Classifications

• • 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
  • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
  • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
  • C08F297/026—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising acrylic acid, methacrylic acid or derivatives thereof
• • 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
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/02—Emulsion paints including aerosols
  • C09D5/022—Emulsions, e.g. oil in water
• • 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
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • 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
  • C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
  • C08F259/02—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing chlorine
  • C08F259/04—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing chlorine on to polymers of vinyl chloride
• • 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
  • C09D11/00—Inks
• • 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
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
• • 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
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
• • 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
  • C09D151/003—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 by reactions only involving unsaturated carbon-to-carbon bonds
• • 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
  • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers

Definitions

• the present invention relates to a method for producing vinyl chloride composite resin particles used for hard molded bodies, soft molded bodies, paints, inks, etc., vinyl chloride composite resin particles, and products thereof.
• Vinyl chloride resins are used for a variety of purposes because they have excellent chemical resistance, water resistance, weather resistance, flame retardancy, processability, and coloring.
• Vinyl chloride resin is used as a molded body by, for example, powdering vinyl chloride resin obtained by polymerization and heat molding. Molded products of vinyl chloride resin include hard molded products that do not use plasticizers and soft molded products that use plasticizers. Since hard molded products do not use plasticizers, they have a problem of relatively low impact resistance. Therefore, as a method for improving impact resistance, a method has been proposed in which in multi-stage emulsion polymerization, an acrylic monomer is polymerized in the first stage, and then vinyl chloride is polymerized in the second stage (Patent Document 1).
• the obtained resin particles tend to have a core/shell structure with a clear boundary between the acrylic resin and the vinyl chloride resin within the particles, and in order to obtain a transparent molded product, It is necessary to reduce the particle size. Therefore, the resin particles obtained by this manufacturing method have restrictions on the applications in which they can be used.
• plasticizers have problems of decreased performance and stickiness due to plasticizer bleed. Additionally, there are some applications in which it is desired to reduce or eliminate the use of plasticizers due to concerns about the health of the plasticizers themselves.
• Patent Document 2 a method of copolymerizing a vinyl chloride monomer and an acrylic macromonomer having a low glass transition temperature
• Patent Document 2 a method of copolymerizing a vinyl chloride monomer and an acrylic macromonomer having a low glass transition temperature
• the macromonomer is highly hydrophobic and does not dissolve in water, making production by emulsion polymerization difficult. As a result, with this method, it is difficult to obtain resin particles having nano-sized particle diameters.
• vinyl chloride resin can be used for coating paints, inks, etc. by dissolving the powdered vinyl chloride resin in a solvent, or by using the latex produced by emulsion polymerization as it is. It is also sometimes used as a binder.
• the weight ratio of vinyl chloride monomer and acrylic monomer is 90% in the first stage (core).
• a core/shell resin has been proposed in which the weight ratio of vinyl chloride monomer and acrylic monomer is polymerized at 0:100 to 40:60 as the second stage (shell) after polymerization at a ratio of 0:10 to 50:50. (Patent Document 5).
• Patent Document 6 a core/shell resin latex in which a vinyl chloride resin is used as a core and an acrylic resin is used as a shell has been proposed.
• the problem to be solved by the present invention is to provide vinyl chloride-based composite resin particles that can improve impact resistance, flexibility, film formability, water resistance, adhesion, etc.
• Another object of the present invention is to provide vinyl chloride-based composite resin particles whose latex has excellent storage stability and whose coating film has a low water absorption rate.
• the present inventor polymerized a monomer mainly composed of vinyl chloride monomer in the first stage (hereinafter referred to as [Step 1]), and in the second stage and subsequent stages (hereinafter referred to as [Step 1]).
• Composite resin particles obtained by polymerizing monomers mainly composed of acrylic monomers (referred to as 2) have improved impact resistance, flexibility, film formability, and water resistance, which are the issues faced by vinyl chloride resins. It has been found that adhesion, etc. can be improved.
• the method for manufacturing composite resin particles according to one embodiment of the present invention includes the following configuration.
• a method for producing composite resin particles including Step 1 and Step 2, and in Step 2, a redox type polymerization initiator containing a polymerization initiator and a reducing agent is used.
• Step 1 (a1) more than 90 parts by weight of vinyl chloride monomer and not more than 100 parts by weight, and (a2) monomer consisting of 0 parts by weight or more and less than 10 parts by weight of an ethylenically unsaturated monomer copolymerizable with vinyl chloride monomer [Here, the total amount of (a1) and (a2) is 100 parts by weight] ] to obtain (A) a vinyl chloride resin; [Step 2] Copolymerizable with (b1) 50 to 100 parts by weight of (meth)acrylic acid alkyl ester monomer and (b2) (meth)acrylic acid alkyl ester in the presence of the vinyl chloride resin (A).
• a hard molded body with improved impact resistance a soft molded body with reduced or no use of plasticizer, film-forming properties, flexibility, water resistance, and adhesion Coating materials such as paints and inks with improved properties can be obtained.
• vinyl chloride-based composite resin particles whose latex has excellent storage stability and whose coating film has a low water absorption rate.
• the first stage in the multi-stage emulsion polymerization, contains (a1) more than 90 parts by weight of vinyl chloride monomer and 100 parts by weight or less, and (a2) chloride monomer.
• a monomer mixture consisting of 0 parts by weight or more and less than 10 parts by weight of an ethylenically unsaturated monomer copolymerizable with a vinyl monomer [here, the total amount of (a1) and (a2) is 100 parts by weight] .
• the mechanism is that the monomers constituting the (B) acrylic resin permeate into the (A) vinyl chloride resin particles obtained in [Step 1] and polymerize within the particles. It is considered that the resin and the acrylic resin (B) do not form a clear core/shell structure within the particles, but exist in an entangled manner. As a result, composite resin particles having characteristics different from those of the prior art can be obtained.
• more than 90 parts by weight and not more than 100 parts by weight means more than 90 parts by weight and not more than 100 parts by weight.
• 50 parts by weight to 100 parts by weight means 50 parts by weight or more and 100 parts by weight or less.
• (A) vinyl chloride resin includes (a1) more than 90 parts by weight of vinyl chloride monomer and 100 parts by weight or less, and (a2) vinyl chloride monomer.
• a monomer mixture consisting of 0 parts by weight or more and less than 10 parts by weight of an ethylenically unsaturated monomer copolymerizable with [the total of (a1) and (a2) is 100 parts by weight] is polymerized or copolymerized by emulsion polymerization. It is obtained by polymerization and is polymerized as the first stage of multi-stage emulsion polymerization.
• Step 1] may be performed once, or may be performed in multiple steps by changing the composition of the monomer mixture.
• the (A) vinyl chloride resin in [Step 1] The composition may be relatively simple, and (a1) vinyl chloride monomer may be used alone. However, copolymerization with other monomers is not ruled out, and if necessary, it is possible to use (a2) an ethylenically unsaturated monomer copolymerizable with vinyl chloride monomer. It is.
• the amount of (a2) used is preferably 0 parts by weight or more and less than 10 parts by weight, more preferably 0 parts by weight to 5 parts by weight.
• the (a2) ethylenically unsaturated monomer copolymerizable with the vinyl chloride monomer used in [Step 1] is not particularly limited, and for example, ethylene , propylene, butene; vinyl esters such as vinyl acetate, vinyl versatate, vinyl propionate, vinyl stearate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, octyl vinyl ether, lauryl vinyl ether; vinylidene such as vinylidene chloride unsaturated carboxylic acids and their acid anhydrides such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, maleic anhydride, itaconic anhydride; methyl (meth)acrylate, ethyl (meth)acrylate, Unsaturated carboxylic acid esters such as monomethyl maleate, dimethyl maleate, and butylbenzyl maleate; Aromatic vinyl compounds such as s
• (E) at least two non-conjugated A compound having a bond can also be used in combination.
• the compound (E) having at least two non-conjugated double bonds used in [Step 1] in one embodiment of the present invention is not particularly limited, and includes, for example, allyl methacrylate, allyl acrylate, Triallyl cyanurate, triallyl isocyanurate, diallyl fumarate, diallyl maleate, diallyl phthalate, triallyl trimellitate, trimethylolpropane diallyl ether, divinyl adipate, divinylbenzene, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1 , 3-butylene dimethacrylate, monoethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylol propane trimethacrylate, polyethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, di
• (E) a compound having at least two non-conjugated double bonds must have two or more allyl groups.
• Particularly preferred are triallyl cyanurate (hereinafter sometimes abbreviated as [TAC]) having three allyl groups, triallyl isocyanurate, and triallyl trimellitate.
• the compound having at least two non-conjugated double bonds may be used alone or in combination of two or more.
• the amount of the compound having at least two non-conjugated double bonds is the total amount of (a1) vinyl chloride monomer and (a2) ethylenically unsaturated monomer copolymerizable with vinyl chloride monomer. Based on 100 parts by weight, the amount is preferably 5 parts by weight or less, more preferably 1 part by weight or less, and even more preferably 0.3 parts by weight or less. If the amount of (E) used is 5 parts by weight or less, the degree of crosslinking of the vinyl chloride resin (A) will not become too high, so it will not impede the penetration of the acrylic monomer polymerized in [Step 2], This is preferable because intra-particle compounding progresses well.
• an ionic or nonionic surfactant commonly used in emulsion polymerization methods can be used.
• Examples of the ionic surfactant used in [Step 1] include polyoxyethylene nonylphenyl ether sulfate, polyoxyethylene allyl ether sulfate, octylphenoxyethoxyethyl sulfonate, polyoxyethylene tridecyl ether sulfate, polyoxyethylene Anionic surfactants with polyoxyalkylene chains such as polycyclic phenyl ether sulfate; sulfonates such as sodium lauryl sulfonate, sodium dodecylbenzenesulfonate, and sodium isooctylbenzenesulfonate; imidazoline laurate, ammonium hydro Examples include ammonium salts such as oxides; sulfosuccinic acid surfactants such as sodium dilauryl sulfosuccinate;
• nonionic surfactant used in [Step 1] examples include polyoxylated surfactants such as polyoxyethylene dodecyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, and polyoxyethylene polyoxypropylene lauryl ether. Examples include alkylenes.
• the surfactants used in [Step 1] may be used alone or in combination of two or more.
• the amount of surfactant used in [Step 1] is preferably 10 parts by weight or less, more preferably 0.5 parts to 8 parts by weight, based on 100 parts by weight of the total monomer mixture (A).
• the surfactant used in [Step 1], (C) using a reactive surfactant having a polymerizable double bond in one molecule It is preferable from the viewpoints of suppressing the generation of new particles during emulsion polymerization, water resistance of the resulting coating film (particularly reduced water absorption, reduced water whitening, etc.), weather resistance, and gloss.
• a reactive surfactant having a polyoxyalkylene group in the molecule by using a reactive surfactant having a polyoxyalkylene group in the molecule, the mechanical stability and storage stability of the resulting composite resin particle latex can be improved.
• Adekariasoap registered trademark
• ER-10 ER- manufactured by ADEKA Co., Ltd. 20
• ER-30, ER-40 SR-05, SR-10, SR-20, SR-1025,
• examples of the polymerization initiator used in [Step 1] include organic peroxides, azo initiators, and peroxodisulfates (also referred to as "persulfates”). , hydrogen peroxide, and the like.
• examples of the organic peroxides include t-butyl hydroperoxide, cumene hydroperoxide, t-butylperoxyisopropyl carbonate, paramenthane hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide. , benzoyl peroxide, lauroyl peroxide, and the like.
• azo initiator examples include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2 , 4-dimethylvaleronitrile) and the like.
• peroxodisulfate examples include ammonium persulfate, potassium persulfate, sodium persulfate, and the like.
• the amount of the polymerization initiator used in [Step 1] is preferably 0.01 to 5 parts by weight, and 0.02 parts by weight based on 100 parts by weight of the total monomer mixture of (a1) + (a2). -3 parts by weight is more preferred. If the amount of the polymerization initiator used is 0.01 parts by weight or more, polymerization will proceed suitably. Moreover, if it is 5 parts by weight or less, heat generation control can be performed suitably.
• the usage amount of the polymerization initiator includes the usage amount of the reducing agent and the redox catalyst when the reducing agent described below is used together, or when the reducing agent and the redox catalyst are used together. The intent is not to.
• the polymerization initiator used in [Step 1] includes sodium sulfite, sodium thiosulfate, sodium hydroxymethanesulfinate, ascorbic acid, sodium ascorbate, Rongalite, Bruggolite ( It can be used as a redox type polymerization initiator in combination with a reducing agent such as FF-6 (registered trademark) or thiourea dioxide.
• a reducing agent such as FF-6 (registered trademark) or thiourea dioxide.
• Bruggolite (registered trademark) FF-6 and thiourea dioxide which do not generate formaldehyde, are particularly preferable as the reducing agent.
• These reducing agents may be used alone or in combination of two or more.
• the amount of the reducing agent used is preferably 0.5 times to 10 times, and 0.6 times to 10 times the weight of the polymerization initiator combined as the redox type polymerization initiator. 7 times the amount is more preferable.
• the amount of the reducing agent used is within the above range, it is preferable because stable polymerization behavior is exhibited.
• the organic peroxide is preferably used as a redox type polymerization initiator in combination with a reducing agent, especially from the viewpoint of polymerization stability and water resistance.
• the redox type polymerization initiator using an organic peroxide and a reducing agent in combination may be used in combination with a redox type catalyst shown below.
• the above redox type polymerization initiator may further be used in combination with a redox catalyst.
• the above redox type polymerization initiator may be used in the presence of a redox catalyst.
• a redox catalyst for example, a transition metal complex produced by using a transition metal salt and a chelating agent in combination can be used.
• the transition metal salt include ferrous (II) sulfate, copper (II) sulfate, copper chloride, etc.
• the chelating agent include disodium ethylenediaminetetraacetate (EDTA ⁇ 2Na), tartaric acid, etc. , ammonia, etc.
• ferrous sulfate (II) is used as the transition metal salt and disodium ethylenediaminetetraacetate (hereinafter sometimes referred to as "EDTA ⁇ 2Na" in this specification) is used as the chelating agent, Fe- EDTA is produced and functions as a redox catalyst.
• EDTA ⁇ 2Na disodium ethylenediaminetetraacetate
• the amount of transition metal salt used in the redox catalyst when used in combination with a redox type polymerization initiator is preferably 0.001 times to 0.05 times the amount of the reducing agent used. More preferably, the amount is 0.002 times to 0.03 times.
• the amount of the chelating agent used in the redox catalyst is preferably 1 to 10 times the weight of the transition metal salt.
• (B) Acrylic resin In one embodiment of the present invention, (B) acrylic resin is produced in the presence of (A) vinyl chloride resin produced in [Step 1], and in [Step 2], the acrylic monomer is It is obtained by polymerizing a mixture of polyvinyl chloride and vinyl chloride, and when combined with vinyl chloride resin, it imparts various functions.
• the mechanism is that the monomers constituting the (A) acrylic resin penetrate into the vinyl chloride resin particles present in the system and polymerize within the particles, whereby the (A) vinyl chloride resin and (B) It is thought that the acrylic resin exists entangled within the particles.
• (B) by adjusting the composition of the monomers constituting the (B) acrylic resin and changing the balance of hydrophilicity and hydrophobicity, (B) There is a possibility that the position of the acrylic resin can be adjusted arbitrarily. That is, when (B) an acrylic resin is made to have a composition that is more hydrophobic than (A) a vinyl chloride resin, conversely, if the composition is made to be more hydrophobic than (A) a vinyl chloride resin, It is considered that when the composition has a high content, it is possible to have a large amount of it present on the outside of the particle. Furthermore, if the hydrophilicity/hydrophobicity is the same as that of (A) vinyl chloride resin, it is thought that the position of the resin will be nearly uniform.
• Step 2 may be performed once, or may be performed in multiple steps by changing the composition of the monomer mixture.
• the polymerization composition of (B) acrylic resin in [Step 2] is (b1) 50 to 100 parts by weight of (meth)acrylic acid alkyl ester monomer, and (b2) It consists of 0 to 50 parts by weight of an ethylenically unsaturated monomer copolymerizable with (meth)acrylic acid alkyl ester [here, the total amount of (b1) and (b2) is 100 parts by weight. ].
• specific examples of the (b1) (meth)acrylic acid alkyl ester monomer used in [Step 2] include methyl (meth)acrylate, ethyl (meth)acrylate, etc. , iso-propyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylic acid 2 - Ethylhexyl, isodecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, and the like.
• These (b1) (meth)acrylic acid alkyl esters may be used alone or in combination of two or more.
• the ethylenically unsaturated monomer copolymerizable with (b2) (meth)acrylic acid alkyl ester used in [Step 2] is (b1) (meth)acrylic acid alkyl ester.
• (b2) include aromatic hydrocarbon vinyl monomers such as styrene, ⁇ -methylstyrene, chlorostyrene, 4-hydroxystyrene, and vinyltoluene; vinyl acetate, vinyl propionate, and vinyl versatate.
• vinyl esters such as; allyl compounds; nitrile group-containing vinyl monomers such as (meth)acrylonitrile; macromonomers AS-6, AN-6, AA-6, AB-6 manufactured by Toagosei Co., Ltd.; Compounds such as AK-5; vinyl methyl ether, propylene, butadiene, vinyl chloride, vinylidene chloride, and the like.
• ethylenically unsaturated monomers copolymerizable with (meth)acrylic acid alkyl ester may be used alone or in combination of two or more.
• a vinyl monomer having an acid group can also be used as (b2) used in [Step 2].
• an acid group such as a carboxyl group or a sulfonic acid group
• the mechanical stability and chemical stability of the resulting composite resin particle latex and its adhesion to a substrate when used as a coating film can be improved.
• vinyl monomers having acid groups include unsaturated carboxylic acids and their acid anhydrides, such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, maleic anhydride, and itaconic anhydride.
• Monomers having a sulfonic acid group such as sodium styrene sulfonate, sodium 2-sulfoethyl methacrylate, ammonium 2-sulfoethyl methacrylate, acrylamide tert-butyl sulfonic acid, and sodium acrylamide tert-butyl sulfonate.
• Vinyl monomers having acid groups may be used alone or in combination of two or more.
• the amount of the vinyl monomer having an acid group used is preferably 0.2 parts by weight to 10 parts by weight, when the total amount of the monomer mixture constituting (A) and (B) is 100 parts by weight.
• the amount is more preferably .5 parts by weight to 10 parts by weight, even more preferably 0.5 parts by weight to 6 parts by weight, even more preferably 1 part by weight to 5 parts by weight.
• the amount of the vinyl monomer having an acid group is 0.2 parts by weight or more, the resulting composite resin particle latex has excellent mechanical stability, chemical stability, and storage stability. Further, if it is 10% by weight or less, a sudden increase in latex viscosity and a decrease in water resistance will not occur, which is preferable.
• a vinyl monomer having a hydroxyl group can also be used as (b2) used in [Step 2]. Having a hydroxyl group is preferable in that it is possible to introduce a crosslinking point with isocyanate, melamine, etc., which improves the dispersibility of the pigment.
• vinyl monomer having a hydroxyl group examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxyethyl vinyl ether, hydroxystyrene; Toagosei Co., Ltd. ) manufactured by Aronix (registered trademark) 5700; placedl (registered trademark) FA-1, FA-4, FM-1, FM-4 manufactured by Daicel Chemical Co., Ltd.; HE-10, HE-20 manufactured by Nippon Shokubai Chemical Co., Ltd.
• hydroxyl group-containing vinyl-based modified hydroxyalkylvinyl monomers HP-10, HP-20; Bremmer (registered trademark) PEP series manufactured by NOF Corporation; NKH-5050; GLM; hydroxyl group-containing vinyl-based modified hydroxyalkylvinyl monomers.
• the vinyl monomers having hydroxyl groups may be used alone or in combination of two or more.
• the amount of the vinyl monomer having a hydroxyl group to be used is preferably 0.2 parts by weight to 50 parts by weight, and 1 part by weight when the total amount of the monomer mixture constituting (A) and (B) is 100 parts by weight. Parts by weight to 30 parts by weight are more preferred, and 2 parts to 20 parts by weight are even more preferred.
• a vinyl monomer having a polyoxyalkylene chain can also be used. Having a polyoxyalkylene chain is preferable in that it improves the mechanical stability and chemical stability of the resulting composite resin particle latex even when a vinyl monomer having an acid group is not used.
• vinyl monomer having a polyoxyalkylene chain examples include, for example, Bremmer (registered trademark) PE-90, PE-200, PE-350, AE-90, AE-200 manufactured by NOF Corporation. , AE-350, PP-500, PP-800, PP-1000, AP-400, AP-550, AP-800, 700PEP-350B, 10PEP-550B, 55PET-400, 30PET-800, 55PET-800, 30PPT -800, 50PPT-800, 70PPT-800, PME-100, PME-200, PME-400, PME-1000, PME-4000, AME-400, 50POEP-800B, 50AOEP-800B, AEP, AET, APT, PLE , ALE, PSE, ASE, PKE, AKE, PNE, ANE, PNP, ANP, PNEP-600; Light Ester (registered trademark) 130MA, 041MA, MTG, Light
• the vinyl monomer having a polyoxyalkylene chain may be used alone or in combination of two or more types.
• the amount of the vinyl monomer having a polyoxyalkylene chain used is preferably 0.2 parts by weight to 10 parts by weight when the total amount of the monomer mixture constituting (A) and (B) is 100 parts by weight. , more preferably from 1 part by weight to 10 parts by weight, and even more preferably from 2 parts by weight to 5 parts by weight.
• (E) a compound having at least two non-conjugated double bonds can be used.
• the generated particles have a crosslinked structure inside, and the water resistance of the formed coating film is improved.
• the amount of the compound having at least two non-conjugated double bonds used is preferably 0.1 parts by weight to 5 parts by weight, when the total amount of the monomer mixture constituting (B) is 100 parts by weight. It is more preferably 0.5 parts by weight to 5 parts by weight, and even more preferably 1 part to 3 parts by weight.
• fluorine-containing vinyl monomer examples include trifluoro(meth)acrylate, pentafluoro(meth)acrylate, perfluorocyclohexyl(meth)acrylate, and 2,2,3,3 methacrylate. -tetrafluoropropyl, ⁇ -(perfluorooctyl)ethyl (meth)acrylate, and the like.
• the fluorine-containing vinyl monomers may be used alone or in combination of two or more.
• the amount of the fluorine-containing vinyl monomer used is preferably 0.1 parts by weight to 50 parts by weight, when the total amount of the monomer mixture constituting (A) and (B) is 100 parts by weight. It is more preferably 1 part by weight to 40 parts by weight, and even more preferably 2 parts by weight to 30 parts by weight.
• a monomer having an alkoxysilyl group is used to impart crosslinking properties and improve adhesion to glass, metal, etc. can be improved.
• the monomer having the alkoxysilyl group examples include vinyltrimethoxysilane, ⁇ -(meth)acryloxypropyltrimethoxysilane, vinyltriethoxysilane, ⁇ -(meth)acryloxypropyltriethoxysilane , ⁇ -(meth)acryloxypropyltripropoxysilane, ⁇ -(meth)acryloxypropyltributoxysilane, vinylmethyldimethoxysilane, ⁇ -(meth)acryloxypropylmethyldimethoxysilane, vinylmethyldiethoxysilane, ⁇ - Examples include (meth)acryloxypropylmethyldiethoxysilane, ⁇ -(meth)acryloxypropylmethyldipropoxysilane, and ⁇ -(meth)acryloxypropylmethyldibutoxysilane.
• the monomer having an alkoxysilyl group may be used alone or in combination of two or more types.
• the amount of the monomer having an alkoxysilyl group to be used is preferably 0.1 to 30 parts by weight, and 0.1 to 30 parts by weight, when the total amount of the monomer mixture constituting (A) and (B) is 100 parts by weight.
• the amount is more preferably 5 parts by weight to 20 parts by weight, and even more preferably 1 part by weight to 10 parts by weight.
• an ethylenically unsaturated monomer having a carbonyl group derived from a keto group or an aldehyde group is used to improve the adhesion to the film. can improve sex.
• ethylenically unsaturated monomer having a carbonyl group examples include acrolein, diacetone acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formylstyrol, and 4 to 7 carbon atoms.
• examples include vinyl alkyl ketones (eg, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone) having the following.
• diacetone acrylamide and diacetone methacrylamide are particularly preferred in terms of reactivity, availability, and economy.
• Ethylenically unsaturated monomers having a carbonyl group derived from a keto group or an aldehyde group may be used alone or in combination of two or more types.
• the amount of the ethylenically unsaturated monomer having a carbonyl group derived from a keto group or an aldehyde group is 0.1% to 10% by weight of the total monomer mixture constituting the (B) acrylic resin composition. is preferable, and 1% to 5% by weight is more preferable.
• an ethylenically unsaturated monomer having a carbonyl group derived from a keto group or an aldehyde group is used as (b2) to prepare the acrylic resin (B).
• the latex After the latex is obtained, it is also possible to impart crosslinking properties by adding (D) a hydrazine derivative having at least two hydrazino groups or semicarbazide groups per molecule to the latex. Thereby, the water resistance, solvent resistance, and adhesion of the resulting coating film, ink, etc. can be improved.
• an ethylenically unsaturated monomer having a carbonyl group derived from a keto group or an aldehyde group and component (D) are added, and an ethylenically unsaturated monomer having a carbonyl group derived from a keto group or an aldehyde group.
• hydrazine derivatives having at least two hydrazino groups or semicarbazide groups per molecule include oxalic acid dihydrazide, malonic acid dihydrazide, glutaric acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, etc.
• a hydrophilic group such as polyether polyols and polyethylene glycol monoalkyl ethers.
• Examples include the resulting water-based polyfunctional semicarbazide, or a mixture of the polyfunctional semicarbazide and a water-based polyfunctional semicarbazide (see JP-A-8-151358 and JP-A-8-245878).
• the hydrazine derivative having at least two hydrazino groups or semicarbazide groups per molecule may be used alone or in combination of two or more.
• the amount of the hydrazine derivative having a hydrazino group or semicarbazide group is such that the total amount of functional groups selected from hydrazide groups, semicarbazide groups, and hydrazone groups is determined based on (B) 1 mole of carbonyl group in the acrylic resin.
• the amount is preferably 0.01 mol to 2 mol, more preferably 0.05 mol to 1.5 mol.
• (B) acrylic resin in [Step 2] becomes too hydrophilic, it will concentrate near the surface of the composite resin particles, and the interface with the (A) vinyl chloride resin will become clear, preventing the desired modification. It may become difficult to obtain quality effects or the viscosity of the latex may increase rapidly. Therefore, (B) 60% by weight or more, more preferably 80% by weight or more of the total monomer mixture constituting the acrylic resin is a hydrophobic monomer having a solubility in water at 20°C of less than 5 g/L. It is desirable that the viscosity of the latex be lowered.
• the acrylic resin (B) will not concentrate near the surface of the particles, making it easier to express the characteristics of vinyl chloride resin, and reducing the latex viscosity. can be lowered, improving productivity and economic efficiency.
• the glass transition temperature (hereinafter referred to as "Tg") of (B) acrylic resin is set to (A ) It is preferable to set the Tg lower than the Tg of the vinyl chloride resin.
• Tg glass transition temperature
• Tg values of the main homopolymers are shown below.
• (b1) and (b2) are monomers having an alkyl group having 8 or more carbon atoms, such as alkyl (meth) having an alkyl group having 8 or more carbon atoms. It is also preferable to use acrylate in an amount of 50% by weight or more based on the total monomer mixture constituting B) the acrylic resin composition. Thereby, adhesion to PET and plasticdan can be improved.
• a redox type polymerization initiator containing a polymerization initiator and a reducing agent is used in [Step 2].
• the polymerization temperature can be kept low, and thermal decomposition of the vinyl chloride component can be suppressed.
• the storage stability of the latex of the resulting composite resin particles can be improved, and the water absorption rate of the coating film can be reduced.
• Examples of the polymerization initiator include organic peroxides, hydrogen peroxide, and the like.
• Examples of the organic peroxides include t-butyl hydroperoxide, cumene hydroperoxide, t-butylperoxyisopropyl carbonate, paramenthane hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide. , benzoyl peroxide, lauroyl peroxide, and the like. These polymerization initiators may be used alone or in combination of two or more.
• the polymerization initiator is an organic peroxide. That is, the redox type polymerization initiator is more preferably a redox type polymerization initiator that is a combination of an organic peroxide and a reducing agent. Thereby, the storage stability of the latex of the resulting composite resin particles can be further improved, and the water absorption rate of the coating film can be further reduced.
• the reducing agent examples include sodium sulfite, sodium thiosulfate, sodium hydroxymethanesulfinate, ascorbic acid, sodium ascorbate, Rongalite, Bruggolite (registered trademark) FF-6, thiourea dioxide, and the like. can. Note that, in consideration of the environment, Bruggolite (registered trademark) FF-6 and thiourea dioxide, which do not generate formaldehyde, are particularly preferable as the reducing agent. These reducing agents may be used alone or in combination of two or more.
• a reducing agent may be used in combination with the polymerization initiator to be used as a redox type polymerization initiator, and a redox type catalyst may also be used in combination.
• the above redox type polymerization initiator may be used in the presence of a redox catalyst.
• a redox catalyst for example, a transition metal complex produced by using a transition metal salt and a chelating agent in combination can be used.
• the transition metal salt include ferrous (II) sulfate, copper (II) sulfate, copper chloride, and the like
• the chelating agent include EDTA/2Na, tartaric acid, ammonia, and the like.
• ferrous sulfate (II) is used as the transition metal salt and EDTA.2Na is used as the chelating agent
• Fe-EDTA is generated and functions as a redox catalyst.
• a reducing agent is used in combination with the above organic peroxide as a redox type polymerization initiator, and a redox type catalyst is further used in combination. is more preferable.
• the polymerization initiator used in the polymerization of the acrylic resin (B) in [Step 2] in addition to the redox type polymerization initiator containing the above-mentioned polymerization initiator and reducing agent, other A polymerization initiator may also be used.
• the polymerization initiator used in the polymerization of the (B) acrylic resin in [Step 2] may not contain persulfates from the viewpoint of water resistance (especially reduction of water absorption rate, reduction of water whitening resistance, etc.). preferable.
• the amount of the polymerization initiator used in [Step 2] is preferably 0.01 parts by weight to 5 parts by weight, and 0.02 parts by weight, based on 100 parts by weight of the total monomer mixture of (b1) + (b2). -3 parts by weight is more preferred. If the amount of the polymerization initiator used is 0.01 parts by weight or more, polymerization will proceed suitably. Moreover, if it is 5 parts by weight or less, heat generation control can be performed suitably. Note that the amount of polymerization initiator used herein does not include the amount of reducing agent used. Furthermore, when a redox catalyst is used in combination, the amount of polymerization initiator used does not include the amount of reducing agent and redox catalyst used.
• the amount of the reducing agent used is preferably 0.5 times to 10 times the weight of the polymerization initiator combined as the redox type polymerization initiator, and 0.6 times to 7 times the weight of the polymerization initiator combined as the redox type polymerization initiator. Double doses are more preferred.
• the amount of the reducing agent used is within the above range, it is preferable because stable polymerization behavior is exhibited.
• the amount of transition metal salt used in the redox catalyst is 0.001 times to 0.05 times the weight of the reducing agent used. is preferable, and 0.002 to 0.03 times the amount is more preferable.
• the amount of the chelating agent used in the redox catalyst is preferably 1 to 10 times the weight of the transition metal salt.
• the surfactants used in the polymerization of the (B) acrylic resin in [Step 2] can be the same as those listed for the (A) vinyl chloride resin in Step 1.
• (C) reactive surfactant having a polymerizable double bond in one molecule is used as part or all of the surfactant in [Step 2]. It is preferable to use these from the viewpoints of suppressing the generation of new particles, water resistance (particularly, reduction of water absorption, reduction of water resistance whitening, etc.), weather resistance, and gloss.
• a reactive surfactant having a polyoxyalkylene group in the molecule is used, mechanical stability and storage stability can be improved.
• (C) a reactive compound having a polymerizable double bond in one molecule as part or all of the surfactant. It is further preferred to use a surfactant. Thereby, it is possible to further improve water resistance (particularly, reduction in water absorption, reduction in water resistance to whitening, etc.) and glossiness, and it is also possible to obtain a coating film without fogging.
• the ratio of (A) vinyl chloride resin to (B) acrylic resin is From the viewpoint of impact resistance, flexibility, and film formability, the weight ratio is preferably 95:5 to 20:80. Note that when used as a hard molded article, from the viewpoint of impact resistance, a ratio of 95:5 to 70:30 is particularly preferable. When used for soft molded articles, paints, inks, etc., the ratio of 70:30 to 30:70 is particularly preferable from the viewpoint of flexibility and film formability.
• the average particle diameter of the composite resin particles after completing [Step 2] is preferably 20 nm to 500 nm, more preferably 50 nm to 300 nm, as measured by dynamic light scattering.
• the average particle diameter of the composite resin particles is 20 nm or more, the viscosity does not increase too much and stability is improved, which is preferable, and when it is 500 nm or less, water resistance is preferable.
• the average particle diameter of the composite resin particles is adjusted to 60 nm to 120 nm to improve adhesion, water resistance, and water whitening resistance. Becomes good.
• the composite resin particles obtained according to an embodiment of the present invention can be used as is in the form of latex, or can be dried and used as powder.
• pigments titanium dioxide, calcium carbonate, kaolin clay, talc, barium sulfate, white carbon, carbon, Bengara, ocher, cyanine blue, etc.
• film-forming aids colloidal silica, plasticizers, solvents, dispersants
• Additives used in coating materials can also be added, such as wetting agents, preservatives, antifreeze agents, light stabilizers, UV absorbers, antifoaming agents, silane coupling agents, etc.
• the method for obtaining the powder includes, for example, adding one or more coagulants selected from the group consisting of acids and salts to the obtained composite resin particle latex and coagulating it, for example, at 40°C or higher.
• coagulants selected from the group consisting of acids and salts
• the material is heat treated at a temperature of 110° C. or lower, washed, dehydrated, dried, and passed through a sieve of a predetermined size.
• pulverizing the material using powder spray drying or the like is also a method of pulverizing the material using powder spray drying or the like.
• the obtained powder can be molded and used as a molded body.
• heat stabilizers, stabilizing aids, lubricants, processing aids, antioxidants, light stabilizers, pigments, inorganic fillers, plasticizers, and the like can be used as necessary.
• the tensile modulus measured in accordance with JIS K 6251 is preferably 5 MPa or more and 500 MPa or less, more preferably 10 MPa. It is not less than 300 MPa, more preferably not less than 15 MPa and not more than 150 MPa.
• molded bodies for soft applications include various molded bodies (for example, soft films, sheets, plates, etc.) obtained by calender molding, injection molding, extrusion molding, and the like. Specifically, representative examples include medical bags, tubes, films and sheets for automobile interiors, desk mats for stationery, soft materials for writing instruments, electric wire covering materials, flooring materials, and various sealing materials.
• the tensile modulus measured in accordance with JIS K 6251 is preferably more than 500 MPa and no more than 2500 MPa, more preferably 550 MPa. It is not less than 2,300 MPa, and more preferably not less than 600 MPa and not more than 2,100 MPa.
• molded bodies for hard applications include various molded bodies (for example, hard films, sheets, plates, etc.) obtained by calender molding, injection molding, extrusion molding, and the like. Specifically, we manufacture printing films and sheets, automobile interior films and sheets, food and pharmaceutical films, sheets, containers, architectural films, sheets, boards, roofing materials, wall materials, window frame materials, gutter materials, and various other products. Typical examples include pipe materials and pipe joints.
• One embodiment of the present invention includes the following configuration.
• a method for producing composite resin particles including Step 1 and Step 2, and in Step 2, a redox type polymerization initiator containing a polymerization initiator and a reducing agent is used.
• Step 1 (a1) more than 90 parts by weight of vinyl chloride monomer and not more than 100 parts by weight, and (a2) monomer consisting of 0 parts by weight or more and less than 10 parts by weight of an ethylenically unsaturated monomer copolymerizable with vinyl chloride monomer [Here, the total amount of (a1) and (a2) is 100 parts by weight] ] to obtain (A) a vinyl chloride resin; [Step 2] Copolymerizable with (b1) 50 to 100 parts by weight of (meth)acrylic acid alkyl ester monomer and (b2) (meth)acrylic acid alkyl ester in the presence of the vinyl chloride resin (A).
• the ethylenically unsaturated monomer (b2) used in step 2 is an ethylenically unsaturated monomer having a carboxyl group, and the ethylenically unsaturated monomer having a carboxyl group
• the amount of monomer used in step 1 and step 2 is 6% by weight or less of the total monomers (A) + (B) used in step 1 and step 2.
• Part or all of the ethylenically unsaturated monomer (b2) used in step 2 is an ethylenically unsaturated monomer having a carbonyl group derived from a keto group or an aldehyde group, [1 ] to [5].
• the polymerization conversion rate of the obtained composite resin particles can be determined by measuring the solid content concentration of the obtained composite resin particle latex and dividing it by the theoretical solid content concentration assuming that all of the monomers introduced have been polymerized. It was calculated and expressed as "%". Note that the solid content concentration of the composite resin particle latex was calculated using the following formula based on the weight data obtained by performing the following operations.
• a certain amount of the obtained composite resin particle latex was poured into an aluminum container whose weight (w 1 ) had been measured in advance, and after the weight (w 2 ) was measured, it was dried for 1 hour in a dryer at 120°C. I let it happen.
• the weight (w 3 ) of the aluminum container containing the solid content after drying was measured.
• Solid content concentration (%) of composite resin particle latex (w 3 - w 1 )/(w 2 - w 1 ) x 100 ⁇ Average particle size and particle size distribution>
• the average particle size and particle size distribution of the obtained composite resin particles were measured using a particle size distribution measuring device using a dynamic light scattering method ("Nanotrac Wave-EX150", manufactured by Microtrac Bell Co., Ltd.). The dilution was adjusted to a concentration such that the loading index in loading was approximately 1, and measurement was performed on a volume basis.
• MTF> The minimum film forming temperature (hereinafter referred to as "MFT") of the obtained composite resin particles was measured using an MFT tester TP-801LT manufactured by Tester Sangyo Co., Ltd.
• the obtained composite resin particle latex was thinly spread in a polyethylene container and dried in a dryer at 60° C. for 16 hours to obtain a solid material.
• the obtained solid was placed in a bag made of 200-mesh wire mesh whose weight (W 1 ) had been measured in advance, and the total weight (W 2 ) of the solid and the bag was measured, and then tetrahydrofuran ( (hereinafter abbreviated as "THF”) at room temperature (23° C.) for 16 hours.
• THF tetrahydrofuran
• THF insoluble content (%) (W 3 ⁇ W 1 )/(W 2 ⁇ W 1 ) ⁇ 100.
• the obtained compound was kneaded for 5 minutes at 190° C. using two rolls (manufactured by Nippon Roll Manufacturing Co., Ltd., 8-inch mixing roll) to produce a sheet. Thereafter, several of the obtained sheets were stacked and pressed at 190°C for 10 minutes at a pressure of 100 kgf/cm 2 using a heat press machine (manufactured by Kamito Metal Industry Co., Ltd., 37 ton press) to perform a tensile test. A piece (JIS K 6251-1 type) (thickness 1 mm) was prepared.
• the obtained composite resin particle latex was thinly poured into a polypropylene container so that the thickness after drying was about 1 mm, and dried in a dryer at 40° C. for 16 hours.
• the dried coating film was demolded and cut into a 20 mm x 15 mm test piece, and its weight (W0) was measured.
• the prepared ink was applied onto the various substrates listed in Table 2 with No.
• the sample was coated using a No. 6 bar coater (13.74 ⁇ m thick), dried for 10 minutes in a dryer at 60° C., and then cured at 23° C. for one day or more to serve as an evaluation test specimen.
• Cellophane tape (width 18 mm) approximately 10 cm in length was attached to the ink surface on the evaluation test specimen to ensure tight contact. The attached cellophane tape was violently peeled off from the left end, and the degree of peeling of the ink was observed.
• a 2 mm thick layer is cut on the ink surface of the evaluation test specimen using a cutter knife so that the number of cells becomes a grid of 25 (25 squares).
• Six incisions were made in the vertical and horizontal directions so that they were perpendicular to each other at intervals, and cellophane tape was pasted on top of the incisions to ensure a tight fit.
• the attached cellophane tape was peeled off vigorously from the edge of the tape at an angle of 45 degrees, and the degree of peeling of the ink was observed.
• the 60 degree specular gloss of the paint-coated surface of the evaluation specimen was measured using a gloss meter (VG 7000, manufactured by Nippon Denshoku Industries Co., Ltd.).
• the lightness (L*) of the paint-coated surface was measured in advance using a colorimeter (handheld colorimeter NR-12A manufactured by Nippon Denshoku Kogyo Co., Ltd.), and the evaluation test specimen was placed in water at 23°C for 24 hours. Soaked. After taking it out of the water, the water on the surface was quickly wiped off and the lightness (L*) was measured. The ⁇ L* value was calculated by subtracting the L* value before water immersion from the L* value after water immersion. The smaller ⁇ L* (closer to 0), the better the water whitening resistance.
• Step 1 (A) Polymerization of vinyl chloride resin latex In a polymerization container equipped with a stirrer, add 120 parts of deionized water, 0.094 parts of sodium formaldehyde sulfoxylate, 0.044 parts of baking soda (sodium hydrogen carbonate), and lauryl sulfate. 0.65 part of sodium, 0.00165 part of ferrous sulfate heptahydrate, and 0.00275 part of disodium ethylenediaminetetraacetate (EDTA.2Na) were charged.
• EDTA.2Na disodium ethylenediaminetetraacetate
• Adekaria Soap (registered trademark) SR-1025 (manufactured by ADEKA Co., Ltd.: active ingredient 25%) was added as a reactive surfactant to an aqueous solution of Adekaria Soap SR-1025 (5%) to an amount of 1.35 parts as an active ingredient. %) was uniformly and continuously added for 165 minutes from 45 minutes after the start of polymerization (inner temperature reached 60°C).
• the polymerization reaction was stopped when the internal pressure in the polymerization container decreased to 0.5 MPa or less. Unreacted vinyl chloride was removed to obtain (A) vinyl chloride resin latex (PVC-1).
• the polymerization conversion rate of the obtained latex (PVC-1) was 75%, the average particle diameter was 92 nm, and the solid content concentration was 33%.
• the polymerization conversion rate of (A) vinyl chloride resin latex (PVC-2) was 74%, the average particle diameter was 85 nm, and the solid content concentration was 33%.
• the amount of TAC of 0.07 parts by weight shown in Table 7 is based on the amount contained in 50 parts by weight of (A) vinyl chloride resin, taking into account the polymerization conversion rate of (A) vinyl chloride resin. parts by weight).
• LaTemul registered trademark
• PD-430S manufactured by Kao Corporation: 25% active ingredients
• 0.049 parts of t-butyl hydroperoxide as a polymerization initiator and 0.030 parts of Bruggolite® FF-6 as a reducing agent were added in 8 portions. Added.
• the latex properties (average particle size, particle size distribution, viscosity, MFT, THF-insoluble content) of the obtained composite resin particle latex HB-1 were measured. The results are shown in Table 7.
• the latex properties (average particle size, particle size distribution, viscosity, MFT, THF-insoluble content) of the obtained composite resin particle latex HB-2 were measured. The results are shown in Table 7.
• Example 3 (Polymerization of composite resin particle latex) (B) The same operation as in Example 2 was performed except that the monomer mixture constituting the acrylic resin was changed to (Ac-2) in Table 6, and the composite resin Lalatex 3 (HB-3) was prepared. Obtained.
• the latex properties (average particle size, particle size distribution, viscosity, MFT, THF-insoluble content) of the obtained composite resin particle latex HB-3 were measured. The results are shown in Table 7.
• Example 4 (Polymerization of composite resin particle latex) (B) The same operation as in Example 2 was performed except that the monomer mixture constituting the acrylic resin was changed to (Ac-3) in Table 6, and the composite resin Lalatex 3 (HB-4) was prepared. Obtained.
• the latex properties (average particle size, particle size distribution, viscosity, MFT, THF-insoluble content) of the obtained composite resin particle latex HB-4 were measured. The results are shown in Table 7.
• Example 5 (Polymerization of composite resin particle latex) (B) The same operation as in Example 2 was performed except that the monomer mixture constituting the acrylic resin was changed to (Ac-4) in Table 6, and the composite resin Lalatex 3 (HB-5) was prepared. Obtained.
• the latex properties (average particle size, particle size distribution, viscosity, MFT, THF-insoluble content) of the obtained composite resin particle latex HB-5 were measured. The results are shown in Table 7.
• the latex properties (average particle size, particle size distribution, viscosity, MFT, THF-insoluble content) of the obtained composite resin particle latex HB-6 were measured. The results are shown in Table 7.
• the temperature was raised to 50°C, and then 0.035 parts of polymerization initiator t-butyl hydroperoxide, 0.0007 parts of ferrous sulfate heptahydrate, and ethylenediaminetetraacetic acid diacetate were added.
• 0.0028 parts of sodium (EDTA/2Na) and 0.35 parts by weight of a reducing agent Bruggolite (registered trademark) FF-6 were added and stirred for 30 minutes.
• Step 2 Next, 0.028 parts of a polymerization initiator t-butyl hydroperoxide and 0.011 parts by weight of a reducing agent Bruggolite® FF-6 were added. Thereafter, to 50 parts by weight of the monomer mixture shown in (Ac-1) in Table 6, the reactive surfactant Aquaron (registered trademark) AR-1025 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.: active ingredient 25 %) as an active ingredient, 0.75 parts by weight of Latemul (registered trademark) PD-430S (manufactured by Kao Corporation: active ingredient 25%) as an active ingredient, and 19 parts by weight of deionized water (interfacial (including the activator brought in) and the emulsified monomer emulsion was uniformly and continuously added over 200 minutes. During that time, 0.049 part of t-butyl hydroperoxide and 0.030 part of Bruggolite® FF-6/ were added in 8 portions.
• Acrylic resin particle latex (AC-1) was obtained.
• the latex properties (average particle size, particle size distribution, viscosity, MFT, THF-insoluble content) of the obtained two-stage acrylic resin particle latex AC-1 were measured. The results are shown in Table 7.
• the composite resin particles obtained in Examples 1 to 6 all have a single peak in particle size distribution, and the average particle size also increases commensurately with the amount of added monomer. It is presumed that (A) vinyl chloride resin and (B) acrylic resin coexist. That is, it is considered that composite resin particles of (A) vinyl chloride resin and (B) acrylic resin were obtained.
• the composite resin particles obtained in Examples 1 to 6 had a lower minimum film-forming temperature than the resin particles of Comparative Example 1, which was polymerized in multiple stages using only the acrylic resin (B).
• the THF-insoluble content was further increased by introducing (E) a compound having at least two non-conjugated double bonds into (A) the vinyl chloride resin.
• the amount of the hydrophobic monomer having a solubility in water at 20° C. of 5 g/L or less is less than 60% by weight in the monomer mixture constituting the (B) acrylic resin composition.
• the latex viscosity increased slightly.
• Example 6 when the amount of the monomer having a carboxyl group used exceeds 5% by weight when the total amount of the monomer mixture constituting (A) and (B) is 100 parts by weight, , the latex viscosity increased slightly.
• a molded sheet could be obtained by rolling and pressing.
• the tensile modulus of the molded sheet obtained was measured, the tensile modulus of the molded sheet obtained from the composite resin particle latex of Example 2 was 1333 MPa, and the tensile modulus of the molded sheet obtained from the composite resin particle latex of Example 5 was 1333 MPa.
• the tensile modulus of the body sheet was 135 MPa.
• the molded product sheet obtained from the composite resin particle latex of Example 2 was suitable as a hard molded product, and the molded product sheet obtained from the composite resin particle latex of Example 5 was suitable as a soft molded product.
• Example 7 Example 1 (composite latex HB-1) except that in [Step 2] (polymerization of composite resin particle latex), the monomer mixture constituting the (B) acrylic resin was changed to Ac-7 in Table 8. The same operation as above was performed to obtain composite resin particle latex 8 (HB-8).
• the latex properties (average particle size, particle size distribution, viscosity, MFT, THF insoluble content) and ink properties (adhesion, water resistance, Alcohol resistance) was measured. The results are shown in Table 9.
• Example 8 In [Step 2] (polymerization of composite resin particle latex), the monomer mixture constituting the (B) acrylic resin was changed to Ac-8 (containing 2 parts of diacetone acrylamide) in Table 8. The same operation as in Example 1 (composite latex HB-1) was performed to obtain composite resin particle latex 9 (HB-9).
• the latex properties (average particle size, particle size distribution, viscosity, MFT, THF insoluble content) and ink properties (adhesion, water resistance, Alcohol resistance) was measured. The results are shown in Table 9.
• the latex properties (average particle size, particle size distribution, viscosity, MFT, THF insoluble content) and ink properties (adhesion, water resistance, Alcohol resistance) was measured. The results are shown in Table 9.
• the latex properties (average particle size, particle size distribution, viscosity, MFT, THF insoluble content) and ink properties (adhesion, water resistance, Alcohol resistance) was measured. The results are shown in Table 9.
• Example 9 composite resin particle latex 9A except that in [Step 2] (polymerization of composite resin particle latex), the monomer mixture constituting the (B) acrylic resin was changed to Ac-9 in Table 8. The same operation as above was performed to obtain composite resin particle latex 11A (HB-11A).
• the latex properties (average particle size, particle size distribution, viscosity, MFT, THF insoluble content) and ink properties (adhesion, water resistance, Alcohol resistance) was measured. The results are shown in Table 9.
• Example 9 composite resin particle latex 9A except that in [Step 2] (polymerization of composite resin latex particles), the monomer mixture constituting the (B) acrylic resin was changed to Ac-10 in Table 8. The same operation as above was performed to obtain composite resin particle latex 12A (HB-12A).
• the latex properties (average particle size, particle size distribution, viscosity, MFT, THF insoluble content) and ink properties (adhesion, water resistance, Alcohol resistance) was measured. The results are shown in Table 9.
• Example 9 composite resin particle latex 9A was used, except that the amount of adipic acid dihydrazide (ADH) added to the obtained composite resin particle latex 12 (HB-12) was changed to 0.5 parts. A similar operation was performed to obtain composite resin particle latex 13A (HB-13A).
• ADH adipic acid dihydrazide
• the latex properties (average particle size, particle size distribution, viscosity, MFT, THF-insoluble content) and ink properties (adhesion, water resistance, Alcohol resistance) was measured. The results are shown in Table 10.
• Latemul registered trademark
• PD-430S manufactured by Kao Corporation: 25% active ingredient
• surfactant 12 parts by weight of deionized water (surfactant).
• a monomer emulsion obtained by adding and emulsifying the monomer (including the amount carried in) was uniformly and continuously added over 120 minutes. During the continuous addition of the monomer emulsion, 0.028 part of t-butyl hydroperoxide as a polymerization initiator and 0.018 part of Bruggolite® FF-6/ as a reducing agent were added in 5 portions. Added.
• the latex properties (average particle size, particle size distribution, viscosity, MFT, THF insoluble content) and ink properties (adhesion, water resistance, Alcohol resistance) was measured. The results are shown in Table 10.
• Latemul registered trademark
• PD-430S manufactured by Kao Corporation: 25% active ingredient
• surfactant 30 parts by weight of deionized water (surfactant).
• a monomer emulsion obtained by adding and emulsifying the monomer (including the amount carried in) was uniformly and continuously added over 120 minutes. During the continuous addition of the monomer emulsion, 0.070 part of t-butyl hydroperoxide as a polymerization initiator and 0.0375 part of Bruggolite® FF-6/ as a reducing agent were added in 10 portions. Added.
• the latex properties (average particle size, particle size distribution, viscosity, MFT, THF insoluble content) and ink properties (adhesion, water resistance, Alcohol resistance) was measured. The results are shown in Table 10.
• Step 1 In a polymerization vessel equipped with a stirrer, 90 parts of deionized water, 0.0715 parts of sodium formaldehyde sulfoxylate, 0.033 parts of baking soda, 0.5 parts of sodium lauryl sulfate, and 0.00165 parts of ferrous sulfate heptahydrate. , and 0.0012 parts of disodium ethylenediaminetetraacetate (EDTA.2Na) were charged.
• EDTA.2Na disodium ethylenediaminetetraacetate
• Step 2 Next, 0.75 parts of polyoxyethylene polyoxypropylene lauryl ether (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Neugen LP-180) was charged into the polymerization container, and after raising the temperature to 50°C again, the polymerization initiator t -0.028 parts of butyl hydroperoxide and 0.011 parts by weight of the reducing agent Bruggolite® FF-6 were added. Thereafter, a monomer emulsion prepared by adding 0.375 parts of sodium lauryl sulfate, 0.375 parts of Neugen LP-180, and 9 parts of deionized water to 25 parts of butyl acrylate was emulsified for 100 minutes. It was added uniformly and continuously. During that time, 0.025 part of t-butyl hydroperoxide and 0.015 part of Bruggolite® FF-6/ were added in 4 portions.
• polyoxyethylene polyoxypropylene lauryl ether manufactured by Daiich
• the latex properties (average particle size, particle size distribution, viscosity, MFT, THF insoluble content) and ink properties (adhesion, water resistance, Alcohol resistance) was measured. The results are shown in Table 10.
• the temperature was raised to 50°C, and then 0.028 part of t-butyl hydroperoxide, 0.0007 part of ferrous sulfate heptahydrate, and ethylenediaminetetraacetic acid were added as polymerization initiators.
• 0.0028 parts of disodium (EDTA.2Na) and 0.011 parts by weight of Bruggolite® as a reducing agent were added.
• Aquaron (registered trademark) AR-1025 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.: 25% active ingredient
• Aquaron (registered trademark) AR-1025 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.: 25% active ingredient
• 0.75 parts by weight of Latemul (registered trademark) PD-430S manufactured by Kao Corporation: 25% active ingredient
• the monomer emulsion obtained by emulsifying the mixture by adding (including the ingredients) was uniformly and continuously added over 200 minutes.
• adipic acid dihydrazide (ADH) was added to the obtained acrylic resin latex for blending (AC-2) in the same manner as in Example 9, and the acrylic resin latex for blending (AC-2A) was added. Obtained.
• the latex properties (average particle size, particle size distribution, viscosity, MFT, THF-insoluble content) of the obtained acrylic resin latex for blending (AC-2A) were measured. The results are shown in Table 10.
• ink properties adheresion, water resistance, and alcohol resistance in ⁇ Evaluation 1 of ink properties> described above. The results are shown in Table 10.
• the composite resin particles obtained in Examples 7 to 15 all had a single peak in particle size distribution, and the average particle size also showed a corresponding increase. It is presumed that the resin and (B) acrylic resin coexist. That is, it is considered that composite resin particles of (A) vinyl chloride resin and (B) acrylic resin were obtained.
• Example 7 Comparing Example 7 and Example 8, it was found that when an ink containing composite resin particle latex was prepared by copolymerizing methacrylic acid and diacetone acrylamide as (b2) and applied to a base material, it was particularly effective for OPP. And the adhesion to nylon film was improved.
• Example 8 Comparing Example 8 and Example 9, by adding (D) adipic acid dihydrazide, which is a hydrazine derivative having a hydrazino group or a semicarbazide group, the THF-insoluble content of the obtained composite resin particles increases, and the solvent resistance increases. sex has improved. Furthermore, when an ink containing the composite resin particle latex was prepared and applied to a substrate, the adhesion to the film was also improved.
• adipic acid dihydrazide which is a hydrazine derivative having a hydrazino group or a semicarbazide group
• Step 1 Polymerization of vinyl chloride resin latex In a polymerization container equipped with a stirrer, add 120 parts of deionized water, 0.094 parts of sodium formaldehyde sulfoxylate, 0.044 parts of baking soda (sodium hydrogen carbonate), and lauryl sulfate. 0.65 part of sodium, 0.00165 part of ferrous sulfate heptahydrate, and 0.00275 part of disodium ethylenediaminetetraacetate (EDTA.2Na) were charged.
• EDTA.2Na disodium ethylenediaminetetraacetate
• the polymerization reaction was stopped when the internal pressure in the polymerization container decreased to 0.5 MPa or less. Unreacted vinyl chloride was removed to obtain (A) vinyl chloride resin latex (PVC-3).
• the polymerization conversion rate of the obtained latex (PVC-3) was 86%, the average particle diameter was 100 nm, and the solid content concentration was 37%.
• the amount of each component shown in Table 11 is the amount (parts by weight) contained in 50 parts by weight of (A) vinyl chloride resin, taking into account the polymerization conversion rate of (A) vinyl chloride resin. It is.
• Example 16> Using the composite resin particle latex 13A (HB-13A) obtained in Example 13, an ink was prepared with the formulations listed in Table 3 according to ⁇ Evaluation of Ink Properties 2> described above, and the ink was prepared with the formulations listed in Table 4. The ink properties (adhesion, water resistance, alcohol resistance, and alcohol abrasion resistance in ⁇ Evaluation of ink properties 2> described above) were measured. The results are shown in Table 11.
• Latex properties of the obtained composite resin particle latex (average particle size, particle size distribution, viscosity, MFT, THF insoluble content) and ink properties similar to those in Examples 16 to 19 ( ⁇ Evaluation of ink properties 2> described above)
• the adhesion, water resistance, alcohol resistance, and alcohol abrasion resistance were measured. The results are summarized in Table 11.
• Example 17 to 18 50% or more of alkyl (meth)acrylate having an alkyl group having 8 or more carbon atoms was used as the monomer constituting component (B); Compared with Example 16, which did not have the same, an improvement in the adhesion of PET and plastican was observed.
• Example 19 contains diacetone acrylamide, which is an ethylenically unsaturated monomer having a carbonyl group derived from a keto group or an aldehyde group, in component (b2), and (D) a hydrazine derivative having a hydrazino group or semicarbazide group.
• diacetone acrylamide which is an ethylenically unsaturated monomer having a carbonyl group derived from a keto group or an aldehyde group
• component (b2) a hydrazine derivative having a hydrazino group or semicarbazide group.
• the amount of adipic acid dihydrazide was increased, and the alcohol abrasion resistance was improved compared to Examples 16 to 18.
• Example 20 introduces 2-ethylhexyl acrylate as the (a2) component and triallyl cyanurate (TAC) as the (E) component into the (A) component, and also introduces (b2) in the (B) component.
• Diacetone acrylamide which is an ethylenically unsaturated monomer having a carbonyl group derived from a keto group or an aldehyde group
• (D) adipic acid dihydrazide which is a hydrazine derivative having a hydrazino group or a semicarbazide group, are further added. The amount was increased, and the THF-insoluble content was improved compared to Example 19.
• Step 1 (A) Polymerization of vinyl chloride resin latex 0.65 parts of sodium lauryl sulfate, which is the first emulsifier, is added to 0.12 parts of Adecaria, a reactive surfactant, continuously added 45 minutes after the start of polymerization. Polymerization was carried out in the same manner as in Synthesis Example 1, except that 1.35 parts of Soap (registered trademark) SR-1025 (manufactured by ADEKA Co., Ltd.: active ingredient 25%) was changed to 1.66 parts of sodium lauryl sulfate. Then, unreacted vinyl chloride was removed to obtain (A) vinyl chloride resin latex (PVC-4).
• Soap registered trademark
• SR-1025 manufactured by ADEKA Co., Ltd.: active ingredient 25%
• the polymerization conversion rate of (A) vinyl chloride resin latex (PVC-4) was 95%, the average particle diameter was 170 nm, and the solid content concentration was 36%.
• Latex properties (average particle size, particle size distribution, viscosity, MFT, THF insoluble content, storage stability, water absorption) and coating film properties (coating film appearance, gloss, water resistance) of the obtained composite resin particle latex HB-22 Whitening property) was measured. The results are shown in Table 12.
• Latex properties (average particle size, particle size distribution, viscosity, MFT, THF insoluble content, storage stability, water absorption) and coating film properties (coating film appearance, gloss, water resistance) of the obtained composite resin particle latex HB-23 Whitening property) was measured. The results are shown in Table 12.
• Step 2 Polymerization of composite resin particle latex
• the emulsifier used in step 2 was mixed with a reactive surfactant from 0.57 parts of sodium lauryl sulfate and 0.45 parts of polyoxyethylene polyoxypropylene lauryl ether (Daiichi Kogyo Seiyaku Co., Ltd., Neugen LP-180).
• Latex properties (average particle size, particle size distribution, viscosity, MFT, THF insoluble content, storage stability, water absorption) and coating film properties (coating film appearance, gloss, water resistance) of the obtained composite resin particle latex HB-24 Whitening property) was measured. The results are shown in Table 12.
• Table 12 shows the latex properties (average particle size, particle size distribution, viscosity, MFT, THF-insoluble content, storage stability, water absorption rate) of the obtained composite resin particle latex HB-25. Furthermore, since the solid content was low and the viscosity was high, it was difficult to make it into a paint, so it was not possible to evaluate the paint film.
• Example 22 reactive surfactant was not used in either Step 1 or Step 2, and a redox type polymerization initiator in which an organic peroxide and a reducing agent were combined was used as the polymerization initiator in Step 2.
• the obtained latex had no problems in storage stability and water absorption rate of 8% or less.
• Example 23 is the same as the production method of Example 22, except that part of the emulsifier used in step 1 is replaced with (C) a reactive surfactant.
• the coating film obtained from the composite resin particle latex obtained in Example 23 showed improved water absorption, gloss, and water whitening resistance compared to the coating film obtained from the composite resin particle latex obtained in Example 22. Ta.
• Example 24 the emulsifier used in step 2 of the production method of Example 23 was also replaced with (C) a reactive surfactant.
• the coating film obtained from the composite resin particle latex obtained in Example 24 has further improved water absorption, gloss, and water whitening resistance compared to the coating film obtained from the composite resin particle latex obtained in Example 23. The cloudy appearance of the paint film disappeared.

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