WO2015186733A1 - Dispersion aqueuse, et stratifié - Google Patents

Dispersion aqueuse, et stratifié Download PDF

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Publication number
WO2015186733A1
WO2015186733A1 PCT/JP2015/066022 JP2015066022W WO2015186733A1 WO 2015186733 A1 WO2015186733 A1 WO 2015186733A1 JP 2015066022 W JP2015066022 W JP 2015066022W WO 2015186733 A1 WO2015186733 A1 WO 2015186733A1
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Prior art keywords
acid
resin
aqueous dispersion
modified
polypropylene resin
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PCT/JP2015/066022
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English (en)
Japanese (ja)
Inventor
剛正 吉野
暢康 奥村
晴樹 大藤
志波　賢人
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ユニチカ株式会社
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Application filed by ユニチカ株式会社 filed Critical ユニチカ株式会社
Priority to KR1020167029223A priority Critical patent/KR102302377B1/ko
Priority to JP2016525202A priority patent/JP6628718B2/ja
Priority to CN201580026430.3A priority patent/CN106459524A/zh
Publication of WO2015186733A1 publication Critical patent/WO2015186733A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • 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
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene

Definitions

  • the present invention relates to an aqueous dispersion which is excellent in adhesiveness to various base materials, and particularly has good adhesiveness in a laminate in which a polyolefin base material and other base materials are bonded.
  • Polyolefin resins such as polypropylene resins are excellent in electrical properties, mechanical properties, chemical properties, formability, hygiene, recyclability, etc., and are used mainly in automobiles, electricity, packaging, daily goods, and the like.
  • a polyolefin resin has a problem that it is difficult to adhere with an adhesive because it does not have a polar group in a molecular chain. Therefore, it has been proposed to use a chlorinated polyolefin resin as an adhesive component when bonding to a polyolefin resin such as a polypropylene resin.
  • chlorinated polyolefin resin generates harmful substances such as acid gas when discarded by incineration, the shift to non-chlorine binder resins is strongly desired in recent years as interest in the environment increases. Yes.
  • Patent Documents 1 and 2 disclose a technique for obtaining an acid-modified polyolefin resin aqueous dispersion without substantially using a surfactant.
  • Patent Document 3 discloses an aqueous dispersion containing an acid-modified polyolefin resin and a polyester resin.
  • Patent Document 4 discloses an aqueous dispersion containing two acid-modified polyolefin resins having different olefin component carbon numbers. Dispersions are disclosed.
  • the coatings obtained from the aqueous dispersions disclosed in Patent Documents 1 to 3 have room for improvement in adhesion to polyolefin resins such as cycloolefin polymers, and are water resistant, alkali resistant, and chemical resistant. Was inferior.
  • the aqueous dispersion containing the acid-modified polyolefin resin and the polyester resin disclosed in Patent Document 3 may increase in viscosity or gel when stored for a long period of time.
  • the coating film obtained from the aqueous dispersion containing two kinds of acid-modified polyolefin resins disclosed in Patent Document 4 has improved adhesion to polyolefin resins such as cycloolefin polymers.
  • the present invention eliminates the above-mentioned drawbacks of the prior art, and is an aqueous dispersion excellent in liquid stability comprising an acid-modified polyolefin resin aqueous dispersion, which has adhesiveness to a polyolefin resin substrate and water resistance. It is an object to provide an aqueous dispersion capable of forming a coating film excellent in alkali resistance and chemical resistance by a low-temperature press and capable of producing a laminate excellent in content resistance. is there.
  • an aqueous dispersion containing a specific acid-modified polyethylene resin and a specific acid-modified polypropylene resin can solve the above problems, and have reached the present invention.
  • the gist of the present invention is as follows. (1) An aqueous dispersion containing an acid-modified polyethylene resin (A), an acid-modified polypropylene resin (B), and an aqueous medium,
  • the acid-modified polyethylene resin (A) contains an olefin component containing ethylene and an unsaturated carboxylic acid component as a copolymerization component, and the content of the unsaturated carboxylic acid component is 0.1 to 15% by mass
  • the acid-modified polypropylene resin (B) contains an olefin component consisting of propylene and butene and an unsaturated carboxylic acid component as a copolymer component
  • An aqueous dispersion, wherein the mass ratio (A / B) of the acid-modified polyethylene resin (A) and the acid-modified polypropylene resin (B) is 95/5 to 50/50.
  • the aqueous dispersion of the present invention contains a specific acid-modified polyethylene resin (A) and a specific acid-modified polypropylene resin (B), thereby providing a coating having good water resistance, alkali resistance, and chemical resistance. Films can be obtained, and laminates excellent in adhesion strength with polyolefin resin substrates such as cycloolefin polymers and various substrates can be obtained with a low-temperature press, and a bag made from this laminate is Excellent content resistance.
  • the aqueous dispersion of the present invention is excellent in liquid stability. Therefore, the aqueous dispersion of the present invention can be suitably used for various applications including optical films that require chemical resistance.
  • the aqueous dispersion of the present invention contains an acid-modified polyethylene resin (A) and an acid-modified polypropylene resin (B) in a specific ratio in an aqueous medium.
  • the acid-modified polyethylene resin (A) contains an olefin component containing ethylene and an unsaturated carboxylic acid component as copolymerization components.
  • the ethylene content in the olefin component is preferably 50% by mass or more, and more preferably 70% by mass or more. If the ethylene content in the olefin component is less than 50% by mass, characteristics such as adhesion to the substrate derived from polyethylene resin may be lost.
  • Examples of the olefin component other than ethylene include alkenes such as propylene, isobutylene, 1-butene, 1-pentene, 1-hexene and 1-octene, and cycloalkenes such as norbornene, and mixtures thereof can also be used.
  • alkenes having 3 to 6 carbon atoms such as propylene, isobutylene, 1-butene, 1-pentene and 1-hexene are preferable, and alkenes having 3 to 4 carbon atoms such as propylene, isobutylene and 1-butene are more preferable.
  • the content of the unsaturated carboxylic acid component as a copolymerization component needs to be 0.1 to 15% by mass.
  • the mass is preferably 0.1% by mass, more preferably 0.1 to 5% by mass, still more preferably 0.5 to 4% by mass, and particularly preferably 1 to 4% by mass.
  • aqueous dispersion of the acid-modified polyethylene resin (A) becomes difficult.
  • the content of the unsaturated carboxylic acid component exceeds 15% by mass, the resulting coating film may have poor water resistance, alkali resistance, and chemical resistance.
  • the unsaturated carboxylic acid component is an unsaturated carboxylic acid or an anhydride thereof, specifically, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, etc.
  • Other examples include half esters and half amides of unsaturated dicarboxylic acids. Among them, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are exemplified, and acrylic acid and maleic anhydride are preferable.
  • the unsaturated carboxylic acid component may be copolymerized in the acid-modified polyethylene resin (A), and the form thereof is not limited. Examples thereof include random copolymerization, block copolymerization, and graft copolymerization.
  • the acid anhydride component introduced into the acid-modified polyethylene resin (A) is easy to take an acid anhydride structure in a dry state, and a part or all of the acid anhydride component is ring-opened in an aqueous medium containing a basic compound described later. However, it tends to be a carboxylic acid or a salt thereof.
  • the method for introducing the unsaturated carboxylic acid component into the unmodified polyethylene resin is not particularly limited.
  • the unmodified polyethylene resin and the unsaturated carboxylic acid component are heated above the melting point of the unmodified polyethylene resin.
  • the method of graft-copolymerizing an unsaturated carboxylic acid component is mentioned.
  • radical generator used for graft copolymerization examples include di-tert-butyl peroxide, dicumyl peroxide, tert-butyl hydroperoxide, tert-butyl cumyl peroxide, benzoyl peroxide, dilauryl peroxide, Examples thereof include organic peroxides such as cumene hydroperoxide, tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, and di-tert-butyl diperphthalate, and azo compounds such as azobisisobutyronitrile. These may be appropriately selected and used depending on the reaction temperature.
  • the unsaturated carboxylic acid component is introduced into the unmodified polyethylene resin by the method as described above, the unreacted unsaturated carboxylic acid monomer remains in the acid-modified polyethylene resin (A). Moreover, if there is much content of the unsaturated carboxylic acid component as a copolymerization component in acid-modified polyethylene resin (A), it exists in the tendency which many unreacted unsaturated carboxylic acid monomers remain
  • the acid-modified polyethylene resin (A) preferably contains a (meth) acrylic acid ester component for the purpose of improving adhesiveness with various thermoplastic resin substrates, including polyolefin resin substrates such as polypropylene resins. .
  • the content of the (meth) acrylic acid ester component in the acid-modified polyethylene resin (A) is preferably 0.5 to 40% by mass, more preferably 1 to 35% by mass, and 3 to 30% by mass. More preferably, it is 5 to 25% by mass, most preferably 10 to 25% by mass.
  • the adhesiveness with the substrate may be lowered, and when it exceeds 40% by mass, the properties derived from the polyethylene resin are lost, Adhesiveness may be reduced.
  • the (meth) acrylic acid ester component include esterified products of (meth) acrylic acid and alcohols having 1 to 30 carbon atoms. Among them, (meth) acrylic acid and carbon atoms of 1 are easy to obtain. Esterified products with ⁇ 20 alcohols are preferred.
  • Such compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic acid.
  • examples include octyl, decyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, and the like. Mixtures of these may be used.
  • methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl acrylate, and octyl acrylate are more preferable from the viewpoint of adhesion to the substrate, and ethyl acrylate. Further, butyl acrylate is more preferable, and ethyl acrylate is particularly preferable.
  • (meth) acrylic acid means “acrylic acid or methacrylic acid”.
  • the acid-modified polyethylene resin (A) may contain 10% by mass or less of other components other than the above components based on the total acid-modified polyethylene resin.
  • Other components include dienes, maleic esters such as dimethyl maleate, diethyl maleate and dibutyl maleate, (meth) acrylic amides, alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, vinyl formate, Vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versatate, vinyl alcohol obtained by saponifying vinyl esters with basic compounds, 2-hydroxyethyl acrylate, glycidyl (meth) acrylate, ( (Meth) acrylonitrile, styrene, substituted styrene, carbon monoxide, sulfur dioxide and the like can be mentioned, and a mixture thereof can also be used.
  • Examples of the acid-modified polyethylene resin (A) include ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester-maleic anhydride copolymer, ethylene-maleic anhydride copolymer, ethylene- Propylene-maleic anhydride copolymer, ethylene-butene-maleic anhydride copolymer, ethylene-propylene-butene-maleic anhydride copolymer, or these acid-modified resins further modified with acrylic ester Is mentioned.
  • the polyethylene resin may be chlorinated in the range of 5 to 40% by mass.
  • the acid-modified polyethylene resin (A) in the present invention preferably has a weight average molecular weight of 5,000 to 100,000, more preferably 10,000 to 80,000, and 20,000 to 70,000. Is more preferably 30,000, and most preferably 30,000 to 60,000. If the weight average molecular weight of the acid-modified polyethylene resin (A) is less than 5,000, the adhesion to the base material tends to decrease or the resulting coating film tends to be hard and brittle, while the weight average molecular weight is If it exceeds 100,000, it tends to be difficult to make the resin water-based. In addition, the weight average molecular weight of resin can be calculated
  • GPC gel permeation chromatography
  • a commercially available acid-modified polyethylene resin (A) may be used.
  • examples include the Nucleel series manufactured by Mitsui DuPont, the Bond First series manufactured by Sumitomo Chemical, the Bondine series manufactured by Sumitomo Chemical, and the Primacor series manufactured by Dow Chemical.
  • an unmodified polyethylene resin such as Novatec series manufactured by Nippon Polyethylene Co., Ltd. or Zeonex series manufactured by Prime Polymer Co., Ltd. may be used in which an unsaturated carboxylic acid component is introduced by a known method. .
  • the acid-modified polypropylene resin (B) contains an olefin component composed of propylene and butene and an unsaturated carboxylic acid component as copolymerization components.
  • the olefin component of the acid-modified polypropylene resin (B) needs to be composed of propylene and butene (1-butene, isobutene, etc.). When other olefins are contained as the olefin component, the resulting aqueous dispersion is bonded at low temperature.
  • the coating film may have poor chemical resistance, and a bag made from the laminate may have poor content resistance.
  • the mass ratio of propylene to butene (propylene / butene) in the olefin component is 60/40 from the viewpoint of reducing the dispersed particle size of the acid-modified polypropylene resin (B) and improving the adhesion to the polypropylene resin substrate. It is preferably ⁇ 95 / 5, more preferably 60/40 to 80/20.
  • the dispersed particle size of the acid-modified polypropylene resin (B) becomes large, making it difficult to disperse the resin in water, and the resulting aqueous dispersion
  • the body tends to have low adhesion to a polypropylene resin substrate or a cycloolefin polymer substrate.
  • the aqueous dispersion of the present invention becomes an aqueous dispersion in which the difference in the number average particle diameter of each of the acid-modified polyethylene resin (A) and the acid-modified polypropylene resin (B) is small as described later, Low temperature adhesion may also be reduced.
  • a plurality of acid-modified polypropylene resins (B) may be mixed and used as necessary.
  • the content of the unsaturated carboxylic acid component as a copolymerization component is 0.000 parts by mass with respect to 100 parts by mass of the olefin component consisting of propylene and butene, from the viewpoint of dispersibility in an aqueous medium. It is preferably 5 to 15 parts by mass, more preferably 0.5 to 10 parts by mass, further preferably 0.5 to 8 parts by mass, and particularly preferably 1 to 7 parts by mass. Most preferably, it is 1.5 to 7 parts by mass.
  • the content of the unsaturated carboxylic acid component is less than 0.5 parts by mass, it may be difficult to make the acid-modified polypropylene resin (B) water-based, while when the content exceeds 15 parts by mass. However, it is easy to make the resin water-based, but the adhesion to the polypropylene resin substrate may be lowered.
  • unsaturated carboxylic acid components acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, aconitic acid, aconitic anhydride, fumaric acid, crotonic acid, citraconic acid, mesaconic acid, allyl succinic acid, etc.
  • compounds having at least one carboxyl group or acid anhydride group in the molecule (in the monomer unit) such as unsaturated dicarboxylic acid half esters and half amides, can also be used.
  • maleic anhydride acrylic acid and methacrylic acid are preferred, and maleic anhydride is more preferred from the viewpoint of easy introduction into a polypropylene resin containing propylene and butene (hereinafter referred to as unmodified polypropylene resin). . Therefore, in this invention, it is preferable to use a propylene / butene / maleic anhydride terpolymer as the acid-modified polypropylene resin (B).
  • the unsaturated carboxylic acid component only needs to be copolymerized in the acid-modified polypropylene resin, and the form thereof is not limited. Examples thereof include random copolymerization, block copolymerization, and graft copolymerization.
  • the acid anhydride component introduced into the acid-modified polypropylene resin (B) easily takes an acid anhydride structure in a dry state, and a part or all of the acid anhydride component is ring-opened in an aqueous medium containing a basic compound described later. However, it tends to be a carboxylic acid or a salt thereof.
  • the method for introducing the unsaturated carboxylic acid component into the unmodified polypropylene resin is not particularly limited.
  • the unmodified polypropylene resin and the unsaturated carboxylic acid component are heated to the melting point of the unmodified polypropylene resin or higher in the presence of a radical generator.
  • the method of graft-copolymerizing an unsaturated carboxylic acid component is mentioned.
  • radical generator used for graft copolymerization examples include di-tert-butyl peroxide, dicumyl peroxide, tert-butyl hydroperoxide, tert-butyl cumyl peroxide, benzoyl peroxide, dilauryl peroxide, Examples thereof include organic peroxides such as cumene hydroperoxide, tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, and di-tert-butyl diperphthalate, and azo compounds such as azobisisobutyronitrile. These may be appropriately selected and used depending on the reaction temperature.
  • the unsaturated carboxylic acid component is introduced into the unmodified polypropylene resin by the method as described above, the unreacted unsaturated carboxylic acid monomer remains in the acid-modified polypropylene resin (B). Moreover, if there is much content of the unsaturated carboxylic acid component as a copolymerization component in acid-modified polypropylene resin (B), it exists in the tendency for many unreacted unsaturated carboxylic acid monomers to remain
  • the acid-modified polypropylene resin (B) in the present invention may contain other components other than those described above as necessary.
  • Other components include (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate, maleic acid such as dimethyl maleate, diethyl maleate, and dibutyl maleate.
  • Acid esters (meth) acrylic amides, alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versatate and vinyl esters Vinyl alcohol, 2-hydroxyethyl acrylate, glycidyl (meth) acrylate, (meth) acrylonitrile, styrene, substituted styrene, vinyl halides, vinylidene halides, carbon monoxide, Diacid Sulfur and the like, may be a mixture thereof. In general, the content of these other components is preferably 10% by mass or less of the acid-modified polypropylene resin (B).
  • acid-modified polypropylene resin (B) may be used.
  • acid-modified polypropylene resin (B) a commercially available unmodified polypropylene resin obtained by introducing an unsaturated carboxylic acid component by a known method may be used.
  • the acid-modified polypropylene resin (B) in the present invention preferably has a weight average molecular weight of 5,000 to 200,000, more preferably 10,000 to 150,000, and more preferably 20,000 to 120,000. Is more preferably 30,000, particularly preferably 30,000 to 100,000, and most preferably 35,000 to 80,000. If the weight average molecular weight of the acid-modified polypropylene resin (B) is less than 5,000, the adhesion with the base material tends to decrease or the resulting coating film tends to be hard and brittle, while the weight average molecular weight is low. If it exceeds 200,000, it tends to be difficult to make the resin water-based. In addition, the weight average molecular weight of resin can be calculated
  • GPC gel permeation chromatography
  • the aqueous dispersion of the present invention contains an aqueous medium together with the acid-modified polyethylene resin (A) and the acid-modified polypropylene resin (B).
  • the acid-modified polyethylene resin (A) and the acid-modified polypropylene resin (B ) Is dispersed or dissolved in an aqueous medium.
  • an aqueous medium is a liquid which has water as a main component, and may contain the basic compound and organic solvent which are mentioned later.
  • ammonia or an organic amine compound which volatilizes during the formation of the coating film is preferable from the viewpoint of water resistance of the coating film, and an organic amine compound having a boiling point of 30 to 250 ° C., more preferably 50 to 200 ° C. is particularly preferable.
  • an organic amine compound having a boiling point of 30 to 250 ° C., more preferably 50 to 200 ° C. is particularly preferable.
  • the boiling point is less than 30 ° C., the rate of volatilization when the resin described later becomes aqueous may increase, and the aqueous formation may not proceed completely.
  • the boiling point exceeds 250 ° C. it becomes difficult to disperse the organic amine compound from the resin coating film by drying, and the water resistance of the coating film may decrease.
  • organic amine compound examples include triethylamine, N, N-dimethylethanolamine, isopropylamine, aminoethanol, dimethylaminoethanol, diethylaminoethanol, ethylamine, diethylamine, isobutylamine, dipropylamine, 3-ethoxypropylamine, 3 -Diethylaminopropylamine, sec-butylamine, propylamine, n-butylamine, 2-methoxyethylamine, 3-methoxypropylamine, 2,2-dimethoxyethylamine, monoethanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine, Examples include pyrrole and pyridine.
  • the compounding amount of the basic compound is preferably 0.5 to 10 times equivalent, preferably 0.8 to 5 times equivalent to the carboxyl group in the acid-modified polyethylene resin (A) or acid-modified polypropylene resin (B). Is more preferable, and 0.9 to 3.0 times equivalent is particularly preferable. If the amount is less than 0.5 times equivalent, the effect of adding a basic compound is not recognized, and if the amount exceeds 10 times equivalent, the drying time during coating formation may be prolonged, or the stability of the aqueous dispersion may be reduced. is there.
  • a hydrophilic organic solvent may be added at the time of aqueous formation in order to promote the aqueous formation of the acid-modified polyethylene resin (A) and the acid-modified polypropylene resin (B) and reduce the dispersed particle size.
  • the content of the hydrophilic organic solvent is preferably 50% by mass or less, more preferably 1 to 45% by mass, still more preferably 2 to 40% by mass, and particularly preferably 3 to 35% by mass with respect to the entire aqueous medium. preferable.
  • the content of the hydrophilic organic solvent exceeds 50% by mass, it cannot be regarded as an aqueous medium substantially and does not deviate from one of the objects of the present invention (environmental protection).
  • the stability of the aqueous dispersion may be reduced.
  • the solubility in water at 20 ° C. is preferably 10 g / L or more, more preferably 20 g / L or more, and more preferably 50 g / L. More than L is more preferable.
  • the hydrophilic organic solvent those having a boiling point of 150 ° C. or less are preferable from the viewpoint of efficiently removing them from the coating film during the film forming process.
  • a hydrophilic organic solvent having a boiling point exceeding 150 ° C. tends to be difficult to scatter from the coating film by drying, and particularly the water resistance of the coating film at low temperature drying and the adhesion to the substrate are reduced. There is.
  • Preferred hydrophilic organic solvents include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, tert- Alcohols such as amyl alcohol, 1-ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol, cyclohexanol, ketones such as methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, cyclohexanone, tetrahydrofuran, dioxane, etc.
  • Ethers ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, 3-methoxybutyl acetate, propion Esters such as methyl, ethyl propionate, diethyl carbonate, dimethyl carbonate, glycol derivatives such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol ethyl ether acetate, and 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 3-methoxy-3-methyl-1-butanol, methoxybutanol, acetonitrile, dimethylformamide, dimethylacetamide, diacetone alcohol, ethyl acetoacetate, 1, Examples include 2-dimethylglycerin
  • ethanol, n-propanol, isopropanol, n-butanol, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, dioxane, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether are water-based acid-modified polyolefin resins. This is preferable because it is more effective in promoting crystallization.
  • a plurality of these hydrophilic organic solvents may be mixed and used.
  • a hydrophobic organic solvent may be further added.
  • the hydrophobic organic solvent those having a solubility in water at 20 ° C. of less than 10 g / L and having a boiling point of 150 ° C. or less for the same reason as described above are preferable.
  • hydrophobic organic solvent examples include olefin solvents such as n-pentane, n-hexane, n-heptane, cycloheptane, cyclohexane and petroleum ether, aromatic solvents such as benzene, toluene and xylene, Examples thereof include halogen solvents such as carbon chloride, 1,2-dichloroethane, 1,1-dichloroethylene, trichloroethylene, 1,1,1-trichloroethane, and chloroform.
  • the addition amount of these hydrophobic organic solvents is preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less with respect to the aqueous dispersion. When the addition amount exceeds 15% by mass, gelation or the like may be caused.
  • the aqueous dispersion of the present invention contains an acid-modified polyethylene resin (A), an acid-modified polypropylene resin (B), and an aqueous medium, and includes an acid-modified polyethylene resin (A) and an acid-modified polypropylene resin (B).
  • the mass ratio (A / B) needs to be 95/5 to 50/50, and is preferably 90/10 to 70/30 from the viewpoints of adhesiveness and heat sealability.
  • the content of the acid-modified polypropylene resin (B) is less than 5% by mass, the adhesion to a polyolefin resin substrate such as a polypropylene resin or a cycloolefin polymer is deteriorated. Adhesiveness with other substrates may be impaired.
  • the amount of unsaturated carboxylic acid monomer in the dry residue of the aqueous dispersion is 10,000 ppm or less. Preferably, it is 5,000 ppm or less, more preferably 3,000 ppm or less, particularly preferably 1,000 ppm or less, and most preferably 300 ppm or less.
  • the dry residue refers to the dry residue of the aqueous dispersion after the additive is added.
  • an unsaturated carboxylic acid component is introduced into an unmodified polyethylene resin or unmodified polypropylene resin by the method as described above, the unreacted unsaturated carboxylic acid monomer is converted into an acid-modified polyethylene resin (A) or an acid-modified polypropylene resin. It remains in (B).
  • the amount of the unsaturated carboxylic acid monomer contained in the dry residue of the aqueous dispersion exceeds 10,000 ppm, the resulting coating film may be inferior in water resistance, chemical resistance and adhesion. In particular, when it exceeds 5,000 ppm, the adhesiveness and chemical resistance may be inferior.
  • the amount of the unsaturated carboxylic acid monomer in the dry residue of the aqueous dispersion containing only the acid-modified polyolefin resin as a solid component is the amount of unsaturated carboxylic acid measured with each raw material of the acid-modified polyolefin resin before the aqueousization It has been confirmed that it matches the total amount of acid monomers. Therefore, the acid-modified polyethylene resin (A) and the acid-modified polypropylene resin (B) constituting the aqueous dispersion are preferably used so that the total amount of unsaturated carboxylic acid monomers is 10,000 ppm or less, It is more preferable to use it so that it may become 5,000 ppm or less.
  • the method for reducing the amount of the unsaturated carboxylic acid monomer in the acid-modified polyethylene resin (A) or the acid-modified polypropylene resin (B) is not particularly limited.
  • the acid-modified polyethylene resin (A) or the acid-modified polypropylene resin (B ) Under reduced pressure, a method in which acid-modified polyethylene resin (A) or acid-modified polypropylene resin (B) is dissolved in a solvent and reprecipitated, and acid-modified polyethylene resin (A in powder or pellet form) ) Or acid-modified polypropylene resin (B) is washed in water or an organic solvent, and is reduced by a Soxhlet extraction method.
  • a method of distilling under reduced pressure a method of separating by dissolving in a solvent and reprecipitation, and a method of washing in water or an organic solvent in the form of powder or pellets are preferable.
  • the amount of the unsaturated carboxylic acid monomer in the dry residue of the aqueous dispersion and the amount of the unsaturated carboxylic acid monomer in the acid-modified polyethylene resin (A) or acid-modified polypropylene resin (B) should be quantified using high performance liquid chromatography described later. Can do.
  • the difference in the number average particle diameter of each of the acid-modified polyethylene resin (A) and the acid-modified polypropylene resin (B) is 20 nm or more from the viewpoint of adhesion to the substrate. Is preferable, and it is more preferable that it is 50 nm or more.
  • the difference in the number average particle diameter between the acid-modified polyethylene resin (A) and the acid-modified polypropylene resin (B) is less than 20 nm, the adhesion to a polyolefin resin substrate and the low-temperature adhesion tend to decrease.
  • the aqueous dispersion in the present invention does not substantially contain a non-volatile aqueous agent.
  • the present invention does not exclude the use of a non-volatile aqueous auxiliary agent, the acid-modified polyolefin resin is stable in an aqueous medium within a weight average particle size of 0.15 ⁇ m or less without using an aqueous auxiliary agent. Can be dispersed.
  • aqueous auxiliary means a drug or compound added for the purpose of promoting aqueous formation or stabilizing the aqueous dispersion in the production of an aqueous dispersion
  • nonvolatile means It means that it does not have a boiling point at normal pressure or has a high boiling point (for example, 300 ° C. or higher) at normal pressure.
  • Substantially no non-volatile aqueous additive means that such an auxiliary is not used at the time of production (resin aqueous), and the resulting aqueous dispersion does not contain this auxiliary as a result. Means.
  • the content of such an aqueous auxiliary agent is zero, but it is contained in an amount of less than about 0.5% by mass with respect to the acid-modified polyolefin resin component as long as the effects of the present invention are not impaired. There is no problem.
  • non-volatile auxiliary agent used in the present invention examples include an emulsifier described later, a compound having a protective colloid effect, a modified wax, an acid-modified compound having a high acid value, and a water-soluble polymer.
  • the emulsifier examples include a cationic emulsifier, an anionic emulsifier, a nonionic emulsifier, and an amphoteric emulsifier.
  • surfactants are also included.
  • anionic emulsifiers include higher alcohol sulfates, higher alkyl sulfonates, higher carboxylates, alkyl benzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, vinyl sulfosuccinates.
  • Nonionic emulsifiers include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid ester, ethylene oxide propylene oxide block copolymer, polyoxyethylene fatty acid amide, ethylene oxide-propylene oxide.
  • Compounds having a polyoxyethylene structure such as copolymers and sorbitan derivatives such as polyoxyethylene sorbitan fatty acid esters
  • amphoteric emulsifiers lauryl betaine, lauryl dimethyl amine oxide, and the like.
  • Compounds having protective colloid action, modified waxes, acid-modified compounds with high acid value, water-soluble polymers include polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, modified starch, polyvinylpyrrolidone Polyacrylic acid and salts thereof, carboxyl group-containing polyethylene wax, carboxyl group-containing polypropylene wax, carboxyl group-containing polyethylene-propylene wax and the like, acid-modified polyolefin waxes having a number average molecular weight of usually 5000 or less and salts thereof, acrylic acid-anhydride Maleic acid copolymer and salts thereof, styrene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid copolymer, isobutylene-maleic anhydride A carboxyl group-containing polymer having an unsaturated carboxylic acid content of 10% by mass or more, such as a mutual
  • the method for producing the aqueous dispersion of the present invention is not limited as long as the acid-modified polyethylene resin (A) and the acid-modified polypropylene resin (B) are uniformly mixed and dispersed in an aqueous medium.
  • an aqueous dispersion of acid-modified polyethylene resin (A) prepared in advance and an aqueous dispersion of acid-modified polypropylene resin (B) are mixed, and water or a hydrophilic organic solvent is added as necessary.
  • Examples thereof include a method of adding, a method of mixing the acid-modified polyethylene resin (A) and the acid-modified polypropylene resin (B), and stirring and heating with water and a solvent. Any of the above methods can easily prepare an aqueous dispersion having a desired component ratio, but the former method is more convenient and preferable.
  • the method for producing the aqueous dispersion of the acid-modified polyethylene resin (A) and the aqueous dispersion of the acid-modified polypropylene resin (B) is not particularly limited, but for example, an acid-modified polyethylene resin ( A) or acid-modified polypropylene resin (B), the above-mentioned hydrophilic organic solvent, the above-mentioned basic compound, water and other raw materials are added, and stirring is performed while maintaining the temperature in the tank at about 40 to 150 ° C. And a method of forming an aqueous dispersion.
  • aqueous dispersion of the acid-modified polyethylene resin (A) commercially available ones can be used.
  • the Saixen series manufactured by Sumitomo Seika Co., Ltd. (Xyxen A, Xyxen L), the Chemipearl series manufactured by Mitsui Chemicals (S -100, S-75N, etc.).
  • the content of the resin composed of the acid-modified polyethylene resin (A) and the acid-modified polypropylene resin (B) in the aqueous dispersion of the present invention is appropriately adjusted depending on the film forming conditions, the thickness and performance of the target adhesive layer, and the like.
  • the content is preferably 1 to 50% by mass, and 5 to 40% by mass. More preferably.
  • a crosslinking agent can be added to the aqueous dispersion of the present invention in order to further improve various coating film performances such as water resistance, chemical resistance and adhesiveness.
  • the crosslinking agent is not particularly limited, and a crosslinking agent having self-crosslinking property, a compound having a plurality of functional groups that react with a carboxyl group in the molecule, a metal complex having a multivalent coordination site, and the like can be used.
  • oxazoline group-containing compounds, carbodiimide group-containing compounds, isocyanate group-containing compounds, epoxy group-containing compounds, melamine compounds, urea compounds, aziridine compounds, zirconium salt compounds, silane coupling agents and the like can be mentioned.
  • the addition amount of the crosslinking agent is not particularly limited, but is preferably 0.01 to 80 parts by mass with respect to 100 parts by mass in total of the acid-modified polyethylene resin (A) and the acid-modified polypropylene resin (B).
  • the aqueous dispersion of the present invention may further contain other polymer, an aqueous dispersion thereof, a tackifier component, an antiblocking agent, and the like.
  • the aqueous dispersion of other polymer is not particularly limited, but polyvinyl acetate, ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, styrene-maleic acid resin, styrene-butadiene resin, butadiene resin, Aqueous dispersion of acrylonitrile-butadiene resin, polyurethane resin, poly (meth) acrylonitrile resin, (meth) acrylamide resin, chlorinated polyethylene resin, chlorinated polypropylene resin, polyester resin, modified nylon resin, phenol resin, silicone resin, epoxy resin, etc. Examples include the body. You may use these in mixture of 2 or more types. In particular, it is preferable to add a polyurethane resin from the viewpoint of adhesiveness to the substrate.
  • the content is not particularly limited, but it is 1 to 300 parts by mass with respect to 100 parts by mass in total of the acid-modified polyethylene resin (A) and the acid-modified polypropylene resin (B). preferable.
  • the tackifier component is not particularly limited, and examples thereof include rosins, terpenes, petroleum resins, coumarone resins, and indene resins.
  • a pigment or a dye may be added according to the purpose of use, or the aqueous dispersion of the present invention may be added to a paint or ink.
  • the pigment or dye to be used is not particularly limited.
  • the pigment examples include titanium dioxide, zinc oxide, chromium oxide, cadmium sulfide, calcium carbonate, barium carbonate, barium sulfate, clay, talc, yellow lead, iron oxide, carbon Inorganic pigments such as black, azo, diazo, condensed azo, thioindigo, indanthrone, quinacridone, anthraquinone, benzimidazole, perylene, perinone, phthalocyanine, halogenated phthalocyanine, anthrapyridine And organic pigments such as dioxazines.
  • the dye include direct dyes, reactive dyes, acid dyes, cationic dyes, vat dyes, and mordant dyes. The above pigments or dyes may be used alone or in combination of two or more.
  • additives such as a leveling agent, an antifoaming agent, an anti-waxing agent, a pigment dispersant, and an ultraviolet absorber may be added to the aqueous dispersion of the present invention as necessary.
  • a good coating film and adhesive layer can be formed by removing the aqueous medium from the aqueous dispersion. Since the aqueous dispersion of the present invention is excellent in film forming ability, known film forming methods such as gravure roll coating, reverse roll coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spray coating, Uniform coating on the surface of various substrates by dip coating, brushing, etc., and setting as near room temperature as necessary, followed by heat treatment for drying or drying and baking Can be bonded to various substrate surfaces.
  • a heating device at this time a normal hot air circulation type oven, an infrared heater, or the like may be used. Further, the heating temperature and the heating time are appropriately selected depending on the characteristics of the base material, the kind of the crosslinking agent, the blending amount, etc., and are not particularly limited. . Further, an aging treatment may be performed at about 20 to 60 ° C. in order to advance the crosslinking reaction.
  • the thickness of the coating film obtained by removing the aqueous medium from the aqueous dispersion of the present invention is not particularly limited, but is preferably 0.5 to 20 ⁇ m, more preferably 3 to 15 ⁇ m, and more preferably 5 to 13 ⁇ m. More preferably, it is particularly preferably 8 to 10 ⁇ m.
  • the thickness is less than 0.5 ⁇ m, the laminate strength is low and the effect as an adhesive is small, and if it exceeds 20 ⁇ m, the drying time becomes long.
  • a different type or the same kind of base material can be bonded together using the coating film formed by removing the aqueous medium from the aqueous dispersion as an adhesive layer to form a laminate.
  • the bonding conditions are not particularly limited, but the temperature is preferably 60 ° C. or higher, and when a thermoplastic resin film is used as the substrate, it is preferably lower than the melting point of the thermoplastic resin.
  • the laminating method include a method of laminating while applying pressure with a hot roll.
  • the aqueous dispersion of the present invention is excellent in adhesiveness with a polyolefin resin, and as a substrate to which the aqueous dispersion of the present invention is applied, a polyolefin resin substrate such as polyethylene, polypropylene, and cycloolefin polymer is preferable.
  • a resin having a relatively low heat resistance for example, a polyolefin resin having a melting point of 180 ° C. or less such as polyethylene or polypropylene. It can be applied to a substrate.
  • Examples of the cycloolefin polymer include cyclic rings in the main chain described in JP-A-10-120768, JP-A-11-43566, JP-A-2004-51949, JP-A-2004-156048, and the like.
  • the thermoplastic olefin resin which has the following olefin frame
  • Examples of commercially available cycloolefin polymers include ARTON manufactured by JSR, ZEONOR and ZEONEX manufactured by Nippon Zeon, TOPAS manufactured by Polyplastics, and APEL manufactured by Mitsui Chemicals.
  • a base material to which the aqueous dispersion of the present invention is applied in addition to the above polyolefin resin base material, metals such as a film or a molded body made of a thermoplastic resin, paper, synthetic paper, glass, aluminum foil, and the like can be given.
  • thermoplastic resins other than polyolefin resins include polyamide resins such as nylon 6, nylon 66, nylon 46, polyethylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate.
  • polyester resins such as polyethylene succinate, polyglycolic acid, polylactic acid, polycarbonate, and polyarylate, polyurethane resins, polyimide resins, ABS resins, acrylic resins, and mixtures thereof.
  • shape of the thermoplastic resin constituting the substrate include films and molded bodies, and laminates thereof.
  • the thermoplastic resin film may be an unstretched film or a stretched film, and the production method is not limited.
  • the thickness of the thermoplastic resin film is not particularly limited, but is usually in the range of 5 to 500 ⁇ m.
  • the thermoplastic resin film may contain a filler. Examples of the filler include, but are not limited to, calcium carbonate, clay, silica, diatomaceous earth, talc, titanium oxide, barium titanate, barium sulfate, and alumina.
  • the thermoplastic resin film may be subjected to various functional treatments such as various barrier coatings, easy adhesion coatings, antistatic coatings, ultraviolet shielding coatings, and various vapor deposition treatments such as silica, alumina, and aluminum.
  • the combination of substrates to be bonded using the aqueous dispersion of the present invention is not particularly limited, but polyolefin resin and metal such as aluminum, polyolefin resin and polyester resin, polyolefin resin and polycarbonate resin, polyolefin resin and acrylic resin, polyolefin resin And a combination of different materials such as polyamide resin, polyolefin resin and triacetyl cellulose, and a combination of polyolefin resins such as polypropylene, and the aqueous dispersion of the present invention has particularly good adhesion to these substrates. .
  • an adhesive of the aqueous dispersion of the present invention is not particularly limited, but various depositions such as an adhesive for optical films such as a touch panel, an anchor coating agent, an adhesive for solar battery backsheet, silica, alumina, aluminum and the like.
  • Adhesives such as the vapor deposition surface of the treated vapor deposition film, adhesives for building materials such as wall materials, adhesives for packaging materials, adhesives for paper containers, adhesives for lid materials, adhesives for in-mold transfer foils, PP steel sheet adhesive, flocking adhesive, secondary battery electrode binder adhesive, secondary battery exterior adhesive, automotive belt molding adhesive, automotive component adhesive, heterogeneous substrate adhesive, etc. Is mentioned.
  • the aqueous dispersion of this invention can be used conveniently also as a coating agent, a primer, a coating material, ink, etc. other than the said adhesive agent.
  • Specific examples include anchor coating agent for PP extrusion lamination, coating agent for secondary battery separator, primer for UV curable coating agent, primer for shoes, primer for automobile bumper, primer for clear box, paint for PP substrate, fiber Examples include sizing agents.
  • MFR Melt flow rate of acid-modified polyethylene resin (A) It measured by the method of JIS6730 description (190 degreeC, 2160g load).
  • Weight average molecular weights of acid-modified polyethylene resin (A) and acid-modified polypropylene resin (B) The weight average molecular weight was determined by GPC analysis (HLC-8020 manufactured by Tosoh Corporation, and two KF-804L and KF805L columns manufactured by SHODEX). And tetrahydrofuran was used as the eluent, and the flow rate was 1 mL / min and measurement was performed at 40 ° C. About 10 mg of resin was dissolved in 5.5 mL of tetrahydrofuran and filtered through a PTFE membrane filter as a measurement sample. The weight average molecular weight was determined from a calibration curve prepared with a polystyrene standard sample. When it was difficult to dissolve in tetrahydrofuran, it was dissolved in orthodichlorobenzene.
  • the amount of unsaturated carboxylic acid monomer was less than 1000 ppm, the amount of resin pellets was changed to 0.5 g, and the amount was similarly determined.
  • the calibration curve was prepared using an unsaturated carboxylic acid monomer standard sample with a known concentration.
  • Aqueous Dispersion and Acid-Modified Polypropylene Resin Aqueous Dispersion (1) Solid Concentration A suitable amount of the aqueous dispersion was weighed, and the mass of the residue (solid content) at 150 ° C. was heated to reach a constant weight, and the solid content concentration was determined.
  • Viscosity of acid-modified polypropylene resin (B) aqueous dispersion The aqueous dispersion after 300 mesh filtration was rotated at a temperature of 20 ° C. using a B-type viscometer (DVL-BII digital viscometer manufactured by Tokimec). The viscosity (mPa ⁇ s) was measured.
  • COP-1 cycloolefin polymer film (ZEONOR ZF-14-100, manufactured by ZEON Corporation, thickness 100 ⁇ m)
  • COP-2 cycloolefin copolymer plate (polyplastics, TOPAS 5013L-10 molded product, 10 cm ⁇ 5 cm ⁇ 2 mm thickness)
  • CPP unstretched polypropylene film (manufactured by Tosero Co., Ltd., thickness 50 ⁇ m)
  • PE unstretched polyethylene film (manufactured by Tamapoly, thickness 40 ⁇ m)
  • PET Biaxially stretched polyethylene terephthalate film (Embret PET manufactured by Unitika Ltd., thickness 50 ⁇ m)
  • PC Polycarbonate plate (Nippon Test Panel, 10cm x 2cm x 2mm thickness)
  • Ac Acrylic board (manufactured by Nippon Test Panel,
  • Peel strength A measurement sample having a width of 15 mm was cut out from each laminate prepared by the following method, and a tensile tester (precision universal material testing machine 2020 manufactured by Intesco) was used to pull a pulling speed of 200 mm / min and a pulling angle of 180. The peel strength between the substrates was measured in degrees. In addition, if the peeling strength was the following numerical value, it was set as the pass. (7.1) Bonding of PET and COP-1 The aqueous dispersion was coated on the corona surface of PET with a Mayer bar so that the thickness of the adhesive layer after drying was 10 ⁇ m, and dried at 120 ° C. for 1 minute. COP-1 was bonded to the adhesive-coated surface of PET and pressed at 125 ° C. with a heat press (sealing pressure 0.5 MPa for 60 seconds). A peel strength of 10 N / 15 mm or more was accepted.
  • the aqueous dispersion of acid-modified polyethylene resin (A) used for the production of the aqueous dispersion was produced by the following method.
  • (Production of acid-modified polyethylene resin aqueous dispersion A-1) Using a stirrer equipped with a hermetic pressure-resistant 1 liter glass container with a heater, 60.0 g of acid-modified polyethylene resin (manufactured by Sumitomo Chemical Co., Ltd., Bondine HX-8290), 60.0 g of isopropanol, 2.2 g Of triethylamine and 177.8 g of distilled water were placed in a glass container and sealed, and then stirred at a rotation speed of the stirring blade of 300 rpm.
  • Table 1 shows the composition of the acid-modified polyethylene resin used in the production of the acid-modified polyethylene resin aqueous dispersions A-1 to A-3 and various characteristics of the aqueous dispersions A-1 to A-3.
  • the acid-modified polypropylene resin (B) used for the production of the aqueous dispersion was produced by the following method.
  • the obtained reaction product was put into a large amount of acetone to precipitate a resin.
  • Production Example 2 Acid-modified polypropylene resin P-2 An acid-modified polypropylene resin P-2 was obtained in the same manner as in Production Example 1 except that the acetone solution of triethylamine was changed to acetone and the subsequent acetone washing was changed to methanol washing.
  • Production Example 3 Acid-modified polypropylene resin P-3
  • the amount of maleic anhydride added was changed to 60.0 g instead of 40.0 g, and the same operation was performed except that the washing step of acetone solution of triethylamine and the washing step of acetone were omitted.
  • Polypropylene resin P-3 was obtained.
  • Production Example 4 Acid-modified polypropylene resin P-4 The same procedure as in Production Example 1 was carried out except that the amount of maleic anhydride added was 24.0 g and the amount of dicumyl peroxide added was 18.5 g. Thus, an acid-modified polypropylene resin P-4 was obtained. .
  • Production Example 5 Acid-modified polypropylene resin P-5 An acid-modified polypropylene resin P-5 was obtained in the same manner as in Production Example 1 except that a propylene-butene copolymer having a mass ratio (propylene / 1-butene) of 97/3 was used.
  • Production Example 6 Acid-modified polypropylene resin P-6 An acid-modified polypropylene resin P-6 was obtained in the same manner as in Production Example 1, except that a propylene-butene copolymer having a mass ratio (propylene / 1-butene) of 65/35 was used.
  • Production Example 7 Acid-modified polypropylene resin P-7 An acid-modified polypropylene resin P-7 was obtained in the same manner as in Production Example 1 except that a propylene-butene copolymer having a mass ratio (propylene / 1-butene) of 50/50 was used.
  • Table 2 shows the properties of the acid-modified polypropylene resins (B) obtained in Production Examples 1 to 9.
  • the aqueous dispersion of acid-modified polypropylene resin (B) used for the production of the aqueous dispersion was produced by the following method.
  • (Production of acid-modified polypropylene resin aqueous dispersion B-1) Using a stirrer equipped with a heat-resistant 1 L glass container with a heater, 60.0 g of acid-modified polypropylene resin P-1, 99.0 g of tetrahydrofuran, 11.6 g of N, N-dimethylethanolamine (DMEA) ) And 159.4 g of distilled water were charged into a glass container and stirred at a rotation speed of the stirring blade of 300 rpm.
  • the liquid component in the flask was subjected to pressure filtration (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) to obtain a milky white uniform acid-modified polypropylene resin aqueous dispersion B-3.
  • aqueous dispersion B-11 was obtained in the same manner as in the production method of the aqueous dispersion B-1, except that P-9 was used instead of the acid-modified polypropylene resin P-1.
  • aqueous dispersion In the production of the aqueous dispersion, the following were used as additives.
  • -Polyurethane resin Polyether-type polyurethane resin aqueous dispersion (manufactured by Enomoto Kasei Co., Ltd., NeoRezR-600, solid content concentration: 33% by mass)
  • -Crosslinking agent aqueous solution of oxazoline group-containing compound (Nippon Shokubai Co., Ltd., Epocros WS-700, solid content concentration 25% by mass)
  • Crosslinking agent aqueous dispersion of epoxy group-containing compound (manufactured by ADEKA, Adeka Resin EM-0517, solid content concentration 51% by mass)
  • Example 1 The acid-modified polyethylene resin aqueous dispersion A-1 and the acid-modified polypropylene resin aqueous dispersion B-1 have a solid content mass ratio of 95/5 between the acid-modified polyolefin resin aqueous dispersion and the acid-modified polypropylene resin aqueous dispersion. The mixture was mixed and stirred at room temperature for 5 minutes to obtain an aqueous dispersion. Various performance evaluation was performed using the obtained aqueous dispersion.
  • Examples 2 to 20 Comparative Examples 1 to 17 As shown in Tables 3 and 4, the types and solid content mass ratios of the acid-modified polyethylene resin (A) aqueous dispersion and the acid-modified polypropylene resin (B) aqueous dispersion were changed, and added in Examples 18 to 20.
  • Comparative Examples 12 to 17 the same operations as in Example 1 were performed except that an aqueous polyester dispersion or an acrylic aqueous dispersion was used instead of the acid-modified polypropylene resin (B) aqueous dispersion. An aqueous dispersion was obtained.
  • Tables 3 and 4 show the results of Examples 1 to 20 and Comparative Examples 1 to 17.
  • the aqueous dispersions of Examples 1 to 20 were excellent in liquid stability, and the obtained coating films were excellent in water resistance, alkali resistance and chemical resistance, and had high peel strength from various substrates and excellent adhesion. It was a thing. Moreover, a laminated body could be obtained with a low-temperature press, and the bag produced from this laminated body was excellent in content resistance. Among them, the coating film obtained from an aqueous dispersion to which a cross-linking agent such as an oxazoline group-containing compound or an epoxy group-containing compound or a polyurethane resin is added has further improved peel strength from various substrates, and is more excellent in adhesiveness. It was.
  • a cross-linking agent such as an oxazoline group-containing compound or an epoxy group-containing compound or a polyurethane resin
  • Comparative Examples 10 to 11 since the acid-modified polyethylene resin (A) has a content of unsaturated carboxylic acid component larger than the specified amount of the present invention, the peel strength from the substrate is low, and the coating film has water resistance and It was inferior in alkali resistance and chemical resistance. Since the aqueous dispersions of Comparative Examples 12 to 17 used a polyester aqueous dispersion or an acrylic aqueous dispersion instead of the acid-modified polypropylene resin (B) aqueous dispersion, the liquid stability may be inferior. The alkali resistance and chemical resistance were poor, the peel strength from the substrate was low, and the adhesiveness was poor.

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Abstract

　L'invention concerne une dispersion aqueuse contenant une résine de polyéthylène modifié par un acide (A), une résine de polypropylène modifié par un acide (B), et un véhicule aqueux. La dispersion aqueuse est caractérisée en ce que : la résine (A) contient un constituant oléfinique contenant de l'éthylène, et un constituant acide carboxylique insaturé, en tant que constituants de copolymère ; la teneur en constituant acide carboxylique insaturé est de 0,1 à 15 % en masse ; la résine (B) contient un constituant oléfinique comprenant du propylène et du butène, et un constituant acide carboxylique insaturé, en tant que constituants de copolymère ; et le rapport des masses (A/B) de la résine (A) et de la résine (B) est de 95/5 à 50/50.
PCT/JP2015/066022 2014-06-03 2015-06-03 Dispersion aqueuse, et stratifié WO2015186733A1 (fr)

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WO2020044920A1 (fr) * 2018-08-29 2020-03-05 住友化学株式会社 Dispersion aqueuse
WO2020203103A1 (fr) * 2019-03-29 2020-10-08 日本製紙株式会社 Composition de résine de dispersion
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WO2023032915A1 (fr) * 2021-09-03 2023-03-09 三井化学株式会社 Corps multicouche
WO2023238823A1 (fr) * 2022-06-07 2023-12-14 Ｔｏｐｐａｎホールディングス株式会社 Film de borne pour dispositif de stockage d'énergie, et dispositif de stockage d'énergie l'utilisant
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