CN108299658B - Aqueous dispersion - Google Patents

Aqueous dispersion Download PDF

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CN108299658B
CN108299658B CN201710025966.4A CN201710025966A CN108299658B CN 108299658 B CN108299658 B CN 108299658B CN 201710025966 A CN201710025966 A CN 201710025966A CN 108299658 B CN108299658 B CN 108299658B
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mass
parts
acid
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CN108299658A (en
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高松达也
远藤晃哉
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Toho Chemical Industry Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
    • C03C17/328—Polyolefins
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
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    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2351/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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    • C08J2435/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
    • C08J2435/06—Copolymers with vinyl aromatic monomers
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/50—Aqueous dispersion, e.g. containing polymers with a glass transition temperature (Tg) above 20°C
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • 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
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Chemical Kinetics & Catalysis (AREA)
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  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Dispersion Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
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Abstract

The present invention provides an aqueous dispersion. The present invention provides an aqueous dispersion of a high-molecular-weight polyolefin resin which is excellent in bundling properties and adhesion of fibers and can be industrially advantageously produced. An aqueous dispersion which comprises: a polyolefin resin (A) having a weight average molecular weight of 2 ten thousand or more, and a polymer dispersion (B) obtained by copolymerizing monomer components containing 50 to 90 mol% of a styrene monomer (B-1) and 10 to 50 mol% of itaconic acid (B-2).

Description

Aqueous dispersion
Technical Field
The present invention relates to an aqueous dispersion of a high molecular weight polyolefin resin which is excellent in bundling properties and adhesion of fibers and can be industrially advantageously produced.
Background
Fiber Reinforced Plastics (FRP) made of reinforcing fibers such as carbon fibers and glass fibers and a matrix resin are lighter than metal materials and have higher mechanical strength and higher elastic modulus than plastics containing no reinforcing fibers. Because of such properties, fiber-reinforced plastics are used in many fields such as aircrafts, automobiles, railway vehicles, and ships.
Conventionally, as glass fibers used as a reinforcing agent for fiber-reinforced plastics in which a polyolefin resin such as polyethylene or polypropylene is used as a matrix resin, glass fibers coated with a sizing agent containing an aqueous emulsion of an acid-modified polypropylene resin have been used (for example, see patent document 1).
In addition, for the purpose of improving the bundling properties of chopped strands, an aqueous emulsion of a high molecular weight polyolefin using a styrene-maleic anhydride copolymer as a polymer dispersant has been proposed (for example, see patent document 2).
Documents of the prior art
Patent document
Patent document 1: japanese examined patent publication (JP-B) No. 6-96463
Patent document 2: international publication No. 2004/074353 pamphlet
Disclosure of Invention
Problems to be solved by the invention
However, since the acid-modified polypropylene resin used in patent document 1 has a low molecular weight, the strength of the dried film formed from the aqueous emulsion is low, and the bundling property of chopped strands of glass fibers cannot be satisfied.
In addition, in the technique described in patent document 2, the adhesion of the high molecular weight polyolefin resin to the glass substrate is insufficient, and further improvement in performance is required.
The present invention has been made in view of the above circumstances, and an object thereof is to provide an aqueous dispersion of a high molecular weight polyolefin resin which is excellent in bundling properties and adhesion properties and can be industrially advantageously produced.
Means for solving the problems
The present inventors have made intensive studies to solve the above problems. As a result, they have found that a polymer polyolefin resin can be efficiently dispersed in an aqueous medium by using a copolymer containing a styrene-based monomer and itaconic acid as a dispersant, and that the polymer polyolefin resin can be industrially produced safely, and thus the present invention has been completed.
Namely, the present invention relates to an aqueous dispersion comprising: a polyolefin resin (A) having a weight average molecular weight of 2 ten thousand or more, and a polymer dispersion (B) obtained by copolymerizing monomer components containing 50 to 90 mol% of a styrene monomer (B-1) and 10 to 50 mol% of itaconic acid (B-2).
The present invention also relates to an aqueous dispersion, wherein the monomer component further contains 2 to 30 mol% of a (meth) acrylate with respect to all monomers constituting the polymeric dispersant (B).
The present invention further relates to an aqueous dispersion, wherein the content of the polyolefin resin (a) is 10 to 50% by mass based on the total mass of the aqueous dispersion, the amount of the polyolefin resin (a) is 100 parts by mass, and the content of the polymeric dispersant (B) is 1 to 35 parts by mass.
The present invention also relates to a sizing agent for fibers, which contains the aqueous dispersion.
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention can provide an aqueous dispersion of a high-molecular-weight polyolefin resin which is excellent in bundling properties and adhesion and can be industrially advantageously produced.
Detailed Description
The aqueous dispersion of the present invention is described in detail below. In the present specification, the term "(meth) acrylate" refers to a general term for acrylate and methacrylate. Also, (meth) containing compounds such as (meth) acrylic acid and the like are a generic name of compounds having "methyl" and compounds not having "methyl" in the name. Therefore, "(meth) propylene" includes both propylene and methacrylic. For example, the term "(meth) acrylic" includes both acrylic and methacrylic.
[ polyolefin resin ]
The weight average molecular weight of the polyolefin resin (A) used in the present invention is 2 ten thousand or more. If the weight average molecular weight is less than 2 ten thousand, the strength of the resulting dried film becomes low. The weight average molecular weight is preferably 3 ten thousand or more, and more preferably 5 ten thousand or more. The upper limit of the weight average molecular weight is not particularly limited, and is preferably 40 ten thousand or less, and more preferably 20 ten thousand or less, in view of emulsifiability. The weight average molecular weight of the polyolefin resin (a) is a value measured by Gel Permeation Chromatography (GPC).
As the polyolefin resin (a), a homopolymer or a copolymer of an olefin compound can be used. Examples of the homopolymer of the olefin compound include homopolymers of α -olefins having 2 to 20 carbon atoms such as polyethylene (low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, or the like), polypropylene, polyisobutylene, poly (1-butene), poly (1-pentene), poly (1-hexene), and the like, and examples of the copolymer include an ethylene-propylene copolymer, an ethylene-1-butene copolymer, an ethylene-1-octene copolymer, an ethylene-1-hexene copolymer, and the like.
Further, a polyolefin resin into which a polar group is introduced may also be used. Specific examples of the polyolefin resin into which a polar group has been introduced include acid-modified polyolefins such as maleic anhydride-modified polyethylene, maleic acid-modified polyethylene, acrylic acid-modified polyethylene, maleic anhydride-modified polypropylene, maleic acid-modified polypropylene, maleic anhydride-modified ethylene-propylene copolymer, and acrylic acid-modified polypropylene; ethylene-vinyl chloride copolymer, ethylene-1, 1-dichloroethylene copolymer, ethylene-acrylonitrile copolymer, ethylene-methacrylonitrile copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylamide copolymer, ethylene-methacrylamide copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-maleic acid copolymer, ethylene-methyl (meth) acrylate copolymer, ethylene-ethyl (meth) acrylate copolymer, ethylene-isopropyl (meth) acrylate copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene-isobutyl (meth) acrylate copolymer, ethylene-2-ethylhexyl (meth) acrylate copolymer, ethylene-maleic anhydride copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl ester copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl ester, ethylene-acrylate copolymer, ethylene-vinyl ester copolymer, ethylene-acrylate copolymer, ethylene-vinyl ester, ethylene-acrylate copolymer, ethylene-vinyl ester copolymer, ethylene-acrylate copolymer, ethylene-vinyl ester-acrylate copolymer, and ethylene-vinyl ester, Ethylene or α -olefin-vinyl monomer copolymers such as ethylene-ethyl acrylate-maleic anhydride copolymers, ethylene- (meth) acrylic acid metal salt copolymers, ethylene-vinyl acetate copolymers or saponified products thereof, ethylene-vinyl propionate copolymers, ethylene-glycidyl (meth) acrylate copolymers, ethylene-ethyl acrylate-glycidyl methacrylate copolymers, and ethylene-vinyl acetate-glycidyl methacrylate copolymers; chlorinated polyolefins such as chlorinated polypropylene and chlorinated polyethylene, and the like.
These polyolefin resins (A) may be used alone or 2 or more kinds may be used in combination. When the polyolefin resin (a) is a copolymer, the form of the copolymer is not particularly limited, and may be any of an alternating copolymer, a random copolymer, a block copolymer, and a graft copolymer.
If necessary, other resins or rubbers may be added to the polyolefin resin (a) within a range not impairing the effects of the present invention.
Examples of the other resin or rubber include α -olefin copolymers such as propylene/butene-1 copolymers; ethylene or α -olefin-diene monomer copolymers such as ethylene/propylene/5-ethylidene-2-norbornene copolymers; polydienes such as polybutadiene and polyisoprene; vinyl monomer-diene copolymers such as styrene-butadiene copolymers; vinyl monomer-diene-vinyl monomer block copolymers such as styrene-butadiene-styrene block copolymers; hydrogenated (vinyl monomer-diene random copolymers) such as hydrogenated (styrene-butadiene random copolymers); hydrogenated (vinyl monomer-diene-vinyl monomer block copolymers) such as hydrogenated (styrene-butadiene-styrene block copolymers); vinyl monomer-diene-vinyl monomer graft copolymers such as acrylonitrile-butadiene-styrene graft copolymers and methyl methacrylate-butadiene-styrene graft copolymers; vinyl polymers such as polyvinyl chloride, polyvinylidene 1, 1-dichloride, polyacrylonitrile, polyvinyl acetate, polyethyl acrylate, polybutyl acrylate, polymethyl methacrylate, polystyrene, etc.; vinyl copolymers such as vinyl chloride-acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, acrylonitrile-styrene copolymer, and methyl methacrylate-styrene copolymer.
Among these polyolefin resins (a), maleic anhydride-modified polypropylene, maleic anhydride-modified ethylene-propylene copolymer, and acrylic acid-modified polypropylene are preferable from the viewpoint of emulsifiability and strength of a dried film.
The polyolefin resin (A) may be a commercially available product or a synthetic product. Examples of commercially available products include, for example, EASTMAN G3216, EASTMAN G3003, EASTMAN G3015 (see EASTMAN CHEMICAL COMPANY, inc.), POLYBOND (registered trademark) 3200, POLYBOND (registered trademark) 1001 (see Chemtura Corporation, inc.), ハイワックス (registered trademark) NP0555A (see sambucol Corporation, inc.), Exxelor (registered trademark) PO 1015, Exxelor (registered trademark) PO 1020 (see Exxonmobil Chemical co., ltd.), TOYOTAC (registered trademark) H1000P, TOYOTAC (registered trademark) H3000P (see toyoyo co., ltd.), ユーメックス (registered trademark) 1001 (see samyo Chemical co., ltd.), and the like. The polymerization method used for the synthesis is not particularly limited, and known methods can be used, and examples thereof include a high-pressure radical polymerization method, a medium-low pressure polymerization method, a solution polymerization method, a slurry polymerization method, a bulk polymerization method, and a gas phase polymerization method. The catalyst used for the polymerization is not particularly limited, and examples thereof include a peroxide catalyst, a ziegler-natta catalyst, and a metallocene catalyst.
[ Polymer dispersing agent ]
The polymer dispersant (B) used in the present invention is a polymer obtained by copolymerizing monomer components including a styrene monomer (B-1) and itaconic acid (B-2). The form of the polymer dispersant (B) is not particularly limited, and may be any of an alternating copolymer, a random copolymer, a block copolymer, and a graft copolymer.
< styrene monomer >
Examples of the styrenic monomer as the component (b-1) of the polymer dispersant of the present invention include aromatic vinyl monomers such as styrene, α -methylstyrene, vinyltoluene, 2, 4-dimethylstyrene, styrene ring-substituted with a halogen, 1-vinylnaphthalene, p-methylstyrene, p-propylstyrene, p-cyclohexylstyrene, and p-dodecylstyrene. Among them, styrene or α -methylstyrene is preferable.
The amount of the component (b-1) in the polymer dispersant is preferably 50 to 90 mol%, more preferably 60 to 80 mol%, based on the total monomers constituting the polymer dispersant. If the amount of the component (b-1) is less than 50 mol%, the viscosity of the polymer dispersant becomes high and the workability is poor, while if it exceeds 90 mol%, the dispersibility of the polyolefin resin (A) becomes insufficient.
Itaconic acid (b-2) is contained in an amount of preferably 10 to 50 mol%, more preferably 10 to 40 mol%, based on the total monomers constituting the polymer dispersant.
The styrene monomer (b-1) and itaconic acid (b-2) are preferably contained in a molar ratio of (b-1) to (b-2) of 1:1 to 5:1, and more preferably 1:1 to 3.5: 1.
The polymeric dispersant used in the present invention may further contain (meth) acrylate. The (meth) acrylate used in the present invention is not particularly limited, and is preferably a (meth) acrylate having an ester moiety having a linear, branched or cyclic alkyl group having 1 to 22 carbon atoms.
Examples of the (meth) acrylate having a linear, branched or cyclic alkyl group having 1 to 22 carbon atoms in the ester portion include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, isopentyl (meth) acrylate, tert-pentyl (meth) acrylate, neopentyl (meth) acrylate, n-hexyl (meth) acrylate, 3-methylpentane-2-yl (meth) acrylate, 3-methylpentane-3-yl (meth) acrylate, 4-methylpentane-2-yl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-2-yl (meth) acrylate, n-pentyl) acrylate, n-2-yl (meth) acrylate, n-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-pentyl (meth) acrylate, n-2-pentyl (meth) acrylate, n-pentyl (meth) acrylate, and (meth) acrylate, n-pentyl (meth) acrylate, and/or a, 1, 3-dimethylbutyl (meth) acrylate, 3, 3-dimethylbutan-2-yl (meth) acrylate, n-heptyl (meth) acrylate, 1-methylhexyl (meth) acrylate, 3-methylhexyl (meth) acrylate, 4-methylhexyl (meth) acrylate, 5-methylhexyl (meth) acrylate, 1-ethylpentyl (meth) acrylate, 1- (n-propyl) butyl (meth) acrylate, 1-dimethylpentyl (meth) acrylate, 1, 4-dimethylpentyl (meth) acrylate, 1-diethylpropyl (meth) acrylate, 1,3, 3-trimethylbutyl (meth) acrylate, 1-ethyl-2 (meth) acrylate, 2-dimethylpropyl ester, n-octyl (meth) acrylate, 1-methylheptyl (meth) acrylate, 2-methylheptyl (meth) acrylate, 5-methylheptyl (meth) acrylate, 1-ethylhexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 1-propylpentyl (meth) acrylate, 2-propylpentyl (meth) acrylate, 1-dimethylhexyl (meth) acrylate, 1, 4-dimethylhexyl (meth) acrylate, 1, 5-dimethylhexyl (meth) acrylate, 1-ethyl-1-methylpentyl (meth) acrylate, and mixtures thereof1-ethyl-4-methylpentyl (meth) acrylate, 1, 4-trimethylpentyl (meth) acrylate, 2,4, 4-trimethylpentyl (meth) acrylate, 1-isopropyl-1, 2-dimethylpropyl (meth) acrylate, 1,3, 3-tetramethylbutyl (meth) acrylate, n-nonyl (meth) acrylate, 1-methyloctyl (meth) acrylate, 6-methyloctyl (meth) acrylate, 1-ethylheptyl (meth) acrylate, n-decyl (meth) acrylate, 1-methylnonyl (meth) acrylate, 1-ethyloctyl (meth) acrylate, 1- (n-butyl) hexyl (meth) acrylate, 1-dimethyloctyl (meth) acrylate, 1-dimethylpentyl (meth) acrylate, 2, 4-trimethylpentyl (meth) acrylate, 1,3, 3-tetramethylbutyl (meth) acrylate, n-methyloctyl (meth) acrylate, 1-methyloctyl (meth) acrylate, n-butyl (meth) acrylate, n-ethylhexyl (meth) acrylate, n-methyloctyl (meth) acrylate, n-octyl (meth) acrylate, n-pentyl (meth) acrylate, n-methyloctyl (meth) acrylate, n-butyl (meth) acrylate, n-butyl (meth) acrylate, n-octyl (meth) acrylate, n-butyl, n-octyl (meth) acrylate, and (meth) acrylate, n-butyl (meth) acrylate, n-butyl, n-acrylate, n-butyl, and (meth) acrylate, n-butyl, n-acrylate, and (meth) acrylate, n-butyl, and (meth) acrylate, n-acrylate, and (meth) acrylate, n-acrylate, and (meth) acrylate, n-acrylate, and (s, 3, 7-dimethyloctyl (meth) acrylate, n-undecyl (meth) acrylate, 1-methyldecyl (meth) acrylate, 1-ethylnonyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, 1-methyltrodecyl (meth) acrylate, n-pentadecyl (meth) acrylate, n-hexadecyl (meth) acrylate, n-heptadecyl (meth) acrylate, n-octadecyl (meth) acrylate, n-nonadecyl (meth) acrylate, n-eicosyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, and mixtures thereof, Norbornyl (meth) acrylate, norbornyl methyl (meth) acrylate, cyanonorbornyl (meth) acrylate, isobornyl (meth) acrylate, bornyl (meth) acrylate, menthyl (meth) acrylate, fenchyl (meth) acrylate, adamantyl (meth) acrylate, dimethyladamantyl (meth) acrylate, tricyclo [5.2.1.02,6]Decyl-8-yl (meth) acrylate, tricyclo [5.2.1.02,6]Decyl-4-methyl (meth) acrylate, cyclodecyl (meth) acrylate, and the like, which may be used alone or in combination of 2 or more. Among them, n-butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and cyclohexyl (meth) acrylate are preferable. In particular, cyclohexyl (meth) acrylate, n-butyl (meth) acrylate, or (meth) acrylic acid is more preferably used from the viewpoints of adjustment of the strength of the coating after drying and emulsifiability of the resulting dispersant2-ethylhexyl ester of acid.
The content of the (meth) acrylate component in the monomer component is preferably 0.1 to 30 mol%, more preferably 1 to 20 mol%, based on the total monomers constituting the polymeric dispersant (B). When the content is within this range, a dispersant having both workability and emulsifiability can be obtained.
The polymer dispersant used in the present invention may further contain other copolymerizable monomer components such as an ethylenically unsaturated monomer and an unsaturated carboxylic acid, if necessary. These other monomer components may be used alone or 2 or more kinds may be used in combination.
< ethylenically unsaturated monomer >
Examples of the ethylenically unsaturated monomer include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-N-butyl (meth) acrylamide, N-t-butyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, (meth) acrylamide monomers such as N-diethyl (meth) acrylamide, N-methyl-N-ethyl (meth) acrylamide, N-hydroxyethyl-N-methyl (meth) acrylamide, and (meth) acryloylmorpholine, and diene compounds such as 1, 3-butadiene and isoprene; ethylenically unsaturated sulfonic acids such as vinylsulfonic acid, methylvinylsulfonic acid, p-styrenesulfonic acid, (meth) allylsulfonic acid, (meth) acryloylsulfonic acid, ethyl (meth) acrylate-2-sulfonate, and 2-acrylamido-2-hydroxypropanesulfonic acid, and salts thereof; halogenated vinyl monomers such as vinyl chloride, vinyl bromide and 1, 1-dichloroethylene; vinyl acetate, and the like.
< unsaturated carboxylic acid >
In addition to itaconic acid (b-2) which is an essential component of the polymer dispersion of the present invention, other unsaturated carboxylic acids may be used within a range not impairing the effects of the present invention. Examples thereof include acrylic acid, methacrylic acid, crotonic acid, maleic anhydride, fumaric acid, citraconic anhydride, and mesaconic acid. These may be used alone, or 2 or more kinds may be used in combination.
The polymer dispersant (B) can be synthesized by a conventionally known polymerization method such as solution polymerization, emulsion polymerization, suspension polymerization, or the like. In the case of solution polymerization, water, lower alcohols such as methanol, ethanol, isopropanol and t-butanol, acetone, methyl ethyl ketone and di-n-butyl alcohol may be used
Figure BDA0001209271980000081
The polymerization may be carried out using a solvent such as an alkane alone or using 2 or more kinds of solvents in combination. In the case of emulsion polymerization or suspension polymerization, polymerization may be carried out in the above-mentioned solvent by using a conventionally known anionic and/or nonionic surfactant.
The polymerization initiator may be any conventionally known polymerization initiator. Specific examples thereof include persulfates such as ammonium persulfate, potassium persulfate and sodium persulfate, redox polymerization catalysts using a combination of these persulfates and a reducing agent, azo or diazo catalysts such as 2,2 '-Azobisisobutyronitrile (AIBN), 2' -azobis- (2, 4-dimethylvaleronitrile), 1 '-azobis (cyclohexane-1-carbonitrile) and 2, 2' -azobis-4-methoxy-2, 4-dimethylvaleronitrile, hydrogen peroxide, t-butyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, 2, 4-dichlorobenzoyl peroxide, and mixtures thereof, Peroxides such as lauroyl peroxide, 2-bis- (4, 4-t-butylperoxycyclohexyl) propane, and tris- (t-butylperoxy) triazine. The amount of the polymerization initiator used is not particularly limited, but is preferably about 0.01 to 0.50 parts by mass based on 100 parts by mass of the total amount of the monomers.
In synthesizing the polymer dispersant (B), a molecular weight modifier is preferably used in order to facilitate the adjustment of the molecular weight of the polymer dispersant (B).
Examples of the molecular weight modifier include n-dodecylmercaptan, t-dodecylmercaptan, n-octylmercaptan, stearylmercaptan, thiophenol, thiobenzoic acid, thiosalicylic acid, naphthylthiophenol, tolylthiophenol, mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptoethylene glycol, thioglycerol, cysteamine hydrochloric acid or a salt thereof, mercaptopropionic acid or a salt thereof, mercaptoacetic acid or a salt thereof, thioacetic acid or a salt thereof, thiomalic acid or a salt thereof, mercaptoacetic acid ester or mercaptopropionic acid ester having an alkyl group such as methyl, ethyl, propyl, butyl, methoxybutyl, n-octyl, or 2-ethylhexyl group, an ester of mercaptoacetic acid with a polyhydric alcohol such as ethylene glycol or trimethylolpropane, terpinolene, α -methylstyrene, or α -methylstyrene dimer. The amount of the molecular weight modifier is not particularly limited, but is preferably about 0.1 to 10 parts by mass based on 100 parts by mass of the total amount of the monomers.
The polymerization time and polymerization temperature are not particularly limited, and, for example, the polymerization time is in the range of 2 to 7 hours and the polymerization temperature is in the range of 70 to 90 ℃.
The obtained copolymer (polymer dispersant) may be neutralized with an inorganic base and/or an organic base at the carboxylic acid moiety in the copolymer as required. Examples of the inorganic base used for neutralization include sodium hydroxide and potassium hydroxide, and examples of the organic base include organic amines such as ammonium, monoethanolamine, diethanolamine, triethanolamine, morpholine and N-methylmorpholine. The neutralization of the copolymer with the base may be complete neutralization or partial neutralization.
The weight average molecular weight (Mw) of the obtained polymeric dispersant (B) is preferably 1,000 to 700,000, more preferably 1,500 to 500,000, and still more preferably 5,000 to 100,000. When the weight average molecular weight is within such a range, the polyolefin resin (A) can be dispersed efficiently. The weight average molecular weight of the polymer dispersant (B) is measured by the method described in the examples described below.
The polymer dispersant (B) may be used by isolation, and may be used in the form of a solution or an aqueous dispersion. However, from the viewpoint of more easily producing the aqueous dispersion of the present invention, the form of the aqueous dispersion is preferred.
[ aqueous Dispersion ]
The aqueous dispersion of the present invention comprises the polyolefin resin (a) having a weight average molecular weight of 2 ten thousand or more and the polymer dispersant (B).
The content (concentration) of the polyolefin resin (a) in the aqueous dispersion of the present invention is preferably 10 to 50% by mass, and more preferably 20 to 40% by mass, based on the total mass of the aqueous dispersion. The content of the polymeric dispersant (B) is preferably 1 to 35 parts by mass, more preferably 2 to 15 parts by mass, based on 100 parts by mass of the polyolefin resin (a).
The method for producing the aqueous dispersion of the present invention is not particularly limited, and for example, it can be obtained by adding the polyolefin resin (a), the polymeric dispersant (B), the aqueous medium, and if necessary, the emulsifier, the neutralizer, and the like to a device such as an autoclave capable of being pressurized and having a normal shear force, heating the mixture to a temperature near or at the softening temperature of the polyolefin resin (a), and stirring the mixture. Here, the aqueous medium is a liquid containing water as a main component, and may contain a water-soluble organic solvent.
Specific examples of the organic solvent that can be used include, for example, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, sec-pentanol, tert-pentanol, 1-ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol, cyclohexanol and the like, ketones such as methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, cyclohexanone and the like, tetrahydrofuran, and dioxane
Figure BDA0001209271980000101
Ethers such as alkanes, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, 3-methoxybutyl acetate, methyl propionate, ethyl propionate, diethyl carbonate, dimethyl carbonate, and other esters, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol ethyl ether acetate, and other glycol derivatives, as well as 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 3-methoxy-3-methyl-1-butanol, methoxybutanol, acetonitrile, dimethylformamide, dimethylacetamide, diacetone alcohol, ethyl acetoacetate, 1, 2-dimethylglycerol, 1, 3-dimethylglycerol, glycerol, and glycerol Trimethylglucamine (TML)And the like. These organic solvents may be used alone or in combination of 2 or more.
The amount of the organic solvent to be added is not particularly limited, and is preferably 0 to 10 parts by mass based on the whole aqueous medium.
The emulsifier is not particularly limited, and a nonionic surfactant is preferably used from the viewpoint of emulsifiability, safety, and suppression of gelation when various additives are added.
Examples of the nonionic surfactant include polyoxyethylene octyl ether, polyoxyethylene decyl ether, polyoxyethylene dodecyl ether, polyoxyethylene myristyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene isostearyl ether, polyoxyethylene behenyl ether, polyoxyethylene-2-ethylhexyl ether, polyoxyethylene alkyl ether (synthetic system), narrow (narrow) type polyoxyethylene alkyl ether, polyoxyethylene octyldodecyl ether, polyoxyethylene styrenated phenyl ether, polyoxyethylene β -naphthyl ether, polyoxyethylene hardened castor oil ether, polyethylene glycol monoalkyl fatty acid ester, polyethylene glycol fatty acid ester, and polyoxyethylene sorbitan monolaurate.
Further, in order to obtain a stable aqueous dispersion, a cationic surfactant, an anionic surfactant, an amphoteric surfactant, a reactive surfactant, a polymer dispersant other than the component (B), or the like may be used in combination as an emulsifier in addition to the above-mentioned nonionic surfactant.
Examples of the cationic surfactant include higher alkyl monoamines such as dodecylamine acetate and stearylamine acetate, alkyl diamine salts such as N-dodecyl-1, 3-diaminopropane adipate and N-dodecylpropylenediamine dioleate, and quaternary ammonium salts such as dodecyltrimethylammonium chloride and behenyltrimethylammonium chloride.
Examples of the anionic surfactant include a sodium salt of a semi-hardened tallow fatty acid soap, a sodium salt of a stearic acid soap, a potassium salt of an oleic acid soap, a sodium salt of a gum rosin-based disproportionated rosin, a dipotassium salt of alkenyl succinic acid, a sodium salt of lauryl sulfate, anhydrous sodium hydrogen sulfite, a sodium salt of polyoxyethylene alkyl (C12, C13) ether sulfate, an ammonium salt of polyoxyethylene lauryl sulfate, sodium dodecylbenzenesulfonate, and an alkylene oxide adduct of a higher alcohol (C6 to 28).
Examples of the amphoteric surfactant include carboxybetaine type, sulfobetaine type, phosphonobetaine type, amidoamino acid type, and imidazoline
Figure BDA0001209271980000111
Betaine surfactants, and the like.
Examples of the reactive surfactant include compounds having a reactive double bond such as an alkylphenylphenol polyoxyethylene adduct or a sulfate ester salt thereof, an allylalkylphenol polyoxyethylene adduct or a sulfate ester salt thereof, and an allyldialkylphenol polyoxyethylene adduct or a sulfate ester salt thereof.
Examples of the polymer dispersant other than the component (B) include polycarboxylic acid-based polymer dispersants having a plurality of carboxyl groups in the molecule, polyamine-based polymer dispersants having a plurality of amino groups in the molecule, polymer dispersants having a plurality of amide groups in the molecule, and polymer dispersants having a plurality of polycyclic aromatic compounds in the molecule.
Examples of the neutralizing agent include potassium hydroxide, sodium hydroxide, magnesium hydroxide, calcium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, calcium carbonate, calcium hydrogencarbonate, magnesium carbonate, magnesium hydrogencarbonate, monolaurylamine, trimethylamine, dimethylmonoethanolamine, triethanolamine, ethylenediamine, ammonia, morpholine, N-methylmorpholine, and N-ethylmorpholine. These may be blended in an appropriate amount according to the use, and the blending is preferably about 0.1 to 10 mass% based on the total amount of the aqueous dispersion.
The average particle diameter of the aqueous dispersion is not particularly limited, and may be arbitrarily adjusted according to the application, but when used as a fiber sizing agent, it is preferably 50 to 1,000nm, and particularly preferably 100 to 300 nm.
The aqueous dispersion of the present invention may further contain a compounding agent generally used, for example, an antioxidant, a surface treatment agent, a lubricant, a slip agent (or a hand modifier), an antistatic agent, a pH adjuster, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a defoaming agent, an anti-aging agent, a leveling agent, and the like.
Examples of the antioxidant include phenol-based antioxidants such as hydroquinone, methoxyhydroquinone, catechol, 2, 6-di-tert-butyl-p-cresol (BHT), and 2, 2' -methylenebis (4-methyl-6-tert-butylphenol); sulfur-containing compounds such as thiourea, tetramethylthiuram disulfide, dimethyldithiocarbamic acid and salts thereof, sodium sulfite, sodium thiosulfate, 2-mercaptobenzothiazole and salts thereof, dilauryl 3,3 '-thiodipropionate (DLTDP), distearyl 3, 3' -thiodipropionate (DSTDP), and the like; phosphorus-containing compounds such as triphenyl phosphite, triethyl phosphite, sodium hypophosphite, triphenyl phosphite (TPP), and triisodecyl phosphite (TDP); nitrogen-containing compounds such as octylated diphenylamine, N-butyl-p-aminophenol, N-diisopropyl-p-phenylenediamine, urea, guanidine, and the like; and so on.
Examples of the surface treatment agent include coupling agents such as an aminosilane-based coupling agent, an epoxy silane-based coupling agent, a vinyl silane-based coupling agent, a methacryl silane-based coupling agent, a ureido silane-based coupling agent, a borane-based coupling agent, a titanate-based coupling agent, an aluminum-based coupling agent, a chromium-based coupling agent, and a zirconium-based coupling agent; colloidal gels such as colloidal silica and colloidal alumina.
Examples of the lubricant include hydrogenated animal and vegetable oils, paraffin wax, and ester-based synthetic oil.
Examples of the slip agent (or the hand modifier) include butyl stearate, tetraethylenepentamine distearate, hydrogenated castor oil, imidazoline fatty acid amide, cationic polyethyleneimine polyamide, bisphenol a poly (oxyethylene) ether glycol, and the like.
Examples of the antistatic agent include various surfactants such as an anionic surfactant and a cationic surfactant.
Examples of the pH adjuster include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, acids such as organic acids such as citric acid, succinic acid, malic acid, and lactic acid, and bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, monoethanolamine, diethanolamine, and triethanolamine.
Examples of the ultraviolet absorber include benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, triazine-based ultraviolet absorbers, cyclic imino ester-based ultraviolet absorbers, and phenyl salicylate-based ultraviolet absorbers.
Examples of the light stabilizer include hindered amine light stabilizers such as 2,2,6, 6-tetramethyl-4-piperidyl stearate and 1,2,2,6, 6-pentamethyl-4-piperidyl stearate.
The aqueous dispersion of the present invention is suitably used for, for example, a sizing agent for inorganic fibers such as glass fibers, a sizing agent for carbon fibers, a metal coating, a lubricant, a toner binder, a heat sealing agent for glass fibers and an olefin resin, floor wax, and the like.
Examples
The present invention will be described in further detail with reference to examples, but the present invention is not limited to the examples. The weight average molecular weight was measured under the following conditions.
The measuring instrument comprises: do ソー GmbH GPC-8020modeIII
Column: GPWXL manufactured by Toho ソー K.K
Measuring temperature: 40 deg.C
A detector: differential refractometer
< production of dispersant >
Production example 1
161.7 parts by mass of styrene, 67.3 parts by mass of itaconic acid, 29.4 parts by mass of butyl acrylate and 246.6 parts by mass of isopropyl alcohol were placed in a five-neck flask equipped with a thermometer, a cooler, a stirrer and a nitrogen inlet tube. The mixture was heated to 80 ℃ under a nitrogen atmosphere, and stirred. Then, 6.6 parts by mass of 2, 2-azobis (2-methylbutyronitrile) was added as a polymerization initiator, and polymerization was carried out at 80 ℃ for 5 hours. After the reaction, the isopropyl alcohol was removed, and the reaction mixture was further heated and dried to obtain polymer dispersant 1 having a weight average molecular weight of 31,500.
Production example 2
In a reaction apparatus similar to that of production example 1, 176.1 parts by mass of styrene, 73.3 parts by mass of itaconic acid, 7.1 parts by mass of cyclohexyl acrylate, and 247.0 parts by mass of isopropyl alcohol were charged. The mixture was heated to 80 ℃ under a nitrogen atmosphere, and stirred. Then, 8.8 parts by mass of 2, 2-azobis (2-methylbutyronitrile) was added as a polymerization initiator, and polymerization was carried out at 80 ℃ for 5 hours. After the reaction, the isopropyl alcohol was removed, and the reaction mixture was further heated and dried to obtain polymer dispersant 2 having a weight average molecular weight of 25,200.
(production example 3)
161.7 parts by mass of styrene, 67.3 parts by mass of itaconic acid, 29.4 parts by mass of butyl acrylate, 246.6 parts by mass of isopropyl alcohol, and 5.0 parts by mass of n-octyl mercaptan were charged in the same reaction apparatus as in production example 1. The mixture was heated to 80 ℃ under a nitrogen atmosphere, and stirred. Then, 6.6 parts by mass of 2, 2-azobis (2-methylbutyronitrile) was added as a polymerization initiator, and polymerization was carried out at 80 ℃ for 5 hours. After the reaction, the isopropanol was removed, and further heating and drying were performed, thereby obtaining a polymeric dispersant 3 having a weight average molecular weight of 12,800.
Production example 4
In a reaction apparatus similar to that of production example 1, 176.1 parts by mass of styrene, 73.3 parts by mass of itaconic acid, 8.5 parts by mass of 2-ethylhexyl acrylate, 245.6 parts by mass of isopropyl alcohol, and 5.0 parts by mass of n-octyl mercaptan were charged. The mixture was heated to 80 ℃ under a nitrogen atmosphere, and stirred. Then, 8.8 parts by mass of 2, 2-azobis (2-methylbutyronitrile) was added as a polymerization initiator, and polymerization was carried out at 80 ℃ for 5 hours. After the reaction, the isopropyl alcohol was removed, and the reaction mixture was further heated and dried to obtain polymer dispersant 4 having a weight average molecular weight of 12,000.
Production example 5
In the same reaction apparatus as in production example 1, 156.5 parts by mass of styrene, 97.8 parts by mass of itaconic acid, 5.9 parts by mass of butyl acrylate and 246.1 parts by mass of isopropyl alcohol were charged, respectively. The mixture was heated to 80 ℃ under a nitrogen atmosphere, and stirred. Then, 8.8 parts by mass of 2, 2-azobis (2-methylbutyronitrile) was added as a polymerization initiator, and polymerization was carried out at 80 ℃ for 5 hours. After the reaction, the isopropanol was removed, and further heat drying was performed, thereby obtaining polymer dispersant 5 having a weight average molecular weight of 26,800.
(production example 6)
In a reaction apparatus similar to that of production example 1, 156.5 parts by mass of styrene, 97.8 parts by mass of itaconic acid, 5.9 parts by mass of butyl acrylate, 246.1 parts by mass of isopropyl alcohol, and 5.0 parts by mass of n-octyl mercaptan were charged. The mixture was heated to 80 ℃ under a nitrogen atmosphere, and stirred. Then, 8.8 parts by mass of 2, 2-azobis (2-methylbutyronitrile) was added as a polymerization initiator, and polymerization was carried out at 80 ℃ for 5 hours. After the reaction, the isopropyl alcohol was removed, and further heating and drying were performed, thereby obtaining a polymeric dispersant 6 having a weight average molecular weight of 10,300.
Production example 7
In a reaction apparatus similar to that of production example 1, 114.6 parts by mass of styrene, 85.8 parts by mass of itaconic acid, 56.3 parts by mass of butyl acrylate, and 247.7 parts by mass of isopropyl alcohol were charged. The mixture was heated to 80 ℃ under a nitrogen atmosphere, and stirred. Then, 8.5 parts by mass of 2, 2-azobis (2-methylbutyronitrile) was added as a polymerization initiator, and polymerization was carried out at 80 ℃ for 5 hours. After the completion of the reaction, the isopropanol was removed, and further heating and drying were performed to obtain polymer dispersant 7 having a weight average molecular weight of 33,400.
Production example 8
212.5 parts by mass of styrene, 40.6 parts by mass of itaconic acid, 6.1 parts by mass of butyl acrylate, 244.3 parts by mass of isopropyl alcohol, and 5.3 parts by mass of n-octyl mercaptan were charged in the same reaction apparatus as in production example 1. The mixture was heated to 80 ℃ under a nitrogen atmosphere, and stirred. Then, 9.2 parts by mass of 2, 2-azobis (2-methylbutyronitrile) was added as a polymerization initiator, and polymerization was carried out at 80 ℃ for 5 hours. After the reaction, the isopropyl alcohol was removed, and further heating and drying were performed, thereby obtaining polymeric dispersant 8 having a weight average molecular weight of 12,500.
Production example 9
212.5 parts by mass of styrene, 46.9 parts by mass of itaconic acid and 249.6 parts by mass of isopropyl alcohol were charged in the same reaction apparatus as in production example 1. The mixture was heated to 80 ℃ under a nitrogen atmosphere, and stirred. Then, 9.2 parts by mass of 2, 2-azobis (2-methylbutyronitrile) was added as a polymerization initiator, and polymerization was carried out at 80 ℃ for 5 hours. After the completion of the reaction, the isopropyl alcohol was removed, and the reaction mixture was further heated and dried to obtain polymer dispersant 9 having a weight average molecular weight of 25,900.
Production example 10
In the same reaction apparatus as in production example 1, 167.7 parts by mass of styrene, 89.7 parts by mass of itaconic acid, and 247.9 parts by mass of isopropyl alcohol were charged. The mixture was heated to 80 ℃ under a nitrogen atmosphere, and stirred. Then, 8.9 parts by mass of 2, 2-azobis (2-methylbutyronitrile) was added as a polymerization initiator, and polymerization was carried out at 80 ℃ for 5 hours. After the completion of the reaction, the isopropanol was removed, and further heating and drying were performed to obtain polymer dispersant 10 having a weight average molecular weight of 27,200.
Production example 11
In the same reaction apparatus as in production example 1, 143.7 parts by mass of styrene, 119.7 parts by mass of itaconic acid, 248.9 parts by mass of isopropyl alcohol and 5.0 parts by mass of n-octyl mercaptan were charged, respectively. The mixture was heated to 80 ℃ under a nitrogen atmosphere, and stirred. Then, 8.9 parts by mass of 2, 2-azobis (2-methylbutyronitrile) was added as a polymerization initiator, and polymerization was carried out at 80 ℃ for 5 hours. After the reaction, the isopropanol was removed, and further heat drying was performed, thereby obtaining a polymer dispersant 11 having a weight average molecular weight of 11,000.
Production example 13
In a reaction apparatus similar to that of production example 1, 200.0 parts by mass of styrene, 15.6 parts by mass of itaconic acid, 46.2 parts by mass of butyl acrylate and 252.2 parts by mass of isopropyl alcohol were charged, respectively. The mixture was heated to 80 ℃ under a nitrogen atmosphere, and stirred. Then, 9.2 parts by mass of 2, 2-azobis (2-methylbutyronitrile) was added as a polymerization initiator, and polymerization was carried out at 80 ℃ for 5 hours. After the completion of the reaction, isopropyl alcohol was removed, and further, heating and drying were performed, thereby obtaining comparative dispersing agent 12 having a weight average molecular weight of 34,200.
Production example 14
In the same reaction apparatus as in production example 1, 91.7 parts by mass of styrene, 157.4 parts by mass of itaconic acid, 14.1 parts by mass of butyl acrylate, 249.7 parts by mass of isopropyl alcohol, and 4.8 parts by mass of n-octyl mercaptan were charged, respectively. The mixture was heated to 80 ℃ under a nitrogen atmosphere, and stirred. Then, 8.5 parts by mass of 2, 2-azobis (2-methylbutyronitrile) was added as a polymerization initiator, and polymerization was carried out at 80 ℃ for 5 hours. After the reaction was completed, isopropyl alcohol was removed, and further heat drying was performed, thereby obtaining a comparative dispersant 13 having a weight average molecular weight of 10,400.
[ Table 1]
Figure BDA0001209271980000171
Production of aqueous Dispersion
(example 1)
An autoclave having a stirrer, a thermometer and an emulsification apparatus with an internal volume of 1.0L and a temperature controller was charged with maleic anhydride-modified polypropylene ("EASTMAN G3003" manufactured by EASTMAN CHEMICAL COMPANY, weight average molecular weight: 120,000, acid value: 8)154.2G, maleic anhydride-modified polypropylene ("ハイワックス NP 0555A" manufactured by Mitsui chemical Co., Ltd., weight average molecular weight: 30,000, acid value: 45)66.1G, (polymer dispersant 1 manufactured by production example 1 (concentration of polymer dispersant 1: 100% by mass), oleic acid ("NAA-34" manufactured by Nippon oil Co., Ltd.), oleic acid diethanolamide ("ブライトン OL-2") 11.5G, polyoxyethylene alkyl ether (manufactured by Toho chemical Co., Ltd., ペグノール C-18)11.0G, polyoxyethylene alkyl ether (manufactured by Qing oil and fat industries, ブラウノン SR-715)6.6g, polyoxyethylene alkyl ether (ペグノール O-16A, manufactured by Toho chemical industries Co., Ltd.), 4.8g, dimethylethanolamine (aminoalcohol 2Mabs, manufactured by Nippon emulsifier Co., Ltd.), 14.4g of N-methylmorpholine (カオーライザー No.21, manufactured by Kao corporation), 3.7g of a 48% potassium hydroxide aqueous solution, and 259.9g of ion-exchanged water, and they were heated to 170 ℃ and aged at 800rpm for 1 hour. Then, the mixture was cooled to 120 ℃ and the internal pressure was reduced, and then 140g of ion-exchanged water of 170 ℃ separately prepared was added thereto, and the mixture was further heated to 170 ℃ and aged at 800rpm for 1 hour. After aging, the mixture was cooled to 40 ℃ to obtain an aqueous dispersion 1 having a solid content concentration of 40% by mass and containing the maleic anhydride-modified polypropylene.
(examples 2 to 12)
Based on the formulations shown in table 2, aqueous dispersions 2 to 12 were obtained in the same manner as in example 1.
Comparative examples 1 to 5
Based on the recipe shown in table 2, the same operation as in example 1 was performed. However, in comparative examples 3 and 4, a large amount of unemulsified maleic anhydride-modified polypropylene was produced.
< evaluation >
1. Emulsion stability
The state of the aqueous dispersion after production was visually observed after 1 month storage at room temperature (25 ℃ C.).
The properties and various evaluation results of the aqueous dispersions obtained in examples 1 to 9 are shown in Table 2.
2.pH
Measured according to JIS K-6833.
3. Viscosity of the oil
Measured according to JIS Z-8802.
4. Average particle diameter
The average Particle diameter of the resin particles was measured from the light intensity distribution of scattered light by NICOMP 380, manufactured by Particle sizing systems.
5. Interfacial shear stress (microdroplet test)
The adhesiveness was evaluated by the micro-drop method using a composite material interface characteristic evaluation apparatus H M410 (manufactured by yoto industries co., ltd.). A glass roving (average filament diameter: 12 μm, material: E-glass) purchased from フェザーフィールド was put into an electric furnace, heat-treated at 600 ℃ for 3 hours to remove a sizing agent attached to the surface of the filaments (single fibers), and then the filaments were taken out from the roving. The obtained filaments were placed on a predetermined position of a table paper dedicated to a composite material interfacial property evaluation device, the emulsion shown in example diluted to 5 to 10 wt% in terms of solid content was sprayed on the filaments by a sprayer, and then the filaments were put into a natural convection dryer in a nitrogen atmosphere, heated at 180 ° c. × 5 minutes, cooled to 100 ℃, heat-treated again at 180 ° c. × 5 minutes, and cooled to room temperature, and droplets (drop) were produced on the glass fiber filaments. This was placed as a sample for measurement in a composite material interface characteristic evaluation device, and the glass fiber filament was moved on the device at a speed of 0.12 mm/min while being held by a blade of the device, and the maximum drawing load F at room temperature when the drop was drawn from the glass fiber filament was measured.
The interfacial shear strength τ was calculated from the following formula, and the adhesion between the glass fiber filaments and the emulsion component (nonvolatile component) was evaluated.
Interfacial shear strength tau (unit: MPa) ═ F/pi dl
F: maximum pull-out load
d: diameter of glass fiber filament
l: particle diameter of droplet-like substance in pulling-out direction
The properties and various evaluation results of the aqueous dispersions obtained in examples 1 to 12 and comparative examples 1 to 5 are shown in table 2.
[ Table 2]
Figure BDA0001209271980000201
As is clear from table 2, in the aqueous dispersion of the present invention, the polyolefin resin was well dispersed, and the adhesion to the glass fiber filaments was also good. On the other hand, as described above, the aqueous dispersions of comparative examples 1,3 and 4 were poor in emulsification, and the aqueous dispersions of comparative examples 1 to 5 were inferior to the dispersant of the present invention in that the adhesion to the glass fiber filaments was low.

Claims (4)

1. An aqueous dispersion comprising:
a polyolefin resin (A) having a weight average molecular weight of 2 ten thousand or more, and
a polymer dispersant (B) obtained by copolymerizing monomer components comprising 50 to 90 mol% of a styrene monomer (B-1) and 10 to 50 mol% of itaconic acid (B-2).
2. The aqueous dispersion according to claim 1, wherein the monomer component further comprises 2 to 30 mol% of a (meth) acrylate with respect to all monomers constituting the polymeric dispersant (B).
3. The aqueous dispersion according to claim 1 or 2, wherein the content of the polyolefin resin (A) is 10 to 50% by mass relative to the total mass of the aqueous dispersion,
the amount of the polyolefin resin (A) is set to 100 parts by mass, and the content of the polymeric dispersant (B) is 1 to 35 parts by mass.
4. A sizing agent for fibers, comprising the aqueous dispersion according to any one of claims 1 to 3.
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Citations (4)

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Publication number Priority date Publication date Assignee Title
CN1751080A (en) * 2003-02-21 2006-03-22 丸芳化成品株式会社 Process for producing aqueous emulsion
CN101712730A (en) * 2009-05-13 2010-05-26 北京瑞仕邦精细化工技术有限公司 Preparation method of water-soluble polymer dispersion
CN103965392A (en) * 2013-02-04 2014-08-06 罗门哈斯公司 Acrylic latex binder and method of preparation
CN105247002A (en) * 2012-11-19 2016-01-13 瀚森公司 Pressure sensitive adhesive compositions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1751080A (en) * 2003-02-21 2006-03-22 丸芳化成品株式会社 Process for producing aqueous emulsion
CN101712730A (en) * 2009-05-13 2010-05-26 北京瑞仕邦精细化工技术有限公司 Preparation method of water-soluble polymer dispersion
CN105247002A (en) * 2012-11-19 2016-01-13 瀚森公司 Pressure sensitive adhesive compositions
CN103965392A (en) * 2013-02-04 2014-08-06 罗门哈斯公司 Acrylic latex binder and method of preparation

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