxane resin is dissolved in an aqueous medium.
• the upper limit of the content of the structural unit (c) is, for example, 15% by weight or less, preferably 10% by weight or less, and more preferably 8% by weight or less.
• the obtained cured product has good water resistance.
• the ratio of the content of the monomer (B) to the content of the monomer (C) with respect to the total amount of 100% by weight of the polysiloxane resin (monomer (B)/ Monomer (C)) is preferably 1/4 to 5/1, more preferably 1/4 to 4/1, even more preferably 1/3 to 3/1, It is more preferably 1/2 to 2/1, and particularly preferably 1/1.5 to 1.5/1.
• the ratio of the content of the monomer (B) to the content of the monomer (C) is within the above range, it can be stably dispersed or dissolved in an aqueous medium, and when it is made into a solution, it is moderately It is possible to provide a polysiloxane resin having a high viscosity.
• Structural unit (d) has the following general formula (II): R 4 n —Si—(OR 5 ) 4-n (II) It is a structural unit derived from the silane compound (D) represented by.
• the silane compound (D) has the following general formula (II): R 4 n —Si—(OR 5 ) 4-n (II) (In the formula, each R 4 is independently an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms or an unsubstituted or substituted aryl group, and when there are multiple R 4 s, they may be the same or different, Each R 5 is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and n is an integer of 0 to 3.) is a silane compound having a hydrolyzable silyl group represented by The silane compound (D) undergoes dehydration condensation with the silane compounds (A) and/or (D) to form polysiloxane.
• the silane compound (D) can also be said to be a silane compound having no radically polymerizable unsaturated group and having a hydrolyzable silyl group.
• the silane compound (D) may be referred to as a monomer (D).
• the structural unit (d) may be composed of only one silane compound (D) represented by general formula (II), or may be composed of a combination of two or more silane compounds (D).
• alkyl group for R 4 in general formula (II) include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, amyl group, isoamyl group, hexyl group, cyclohexyl group, cyclohexyl Examples include methyl group, cyclohexylethyl group, heptyl group, isoheptyl group, n-octyl group, isooctyl group, 2-ethylhexyl group and the like.
• aryl group for R 4 in general formula (II) include a phenyl group, a naphthyl group, a benzyl group and the like.
• R 5 in general formula (II) is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl and decyl. and the like.
• Specific compounds represented by general formula (II) include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyl triethoxysilane, ethyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltriisopropoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltriisopropoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane Silane, hexyltriisopropoxysilane, octyltrimethoxysilane, octyltriethoxysilane,
• n in general formula (II) may be an integer of 0 to 3, but a trialkoxysilane compound in which n is 1 is particularly preferred.
• n 1, there are three crosslinkable hydrolyzable silyl groups, a polymer having a network structure can be formed, and improvement in durability and weather resistance of the obtained polysiloxane resin can be expected.
• Specific examples of the compound represented by formula (II) in which n is 1 include methyltrimethoxysilane, phenyltrimethoxysilane and the like from the viewpoint of availability.
• the number of carbon atoms in the alkyl group of R 5 in general formula (II) is preferably 1 to 3, most preferably. is 1.
• the content of the structural unit (d) is, for example, 15% by weight or more, preferably 25% by weight or more, relative to 100% by weight of the total amount of the polysiloxane resin. , more preferably 35% by weight or more.
• the content of the structural unit (d) is 15% by weight or more, effects such as high weather resistance, toughness and low tackiness can be obtained.
• the upper limit of the content of the structural unit (d) is not particularly limited as long as the effect of the present invention is exhibited, but is, for example, 80% by weight or less.
• the total content of the structural units (a) and (d) is 100% by weight of the polysiloxane resin.
• it is 10% by weight or more, preferably 20% by weight or more, and more preferably 40% by weight or more.
• the present polysiloxane resin exhibits excellent weather resistance, toughness, tackiness and the like.
• the upper limit of the total content of the structural units (a) and (d) is not particularly limited as long as the effect of the present invention is exhibited, but is, for example, 90% by weight or less.
• the structural unit (e) is derived from the monomer (E) having a radically polymerizable unsaturated group other than the above (A), (B) and (C).
• the monomer (E) from which the structural unit (e) is derived is directly or indirectly bonded to the monomer (A) and/or (B) and/or (C) by radical polymerization to form a structural unit ( Binds to a) and/or (b) and/or (c).
• the monomer (E) from which the structural unit (e) is derived is not particularly limited as long as it is a monomer having a radically polymerizable unsaturated group other than the above (A), (B) and (C). , for example, (meth)acrylic acid alkyl esters as shown below and monomers other than (meth)acrylic acid alkyl esters.
• the (meth)acrylic acid alkyl ester is a (meth)acrylic acid ester having an alkyl group having 1 to 18 carbon atoms and does not contain a functional group such as a hydroxyl group or an epoxy group (meta ) alkyl monomers.
• the alkyl group in the (meth)acrylic acid alkyl ester may be linear or branched, or may be a cyclic cycloalkyl group.
• Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, benzyl (meth) acrylate, Cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)methacrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate and the like.
• Monomers other than (meth)acrylic acid alkyl esters include, for example, nitrile group-containing radically polymerizable monomers such as (meth)acrylonitrile; hydroxyl group-containing radically polymerizable monomers such as glycidyl (meth)acrylate; - hydroxypropyl (meth) acrylate; 2-hydroxypropyl (meth) acrylate; ethylene glycol di (meth) acrylate, a monomer having two or more polymerizable unsaturated bonds such as allyl (meth) acrylate; trifluoro ( Fluorine-containing radical polymerization of meth)acrylate, pentafluoro(meth)acrylate, perfluorocyclohexyl(meth)acrylate, 2,2,3,3-tetrafluoropropyl methacrylate, ⁇ -(perfluorooctyl)ethyl(
• the content of the structural unit (e) is, for example, 10% by weight or more, preferably 20% by weight or more, relative to 100% by weight of the total amount of the polysiloxane resin. , more preferably 30% by weight or more.
• the upper limit of the content of the structural unit (e) is not particularly limited as long as the effect of the present invention is exhibited, but is, for example, 90% by weight or less, preferably 80% by weight or less, and more preferably 70% by weight. % by weight or less.
• the weight average molecular weight of the present polysiloxane resin is, for example, 1,000 to 1,000,000, preferably 3,000 to 500,000, more preferably 4,000 to 100,000.
• the weight average molecular weight of the main chain in the present polysiloxane resin is 100 to 500,000, preferably 500 to 100,000, more preferably 1,000 to 50,000. If the weight average molecular weight of the present polysiloxane resin is within the above range, there is an advantage that weather resistance and durability can be compatible with viscosity.
• the polysiloxane structure (structural unit (a), or structural units (a) and (d)) that is the main chain in the polysiloxane-based resin, and the graft chain that is the side chain (structural
• the ratio with the units (b), (c), (e)) is, for example, 20:80 to 80:20, preferably 30:70 to 75:25, more preferably 35:65. ⁇ 70:30.
• the upper limit of the above ratio is preferably 85:15 or less from the viewpoint of storage stability.
• the lower limit of the above ratio is preferably 30:70 or more from the viewpoint of water resistance, weather resistance, low tackiness, and the like.
• the ratio of each structural unit contained in the present polysiloxane resin is determined from the amount of each monomer contained in the present polysiloxane resin. , is proportional to the amount excluding the structure separated by dehydration condensation reaction or the like. That is, the amount (% by weight) of each structural unit with respect to 100% by weight of the total amount of the present polysiloxane resin takes into account the amount of weight to be reduced during the synthesis of the polysiloxane resin from the blending amount of the monomers constituting each structural unit. It can be said that it is the quantity.
• the weight average molecular weight of the polysiloxane resin is not particularly limited, but is, for example, 5,000 to 500,000, preferably 8,000 to 100,000, and more preferably 10,000 to 80,000.
• the weight average molecular weight of the polysiloxane resin is measured using a high-speed GPC device HLC-8320GPC manufactured by Tosoh Corporation.
• the resin composition according to one embodiment of the present invention (hereinafter referred to as "this resin composition") is prepared according to the above [2. polysiloxane-based resin].
• the present polysiloxane-based resin contained in the present resin composition can be stably dispersed or dissolved in an aqueous medium, and can provide a polysiloxane-based resin having an appropriate viscosity when water-based. , useful in water-based paint applications.
• the present resin composition can preferably be an aqueous medium.
• the resin composition described in [2. polysiloxane resin] for example, water at a ratio of 30% by weight or more and a non-aqueous solvent at a ratio of 10% by weight or less, preferably water at 35% by weight or more, and , a non-aqueous solvent at a ratio of 5% by weight or less, more preferably, water at a ratio of 37% by weight or more, and a non-aqueous solvent at a ratio of 3% by weight or less.
• Non-aqueous solvent as used herein means all solvents other than water.
• the “non-aqueous solvent” used herein may be a mixed solvent containing water, and includes solvents containing less than 50% by weight of water.
• the non-aqueous solvent is not particularly limited as long as it satisfies the above definition.
• Examples include hydrocarbons such as toluene, xylene, n-hexane, and cyclohexane; acetic esters such as ethyl acetate and butyl acetate; cellosolves such as butyl cellosolve; ether esters such as cellosolve acetate; ketones such as methyl ethyl ketone, ethyl acetoacetate, acetylacetone, methyl isobutyl ketone and acetone; Alcohols etc. are mentioned.
• hydrocarbons such as toluene, xylene, n-hexane, and cyclohexane
• acetic esters such as ethyl acetate and butyl acetate
• cellosolves such as butyl cellosolve
• ether esters such as cellosolve acetate
• ketones such as methyl ethyl ketone, ethyl
• the present resin composition is the above [2.
• Polysiloxane-based resin] may contain a curing catalyst in addition to the polysiloxane-based resin.
• a curing catalyst that promotes the hydrolytic condensation reaction of the hydrolyzable silyl groups promotes the cross-linking reaction.
• the curing catalyst is not particularly limited, but examples include organometallic compounds and basic catalysts. Among them, organic tin compounds and amine compounds are preferable from the viewpoint of activity.
• organometallic compounds examples include organotin compounds and organotitanium compounds. Among them, an organic tin compound is preferable from the viewpoint that the cured film is less likely to be colored.
• organic tin compounds include dibutyltin dilaurate, dibutyltin dimaleate, dibutyltin dioleyl maleate, dioctyltin dilaurate, dibutyltin diacetate, dibutyltin dimethoxide, dibutyltin thioglycolate, dibutyltin bisisononyl 3-mercaptopropio.
• dibutyltin bisisooctylthioglycolate dibutyltin bis-2-ethylhexylthioglycolate, dimethyltin bisdodecyl mercaptide, dimethyltin bis(octylthioglycolic acid ester) salt, tin octylate and the like.
• dibutyltin thioglycolate dibutyltin bisisononyl 3-mercaptopropionate
• dibutyltin bisisooctylthioglycolate dibutyltin bis-2-ethylhexylthioglycolate
• dimethyltin bis Mercaptide compounds such as dodecyl mercaptide, dibutyltin bisdodecyl mercaptide, dimethyltin bis(octylthioglycolic acid ester) salts are preferred.
• Examples of basic catalysts include inorganic base compounds and amine compounds. Among them, amine compounds can be preferably used.
• amine compounds include triethylamine, n-butylamine, hexylamine, triethanolamine, diazabicycloundecene, and ammonia.
• the present resin composition may contain additives commonly used in the technical field (in particular, the field of paints) as long as the effects of the present invention are exhibited.
• additives include pigments, fillers, plasticizers, film forming aids, wetting agents, dispersants, thickeners, antifoaming agents, preservatives, antioxidants, anti-settling agents, leveling agents. , ultraviolet absorbers, antistatic agents, antifreeze agents, antibacterial agents, antifungal/antialgae agents, tackifiers, antirust agents, hydrophilizing agents, and the like.
• As an additive only 1 type may be contained and 2 or more types may be contained. The amount of these additives can be appropriately set by those skilled in the art according to the purpose of use.
• Antifoaming agents that can be contained in the present resin composition include, more specifically, silicone antifoaming agents, surfactant antifoaming agents, polyether antifoaming agents, higher alcohol antifoaming agents, acrylic antifoaming agents, A foaming agent etc. are mentioned. Among these, silicone-based antifoaming agents are preferred because they have the advantage of being more excellent in antifoaming properties.
• the hydrophilizing agent that the present resin composition may contain includes silicates (silicates), surfactants, and the like.
• silicates are preferable because they have the advantage of being able to provide a cured film having excellent weather resistance and durability.
• a water-based solution or dispersion (hereinafter also referred to as “the solution or the dispersion”) is provided comprising the resin composition.
• the term “water-based solution” refers to a liquid that has a transparent appearance when the resin solid content concentration is 20% and the proportion of water in the total medium is 90% by weight or more. means a liquid having a haze value of 20.0 or less at 1 atmosphere and 25°C.
• the term “water-based dispersion” refers to a liquid that has a cloudy appearance when the resin solid content concentration is 20% and the proportion of water in the total medium is 90% by weight or more. More specifically, it means a liquid with a haze value higher than 20.0 at 1 atmosphere and 25°C. The haze value is measured using COH400 manufactured by Nippon Denshoku Industries Co., Ltd. using pure water as a standard solution.
• the present solution or the present dispersion contains the above-mentioned present resin composition, it can be stably dispersed or dissolved in a solution using water as a medium, and when used as a water-based paint, a paint having an appropriate viscosity is obtained. It is useful because it can be obtained.
• a water-based paint (hereinafter also referred to as "the present water-based paint") containing the present resin composition, the present solution, or the present dispersion is provided. Since the present water-based paint contains the above-described present aqueous solution or present dispersion, it can be stably dispersed or dissolved in a solution containing water as a medium, and has an appropriate viscosity, which is useful.
• the water-based paint may contain additives commonly used in the technical field (especially the field of paint). Additives that the present water-based paint may contain are described in [3. The description in the (additives) section in the resin composition] section is incorporated as appropriate.
• the water-based paint preferably contains an antifoaming agent.
• Antifoaming agents that can be contained in the water-based paint include, more specifically, silicone antifoaming agents, surfactant antifoaming agents, polyether antifoaming agents, higher alcohol antifoaming agents, and acrylic antifoaming agents. agents and the like. Among these, silicone-based antifoaming agents are preferable because they have excellent antifoaming properties and give a cured film having a more excellent appearance.
• the water-based paint preferably contains a hydrophilizing agent because it has the advantage of being able to improve the weather resistance, durability, etc. of the resulting cured film and provide a highly antifouling (stain-resistant) cured film.
• the hydrophilizing agent that can be contained in the water-based paint includes silicates, surfactants, and the like. Among these, silicates are preferable because the weather resistance and durability of the resulting cured film can be further improved, and the antifouling properties can be further improved.
• a cured film is provided by curing the present resin composition or applying the present solution, the present dispersion or the present water-based paint. Any known curing method can be used to prepare the cured film.
• the cured film according to one embodiment of the present invention can also be said to be a cured film obtained by curing the present resin composition, or applying and curing the present solution, the present dispersion or the present water-based paint.
• the method of applying the present solution, the present dispersion or the present water-based paint is not particularly limited. It can also be applied by a reverse coating method, a gravure coating method, a bar coating method, a die coating method, a spray coating method, a kiss coating method, a wire bar coating method, a curtain coating method, or the like.
• This solution, this dispersion or this water-based paint may be applied directly onto the substrate.
• Forming an undercoat layer by coating, and applying the present solution, the present dispersion or the present water-based paint on the undercoat layer, in other words, the present solution, the present dispersion or the present water-based paint through the undercoat is preferably applied onto the substrate.
• the base material to which the present solution, the present dispersion liquid or the present water-based paint (or undercoat) is applied is not particularly limited, and may be either an organic base material or an inorganic base material.
• the cured film according to one embodiment of the present invention is preferably a cured film obtained by applying the present solution, the present dispersion or the present water-based paint onto the undercoat layer. That is, in one embodiment of the present invention, a laminate is provided in which an undercoat layer and a main cured film are laminated in this order. It can also be said that the laminate according to one embodiment of the present invention is a laminate obtained by laminating an undercoat layer and a main cured film on a substrate in this order.
• undercoats that form the undercoat layer include primers, sealers, fillers, and the like.
• the primer is not particularly limited, and various primers commonly used in the paint field can be used.
• any oil-based, water-based, or antirust primer may be used.
• Specific examples of primers include epoxy-based primers, urethane-based primers, silicon-based primers, zinc-rich primers, and the like.
• the sealer is not particularly limited, and various sealers commonly used in the paint field can be used. For example, any oil-based, water-based, or antirust sealer may be used. Specific examples of sealers include epoxy sealers, urethane sealers, silicon sealers, zinc rich sealers, and the like.
• a method for producing a polysiloxane resin according to one embodiment of the present invention comprises a monomer (A), a monomer (B), and a monomer (C ) and dehydration condensation and radical polymerization.
• the dehydration condensation and radical polymerization may be performed separately or simultaneously.
• the production method optionally further comprises separately adding the monomer (D) and / or the monomer (E) , or may be reacted simultaneously.
• the method of performing dehydration condensation and radical polymerization of each monomer at the same time includes, for example, a method including (step 1) and (step 2) shown below.
• step 1) a method including (step 1) and (step 2) shown below.
• step 2) a method including (step 1) and (step 2) shown below.
• the present manufacturing method is not limited to this.
• step 1 monomer (A), or monomers (A) and (D) (hereinafter “monomer (A)” and “monomers (A) and (D) may be collectively referred to as a “silane compound for dehydration condensation”), water, and, if necessary, a dehydration condensation catalyst, are subjected to dehydration condensation. It can also be said that step 1 is a step of obtaining a cocondensate of a silane compound for dehydration condensation.
• Step 2 After the weight average molecular weight of the entire mixture in step 1 reaches a molecular weight within a specific range, the reaction vessel is charged with a monomer (B), a monomer (C), and a radical polymerization initiator. and, optionally, the monomer (E) are continuously added to perform at least radical polymerization.
• dehydration condensation may occur between hydrolyzable silyl groups derived from the silane compound for dehydration condensation simultaneously with the radical polymerization.
• the number of moles of water added in step 1 is, for example, 0.25 times or more, preferably 0.5 times the total number of moles of the silane compound for dehydration condensation. more than double.
• the number of moles of water is 0.25 or more times the total number of moles of the dehydration-condensation silane compound, the condensation can be appropriately performed, and sufficient water resistance, weather resistance, and low tackiness can be obtained. I can expect it.
• the number of moles of water is not particularly limited as long as it is large, but from the viewpoint of production cost, it is preferably suppressed to 4.0 times or less the total number of moles of the silane compound for dehydration condensation. Based on these points of view, the number of moles of water is preferably 0.25 to 4.0 times, more preferably 0.5 to 3.0 times, the total number of moles of the silane compound for dehydration condensation. 0 to 2.5 times is particularly preferred.
• step 1 the silanol group produced by hydrolyzing the hydrolyzable silyl group undergoes dehydration condensation with the silanol group and dealcoholization condensation with the hydrolyzable silyl group. It becomes a factor that lowers the storage stability of the resin.
• silanol groups are solvated with hydrophilic solvents such as alcohols, a certain amount or more of silanol groups also has the effect of improving the storage stability of the resulting cocondensate and polysiloxane resin.
• the cocondensate tends to gel when it is concentrated in the vacuum distillation step, it may not be possible to concentrate it to a high concentration. From this point of view, the number of moles of water to be added is more preferably 2.0 times or less the total number of moles of the monomer (A) and the monomer (D).
• the amount of the monomer (A) when condensing the monomer (A) and the monomer (D) is the same as the monomer (A) and the monomer ( For example, it is 1 to 10% by weight, preferably 2 to 8% by weight, more preferably 3 to 6% by weight, relative to the total weight of D).
• the amount of the monomer (A) is within the above range, it becomes uniformly dispersed or soluble in water due to sufficient graft polymerization with the monomer (B) and the monomer (C), and It is effective in obtaining a solution having an appropriate viscosity when made into a solution.
• the dehydration-condensation catalyst in step 1 is not particularly limited as long as it is a substance capable of promoting the dehydration-condensation reaction of the mixture containing the dehydration-condensation silane compound and water.
• dehydration condensation catalysts include, for example, acidic catalysts and basic catalysts.
• an organic acid is preferable because of compatibility with the silane compound for dehydration condensation and the diluent solvent, and a phosphoric acid ester and a carboxylic acid can be preferably used.
• organic acids include ethyl acid phosphate, butyl acid phosphate, dibutyl pyrophosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, isotridecyl acid phosphate, dibutyl phosphate, bis(2-ethylhexyl) phosphate, Examples include formic acid, acetic acid, butyric acid, and isobutyric acid.
• an organic base catalyst is preferable because of compatibility with the dehydration-condensation silane compound and the diluent solvent, and an amine compound can be suitably used.
• organic bases include triethylamine, diazabicycloundecene, 1,4-diazabicyclo[2.2.2]octane and the like.
• the above acidic catalysts and basic catalysts can be used alone, or two or more of them can be used in combination.
• the amount (total amount) of the acidic catalyst and basic catalyst added is preferably 0.1 ppm to 50000 ppm, more preferably 1 ppm to 10000 ppm, relative to the total amount of the monomer (A) and the monomer (D). , 5 ppm to 1000 ppm are particularly preferred, and 10 ppm to 500 ppm are most preferred.
• the amount of the acidic catalyst and the basic catalyst added is less than 0.1 ppm, they hardly act as catalysts.
• the amount of acidic catalyst and basic catalyst is large, the reaction time can be shortened, but it is often difficult to separate and remove them from the cocondensate after the reaction is completed.
• the remaining acidic catalyst and basic catalyst may reduce the storage stability of the cocondensate and the present polysiloxane resin. is.
• the mixture in step 1 in this production method may contain a diluent solvent in addition to the dehydration-condensation silane compound, water, and dehydration-condensation catalyst. Since the silane compound for dehydration condensation is hydrophobic and water is used during the reaction, the dilution solvent is preferably water-soluble. Although the amount of the diluent solvent is not limited, it is not preferable from the production cost point of view because the concentration of the obtained polysiloxane becomes low when the amount is large.
• Diluent solvents include ether esters such as cellosolvecetate; ketones such as methyl ethyl ketone, ethyl acetoacetate, acetylacetone, methyl isobutyl ketone and acetone; methanol, 2-propanol, n-butanol, isobutanol, hexanol, octanol and the like. Alcohols etc. are mentioned.
• the diluent solvent is preferably alcohols, more preferably 2-propanol.
• the radical polymerization initiator in step 2 is not particularly limited as long as it is a substance capable of undergoing a radical polymerization reaction with the substance having a radically polymerizable group used in step 1.
• the radical polymerization initiator includes, for example, 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2' -azobis(2-methylbutyronitrile), tert-butyl peroxypivalate, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, di-tert-butyl peroxide, cumene hydroperoxide Oxide, diisopropyl peroxycarbonate, and the like.
• the amount of the radical polymerization initiator is, for example, 0.01 to 10% by weight, preferably 0.05 to 7% by weight, relative to 100% by weight of the total amount of the polysiloxane resin. %, more preferably 0.1 to 5% by weight.
• the amount of the radical polymerization initiator is 0.01% by weight or more, polymerization proceeds appropriately.
• the amount of the radical polymerization initiator is 10% by weight or less, a polymer having an appropriate molecular weight can be obtained.
• any desired Additives may be added. Such additives can be appropriately selected by those skilled in the art.
• the monomer (A), the monomer (B), the monomer (C), the monomer (D), and the monomer (E) are the above [2. polysiloxane-based resin].
• the amount of each of the above components is such that the content of "structural unit (a)" to “structural unit (e)" in the polysiloxane resin is the above [2.
• Polysiloxane-based resin] can be appropriately set by those skilled in the art so as to fall within the range described in .
• dehydration condensation and radical polymerization in this production method can be carried out in a non-aqueous solvent.
• non-aqueous solvents include the above [3. Resin composition] can be used.
• the production method preferably includes a step of replacing the non-aqueous solvent with an aqueous solvent after the dehydration condensation and radical polymerization steps.
• a polysiloxane-based resin that can be stably dispersed or dissolved in an aqueous medium and that can be used as a water-based paint can be obtained.
• the production method may be the method described in Examples.
• the present polysiloxane-based resin obtained by this production method is used, for example, for interior and exterior use in buildings, for automobiles such as metallic bases or clears on metallic bases, for direct coating of metals such as aluminum, stainless steel, silver, etc., for slate, concrete, roof tiles, Direct coating for ceramics such as mortar, gypsum board, asbestos slate, asbestos board, precast concrete, lightweight aerated concrete, calcium silicate board, tile, brick, etc., paint or surface treatment agent for glass, natural marble, granite, etc. It is preferably used as.
• one aspect of the present invention includes the following.
• ⁇ 1> As a structural unit, having a polymer containing a structural unit derived from a monomer having a radically polymerizable group,
• the monomer includes (i) a monomer that is soluble in water and does not form micelles in water, and (ii) a monomer that can form micelles in water, a polysiloxane resin .
• the (i) monomer that is soluble in water and does not form micelles in water has a salt structure consisting of an acid and a base;
• the following general formula (II): R 4 n —Si—(OR 5 ) 4-n (II) (In the formula, each R 4 is independently an unsubstituted or substituted alkyl group having 1 to
• ⁇ 5> Containing 1 to 20% by weight of the structural unit (b) and containing 1 to 10% by weight of the structural unit (c) with respect to 100% by weight of the total amount of the polysiloxane resin, ⁇ 3> Or the polysiloxane resin according to ⁇ 4>.
• ⁇ 6> The poly according to any one of ⁇ 3> to ⁇ 5>, wherein the total amount of the structural units (a) and (d) is 10% by weight or more relative to the total amount of 100% by weight of the polysiloxane resin.
• ⁇ 7> A resin composition comprising the polysiloxane resin according to any one of ⁇ 1> to ⁇ 6>.
• ⁇ 8> A water-based solution or dispersion containing the resin composition according to ⁇ 7>.
• a water-based paint comprising the resin composition according to ⁇ 7> or the water-based solution or dispersion according to ⁇ 8>.
• the water-based paint according to ⁇ 9> which contains a silicone antifoaming agent.
• ⁇ 12> A laminate obtained by laminating the undercoat layer and the cured film according to ⁇ 11> in this order.
• ER-10 "Adekari Soap ER-10” manufactured by ADEKA Corporation, commercial classification "reactive nonionic emulsifier", compound represented by the following formula (B):
• Radical polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile): manufactured by Tokyo Chemical Industry Co., Ltd. (antifreezing agent) Propylene glycol (lubricant) : "Dispex Ultra FA 4437” manufactured by BASF Japan (dispersant) : "SMA1440H Solution” manufactured by Cray Valley : “Disperbyk-2090” manufactured by Big Chemie Japan (pigment) : "PFC105” manufactured by Ishihara Sangyo Co., Ltd.
• the solution was diluted with water so that the volatile component of the polysiloxane resin was 50%, and the viscosity of the solution containing the polysiloxane resin was measured at 23° C. using a BM viscometer (rotor No. 2, 6 rpm).
• test piece (cured film on the test piece) prepared by the method described later is subjected to an accelerated weather resistance test. carried out.
• the 60° gloss value of the test piece was measured before and after 400 hours of the accelerated weather resistance test, and the gloss retention rate was calculated. Higher gloss retention indicates better weather resistance.
• test conditions for the accelerated weather resistance test are as follows.
• Illuminance 85mW/ cm2 Irradiation 63°C 50% 6 hours Condensation 30°C 98% 2 hours Shower 30 seconds before and after condensation.
• Example 1 (Preparation of cocondensate (main chain)) A reactor equipped with a stirrer, thermometer and reflux condenser was charged with 2.7 parts by weight of TSMA, 42.2 parts by weight of M-TMS, 14.7 parts by weight of Ph-TMS, and 15.4 parts by weight of pure water. and 0.017 parts by weight of DBP were charged and reacted with stirring at a reaction temperature of 105° C. for 3 hours to obtain a cocondensate.
• the cocondensate After heating, the cocondensate, ATBS-Na 5 parts by weight, SR-10 1 part by weight, MMA 32 parts by weight, BA 32 parts by weight, 2,2-azobis(2,4-dimethyl A mixed solution of 1.2 parts by weight of valeronitrile), 10 parts by weight of pure water, and 10 parts by weight of 2-propanol was dropped from the dropping funnel at a constant speed over 5 hours. Next, a mixed solution of 0.12 parts by weight of 2,2-azobis(2,4-dimethylvaleronitrile) and 5 parts by weight of 2-propanol was dropped at a constant rate over 1 hour. Subsequently, the mixture was stirred at 75° C.
• Example 2 to 5 Comparative Examples 1 to 4
• a graft cocondensate (polysiloxane-based resin) was obtained in the same manner as in Example 1, except that the amount of each monomer used was changed to the amount shown in Table 1. The stability and viscosity of the obtained polysiloxane resin were measured. Table 1 shows the results.
• the polysiloxane resins of Examples 1 to 5 gave good results in both stability and viscosity. That is, according to one embodiment of the present invention, it was shown that a polysiloxane resin that can be stably dispersed or dissolved in an aqueous medium and has an appropriate viscosity can be provided.
• the polysiloxane resins of Comparative Examples 1 to 3 showed sedimentation in an aqueous medium, resulting in poor stability. Also, the polysiloxane resins of Comparative Examples 3 and 4 had very high viscosities.
• Examples 6 to 23 (Production of water-based paint) Using the polysiloxane resins of Examples 1 to 5, each component was blended according to the formulation shown in Table 2 or Table 3 to prepare a water-based paint (white base paint).
• the prepared water-based paint was applied to glass using an applicator with a coating film thickness of 6 mils (6 mil), and cured for 1 week at a temperature of 23° C. and a humidity of 50% to prepare a coating film (cured film).
• Examples 24 to 37 (Preparation of cured film) With reference to International Publication No. 2016/052636, using the water-based paints of Examples 6-10 and 12-13, cured films were prepared, and the weather resistance of the cured films was measured. Briefly, an aluminum plate (50 mm ⁇ 150 mm) coated with Hypon Fine Primer II (manufactured by Nippon Paint) as a primer, using an air spray, on the surface of the primer layer, the dry film thickness (film thickness of the cured film after drying ) was about 40 ⁇ m, a water-based paint prepared according to the formulation shown in Table 4 or 5 was applied and dried at 23° C. and 50% RH for 4 hours (first application).
• Hypon Fine Primer II manufactured by Nippon Paint
• the present polysiloxane resin can be stably dispersed or dissolved in an aqueous medium, and when used as a water-based paint, a paint having an appropriate viscosity can be obtained. Therefore, the present polysiloxane-based resin can be suitably used in various fields such as coating agents.

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