WO2022225024A1 - Composition de résine en émulsion et agent de revêtement - Google Patents

Composition de résine en émulsion et agent de revêtement Download PDF

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Publication number
WO2022225024A1
WO2022225024A1 PCT/JP2022/018470 JP2022018470W WO2022225024A1 WO 2022225024 A1 WO2022225024 A1 WO 2022225024A1 JP 2022018470 W JP2022018470 W JP 2022018470W WO 2022225024 A1 WO2022225024 A1 WO 2022225024A1
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Prior art keywords
emulsion
resin composition
acid
resin
composition
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PCT/JP2022/018470
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English (en)
Japanese (ja)
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紀人 酒井
純己 福田
潤 磯部
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三菱ケミカル株式会社
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Publication of WO2022225024A1 publication Critical patent/WO2022225024A1/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
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C08L1/12—Cellulose acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
    • C09D101/08—Cellulose derivatives
    • C09D101/10—Esters of organic acids
    • C09D101/12—Cellulose acetate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic

Definitions

  • the present invention relates to an emulsion resin composition containing a biodegradable resin. More particularly, it relates to emulsion resin compositions and coating agents containing aliphatic polyester resins.
  • an emulsion resin composition having excellent biodegradability an emulsion composition obtained by emulsifying an aliphatic polyester resin such as polylactic acid or polybutylene succinate using a dispersant such as polyvinyl alcohol has been proposed. Development of various applications such as adhesives, paints, and coating agents is expected (Patent Document 1).
  • the properties required for the coating agent such as film-forming properties and heat-sealing properties, may be insufficient, and the practicality of the composition may be insufficient. From this point of view, further improvement is required.
  • the present invention has been made in view of the above-mentioned problems, and is an emulsion resin that facilitates the production of an emulsion composition while containing an aliphatic polyester resin and provides an emulsion composition that is excellent in stability. Compositions and the like are provided.
  • the present invention also provides a resin composition for emulsion, etc., from which an emulsion composition having excellent film-forming properties and heat-sealing properties can be obtained.
  • the present inventors unexpectedly found that the production of an emulsion composition becomes easier by blending a specific additive together with an aliphatic polyester resin. It was found that the stability of the object increases.
  • an emulsion having excellent film-forming properties and heat-sealing properties can be obtained by blending a specific additive together with an aliphatic polyester resin. It has been found that compositions are obtained.
  • a resin composition for emulsion containing (A) an aliphatic polyester-based resin and (B) one or more additives selected from the group consisting of a cellulose acetate-based resin and an ester-based plasticizer.
  • a resin composition for emulsion according to [1] wherein the mass ratio [(B)/(A)] of the additive (B) to the aliphatic polyester resin (A) is 0.05 to 0.5. .
  • the coating agent according to [9], wherein the object to be coated is a paper substrate.
  • the coating agent according to [9], wherein the object to be coated is a plastic substrate.
  • a resin composition for emulsion, etc. which facilitates the production of an emulsion composition while containing an aliphatic polyester-based resin, and which is capable of obtaining an emulsion composition having excellent stability. be able to.
  • An emulsion resin composition according to an example of the embodiment of the present invention is an emulsion resin composition containing (A) an aliphatic polyester resin and (B) an additive, wherein the (B) additive is It is one or more selected from the group consisting of cellulose acetate-based resins and ester-based plasticizers.
  • the resin composition for emulsion according to an example of the embodiment of the present invention contains (A) an aliphatic polyester resin, and (B) the additive as a dispersoid, further (C) a dispersant, and (D) )
  • a water-based emulsion resin composition containing a dispersion medium is suitable.
  • an emulsion composition containing the emulsion resin composition according to one example of the embodiment of the present invention is suitable.
  • Such an emulsion composition is obtained by a known production method such as a phase inversion emulsification method using the resin composition for emulsion according to one example of the embodiment of the present invention.
  • Component (A) is not particularly limited as long as it is a polyester resin in which the molar ratio of the aliphatic structure (including the alicyclic structure) is the maximum ratio with respect to the overall structure. It may be an aliphatic-aromatic polyester-based resin having an aromatic structure in it.
  • (A1) an aliphatic polyester resin having an aliphatic diol unit and an aliphatic dicarboxylic acid unit as main structural units is preferable.
  • the "unit” means a structural unit contained in the aliphatic polyester resin derived from the monomer component used in the production of the aliphatic polyester resin
  • the "main structural unit” It means that 50 mol % or more of the total structural units of the aliphatic polyester-based resin are contained in the structural units derived from the target monomer component.
  • the content of structural units derived from the target monomer is preferably 60 mol % or more, more preferably 70 mol % or more, and even more preferably 80 to 100 mol %.
  • the aliphatic diol and the aliphatic dicarboxylic acid component are 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more in the total monomer components used in the polymerization reaction of the aliphatic polyester resin. More preferably, it is produced by polymerizing a raw material containing 80 to 100 mol %.
  • the component (A1) is, for example, an aliphatic polyester resin having, as main structural units, an aliphatic diol unit represented by the following formula (1) and an aliphatic dicarboxylic acid unit represented by the following formula (2).
  • R 11 represents a divalent chain aliphatic hydrocarbon group which may have an oxygen atom in the chain, and when copolymerized, it is not limited to one type.
  • R 21 represents a direct bond or represents a divalent chain aliphatic hydrocarbon group, and when it is copolymerized, it is not limited to one type. ]
  • the aliphatic diol that gives the diol unit of formula (1) is not particularly limited, but for example, an aliphatic diol having 2 to 10 carbon atoms is preferable, and an aliphatic diol having 4 to 6 carbon atoms is more preferable.
  • 1,4-butanediol is preferred.
  • the aliphatic diols may be used singly or in combination of two or more.
  • the aliphatic dicarboxylic acid component that gives the aliphatic dicarboxylic acid unit of formula (2) is an aliphatic dicarboxylic acid or an aliphatic dicarboxylic acid derivative such as an alkyl ester thereof, and the aliphatic dicarboxylic acid is not particularly limited, but For example, aliphatic dicarboxylic acids having 2 to 40 carbon atoms are preferred, and aliphatic dicarboxylic acids having 4 to 10 carbon atoms are more preferred. Specific examples include succinic acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid and the like.
  • succinic acid, adipic acid and sebacic acid are preferred, succinic acid and adipic acid are more preferred, and succinic acid is particularly preferred.
  • the aliphatic dicarboxylic acid components may be used alone or in combination of two or more.
  • component (A1) examples include aliphatic polyester resins containing 1,4-butanediol and succinic acid, and aliphatic polyester resins containing 1,4-butanediol, adipic acid, and succinic acid. mentioned. More specific examples include polybutylene succinate, polybutylene succinate adipate, and the like. Among these, polybutylene succinate and polybutylene succinate adipate are preferred.
  • the proportion of structural units derived from succinic acid in the total dicarboxylic acid units of the aliphatic polyester resin is usually 50 to 100 mol%, preferably 80 to 100 mol%, more preferably is 90 to 100 mol %.
  • the ratio of structural units derived from succinic acid in the total dicarboxylic acid units of the aliphatic polyester resin is usually 50 to 95 mol%, preferably 60 to 93. mol %, more preferably 70 to 90 mol %, and the proportion of structural units derived from adipic acid in all dicarboxylic acid units is usually 5 to 50 mol %, preferably 7 to 40 mol %, more preferably 10 to 30 mol %.
  • the (A1) component preferably has the following physical properties.
  • the weight average molecular weight (Mw) of component (A1) is preferably 10,000 or more, more preferably 20,000 or more, still more preferably 50,000 or more, and preferably 1,000,000 or less, and more preferably 1,000,000 or less. It is preferably 500,000 or less, more preferably 400,000 or less.
  • the weight average molecular weight (Mw) is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.
  • the melt flow rate (MFR) of component (A1) is usually 0.1 g/10 minutes or more, preferably 0.5 g/10 minutes or more, more preferably 1 g/10 minutes, when measured at 190°C and 2.16 kg. It is 10 minutes or more, and is usually 1,000 g/10 minutes or less, preferably 500 g/10 minutes or less, more preferably 100 g/10 minutes or less, still more preferably 50 g/10 minutes or less.
  • the melting point of component (A1) is preferably 70°C or higher, more preferably 75°C or higher, and is preferably 250°C or lower, more preferably 200°C or lower, and particularly preferably 150°C or lower. When there are multiple melting points, at least one melting point is preferably within the above range.
  • the physical properties of the (A) aliphatic polyester resin used in the present invention are, unless otherwise specified, [(A1) an aliphatic polyester resin having an aliphatic diol unit and an aliphatic dicarboxylic acid unit as main structural units ] are the same as the physical properties described in the section above.
  • Aliphatic polyester resin having an aliphatic oxycarboxylic acid unit as a main structural unit Specific examples of the aliphatic oxycarboxylic acid component that provides the aliphatic oxycarboxylic acid unit of component (A2) include, for example, lactic acid, glycolic acid, 2-hydroxy-n-butyric acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxycaproic acid, 6-hydroxycaproic acid, 2-hydroxy-3,3-dimethylbutyric acid, 2-hydroxy-3-methylbutyric acid, 2-hydroxyisocaproic acid, 3-hydroxyvaleric acid, malic acid, citric acid etc., or lower alkyl esters or intramolecular esters thereof.
  • Lactone compounds such as ⁇ -caprolactone are also included in aliphatic oxycarboxylic acids in the present invention.
  • optical isomers When optical isomers are present in these compounds, they may be D-, L-, or racemic isomers, and may be solid, liquid, or aqueous solution.
  • lactic acid, glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 6-hydroxycaproic acid, and 3-hydroxyvaleric acid are preferred.
  • These aliphatic oxycarboxylic acids may be used alone or in combination of two or more.
  • component (A2) include polylactic acid, polyglycolic acid, poly-3-hydroxybutyrate, poly-4-hydroxybutyrate, poly(3-hydroxybutyrate-co-3-hydroxyvalerate), polycaprolactone and the like.
  • polylactic acid may be a copolymer of the aforementioned polylactic acid and other oxycarboxylic acid, and may contain a small amount of units derived from a chain extender.
  • Other oxycarboxylic acids include optical isomers of lactic acid (D-lactic acid for L-lactic acid, L-lactic acid for D-lactic acid), glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, Bifunctional aliphatic oxycarboxylic acids such as 2-hydroxy-n-butyric acid, 2-hydroxy-3,3-dimethylbutyric acid, 2-hydroxy-3-methylbutyric acid, 2-methyllactic acid, 2-hydroxycaproic acid, and caprolactone , butyrolactone, valerolactone, and other lactones. Units derived from such other oxycarboxylic acids are preferably used in an amount of less than 15 mol % of all structural units of polylactic acid.
  • the weight average molecular weight (Mw) of component (A2) is preferably 60,000 or more, more preferably 80,000 or more, particularly preferably 100,000 or more, and preferably 700,000 or less, more preferably 400,000 or less, particularly preferably 300,000 or less.
  • the weight average molecular weight (Mw) is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.
  • Component (A3) is, for example, an aliphatic diol unit represented by the above formula (1), an aliphatic dicarboxylic acid unit represented by the above formula (2), and the following formula (3). It contains an aromatic dicarboxylic acid unit as an essential component. Furthermore, it may have the aforementioned oxycarboxylic acid unit.
  • R 31 represents a divalent aromatic hydrocarbon group, and when it is copolymerized, it is not limited to one type. ]
  • the above [(A1) the aliphatic diol unit and the aliphatic dicarboxylic acid unit are mainly Aliphatic polyester-based resin possessed as a structural unit], and preferable ones are also the same.
  • the aromatic dicarboxylic acid component that gives the aromatic dicarboxylic acid unit of formula (3) is not particularly limited, but examples thereof include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and diphenyldicarboxylic acid. These may be acid anhydrides.
  • derivatives of aromatic dicarboxylic acids include lower alkyl esters of these aromatic dicarboxylic acids.
  • terephthalic acid, isophthalic acid, or lower alkyl (eg, alkyl having 1 to 4 carbon atoms) ester derivatives thereof are preferred. These may be used individually by 1 type, and may be used in mixture of 2 or more types.
  • terephthalic acid and/or terephthalic acid methyl esters or mixtures containing terephthalic acid and/or terephthalic acid methyl esters and isophthalic acid and/or isophthalic acid methyl esters are preferred.
  • aliphatic-aromatic polyester resin examples are preferably polybutylene alkylate terephthalate, more preferably polybutylene adipate terephthalate or polybutylene succinate terephthalate, and particularly preferably polybutylene adipate terephthalate.
  • the aliphatic polyester resin may be used alone or in combination of two or more.
  • two or more aliphatic polyester resins having different diol units or dicarboxylic acid units may be mixed and used.
  • the content of component (A) is not particularly limited, but is preferably 15% by mass or more, more preferably 20% by mass or more, and even more preferably, based on the total amount of the emulsion resin composition (or the total amount of the emulsion composition). It is 30% by mass or more. Also, it is preferably 50% by mass or less, more preferably 48% by mass or less, and even more preferably 46% by mass or less.
  • Additives are one or more selected from the group consisting of (b1) cellulose acetate resins and (b2) ester plasticizers.
  • (B) additives (b1) one or more cellulose acetate resins and (b2) one or more ester plasticizers can be used in combination.
  • a basic acid ester plasticizer can also be used in combination.
  • cellulose acetate resin As the component (b1), commonly used known cellulose acetate resins can be used. Specific examples include cellulose acetates such as diacetyl cellulose and triacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate, cellulose acetate phthalate, and cellulose acetate benzoate. These can be used alone or in combination of two or more. Among these, cellulose acetate butyrate is preferred.
  • component (b1) Commercially available products of component (b1) include, for example, CAB-551-0.01, CAB-551-0.2, CAB-553-0.4, CAB-531-1 and CAB-500 manufactured by EASTMAN CHEMICAL. -5, CAB-321-0.1, CAB-381-0.1, CAB-381-0.5, CAB-381-2, CAB-321-20, CAP-504-0.2, CAP-482 -0.5, CAP-482-20 and the like.
  • the weight average molecular weight (Mw) of component (b1) is not particularly limited, but is usually 8,000 or more, preferably 10,000 or more, more preferably 15,000 or more. Also, it is usually 150,000 or less, preferably 100,000 or less, more preferably 70,000 or less.
  • the weight average molecular weight (Mw) is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.
  • the acetylation degree of component (b1) is not particularly limited, but is preferably 0.6% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more. Also, it is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less.
  • the degree of acetylation means the amount of bound acetic acid per unit mass of cellulose, and is determined by measuring and calculating the degree of acetylation according to ASTM: D-817-91 (test method for cellulose acetate, etc.). be.
  • the 6% viscosity of component (b1) is not particularly limited, but is preferably 10 mPa ⁇ s or more, more preferably 20 mPa ⁇ s or more, and even more preferably 30 mPa ⁇ s or more. Also, it is preferably 20,000 mPa ⁇ s or less, more preferably 10,000 mPa ⁇ s or less, and even more preferably 5,000 mPa ⁇ s or less.
  • the 6% viscosity is obtained by dissolving a cellulose acetate resin in a 95% aqueous solution of acetone to a concentration of 6 wt/vol% and measuring the flow-down time using an Ostwald viscometer.
  • Component (b2) is a plasticizer having an ester bond in its molecule, and commonly used known ester plasticizers can be used.
  • ester plasticizers such as adipate plasticizers, sebacate plasticizers, azelaic ester plasticizers, phthalate plasticizers, phosphate ester plasticizers, citric acid Ester-based plasticizers, glycolic acid ester-based plasticizers, trimellitic acid ester-based plasticizers, ricinoleic acid ester-based plasticizers, benzoic acid ester-based plasticizers, acetic ester-based plasticizers, and the like can be mentioned. These can be used alone or in combination of two or more.
  • adipate plasticizers include dimethyl adipate, dibutyl adipate, dioctyl adipate, isobutyl adipate, isodecyl adipate, diisononyl adipate, divinyl adipate, dibenzyl adipate, adipic acid and aromatic alcohols, and Mixed group esters with aliphatic alcohols and the like are included.
  • Examples of mixed-base esters of adipic acid and aromatic alcohols and aliphatic alcohols include benzylalkyldiglycol adipate.
  • the alkyl group in the benzylalkyldiglycol adipate may be linear or branched, and although the number of carbon atoms in the alkyl group is not particularly limited, it is usually about 1-20.
  • straight-chain alkyl groups are preferred, more preferably straight-chain alkyl groups having 1 to 8 carbon atoms, and still more preferably straight-chain alkyl groups having 1 to 4 carbon atoms. More specific examples include benzylmethyldiglycol adipate, benzylethyldiglycol adipate, benzylpropyldiglycol adipate, and benzylbutyldiglycol adipate.
  • sebacate-based plasticizers examples include dimethyl sebacate, dibutyl sebacate, di-2-ethylhexyl sebacate, dioctyl sebacate, and diisooctyl sebacate.
  • azelate-based plasticizers examples include dioctyl azelate, 2-ethylhexyl azelate, isobutyl azelate, isodecyl azelate, diisononyl azelate, dihexyl azelate, divinyl azelate, and dibenzyl azelate.
  • Phthalate plasticizers include, for example, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, diisooctyl phthalate, di-2-ethylhexyl phthalate, and diisophthalate. -ethylhexyl, dinonyl phthalate, diisononyl phthalate, diisodecyl phthalate, ditridecyl phthalate, dibutylpentyl phthalate, dicyclohexyl phthalate, diundecyl phthalate, diphenyl phthalate and the like.
  • phosphate plasticizers include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, 2-ethylhexyl diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, and diphenylethyl phosphate. etc.
  • citric ester-based plasticizers examples include triethyl citrate, acetyl triethyl citrate, tributyl citrate, acetyl tributyl citrate, and acetyl tri-2-ethylhexyl citrate.
  • glycolic acid ester plasticizers examples include triacetin, tributyrin, methylphthalyl ethylglycolate, ethylphthalyl ethylglycolate, butylphthalyl butylglycolate, and the like.
  • trimellitate plasticizers examples include trioctyl trimellitate, tri-2-ethylhexyl trimellitate, diisooctyl monoisodecyl trimellitate, and triisononyl trimellitate.
  • ricinoleic acid ester plasticizers examples include methylacetyl ricinoleate and butylacetyl ricinoleate.
  • Benzoic acid ester-based plasticizers include, for example, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, polyethylene glycol dibenzoate, and the like.
  • aliphatic dibasic ester plasticizers are preferred, more preferably adipate plasticizers, and even more preferably benzylalkyldiglycol. Adipate.
  • the weight average molecular weight (Mw) of component (b2) is not particularly limited, but is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more. Also, it is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 1,000 or less.
  • the weight average molecular weight (Mw) is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.
  • the mass ratio [(B)/(A)] of component (B) to component (A) is preferably 0.05 to 0.5, more preferably 0.07 to 0.5, and even more preferably is 0.09 to 0.5, particularly preferably 0.1 to 0.4, and may be 0.15 to 0.3. If the content of component (B) is too low, the production of the emulsion composition tends to be difficult, and the resulting emulsion composition tends to be less stable.
  • the content of component (B) is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 2% by mass or more, based on the total amount of the emulsion resin composition (or the total amount of the emulsion composition). It is preferably 3% by mass or more, particularly preferably 5% by mass or more. Also, it is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 15% by mass or less.
  • dispersant As the dispersant (C), a commonly used known general dispersant can be used. Examples include water-soluble polymers and various surfactants. These may be used alone or in combination of two or more.
  • water-soluble polymers include, but are not limited to, polyvinyl alcohol-based resin (hereinafter referred to as "PVA-based resin"), methylcellulose, ethylcellulose, hydroxymethylcellulose, hydroxypropylmethylcellulose, hydroxybutylmethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, Cellulose derivatives such as aminomethylhydroxypropylcellulose and aminoethylhydroxypropylcellulose, starch, tragacanth, pectin, glue, alginic acid or its salts, gelatin, polyvinylpyrrolidone, polyacrylic acid or its salts, polymethacrylic acid or its salts, polyacrylamide, polymethacrylamide, copolymers of vinyl acetate with unsaturated acids such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, etc.; Examples thereof include copolymers, copolymers of vinyl ether and the above-ment
  • surfactants include nonionic surfactants, cationic surfactants, and anionic surfactants.
  • PVA-based resins are preferably used from the viewpoint of enhancing the stability of the emulsion composition.
  • PVA-based resin examples of PVA-based resins used in the present invention include unmodified PVA-based resins and modified PVA-based resins.
  • the unmodified PVA resin can be produced by saponifying a vinyl ester polymer obtained by polymerizing a vinyl ester compound.
  • vinyl ester compounds examples include vinyl formate, vinyl acetate, vinyl trifluoroacetate, vinyl propionate, vinyl butyrate, vinyl caprate, vinyl laurate, vinyl versatate, vinyl palmitate, and vinyl stearate. vinyl acetate is preferred.
  • the vinyl ester compounds may be used alone or in combination of two or more.
  • the modified PVA-based resin can be produced by copolymerizing the vinyl ester-based compound and an unsaturated monomer copolymerizable with the vinyl ester-based compound, followed by saponification.
  • Examples of the unsaturated monomer copolymerizable with the vinyl ester compound include olefins such as ethylene, propylene, isobutylene, ⁇ -octene, ⁇ -dodecene and ⁇ -octadecene, 3-buten-1-ol, Hydroxy group-containing ⁇ -olefins such as 4-penten-1-ol and 5-hexene-1-ol and derivatives such as acylated products thereof; acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid , unsaturated acids such as undecylenic acid, salts thereof, monoesters, or dialkyl esters; amides such as diacetone acrylamide, acrylamide, and methacrylamide; olefin sulfonic acids such as ethylenesulfonic acid, allylsulfonic acid, and methallylsulfonic acid; Its salt etc. are mentioned
  • the modified PVA-based resin has a primary hydroxyl group in the side chain, for example, the number of the primary hydroxyl group in the side chain is usually 1 to 5, preferably 1 to 2, particularly preferably 1. is mentioned. Furthermore, it is preferable that the modified PVA-based resin has a secondary hydroxyl group in addition to the primary hydroxyl group. Examples of such modified PVA-based resins include PVA-based resins having hydroxyalkyl groups in side chains and PVA-based resins having 1,2-diol structural units in side chains.
  • the average saponification degree of the PVA-based resin is preferably 70 mol% or more, more preferably 72 to 99 mol%, even more preferably 78 to 95 mol%, and particularly preferably 82 to 90 mol%. If the average degree of saponification is too small, the water resistance of the film obtained using the resin composition for emulsion tends to be lowered.
  • the average degree of saponification is preferably 72 mol% or more, more preferably 75 to 99 mol%, and even more preferably 80 to 95. in mol %. If the average degree of saponification is too small, the water resistance of the film obtained using the resin composition for emulsion tends to be lowered.
  • a modified PVA-based resin when used as the PVA-based resin, its average saponification degree is preferably 72 mol% or more, more preferably 75 to 99 mol%, and even more preferably 80 to 95. in mol %. If the average degree of saponification is too small, the water resistance of the film obtained using the resin composition for emulsion tends to be lowered.
  • the above average degree of saponification is measured according to JIS K 6726 3.5.
  • the viscosity of a 4% by mass aqueous solution of the PVA-based resin at 20°C is preferably 10 to 70 mPa ⁇ s, more preferably 15 to 45 mPa ⁇ s, and even more preferably 20 to 40 mPa ⁇ s. If the viscosity is too low, the emulsion composition tends to be less stable.
  • the unmodified PVA resin When an unmodified PVA resin is used as the PVA-based resin, the unmodified PVA resin preferably has a 4% by mass aqueous solution viscosity at 20° C. of 5 to 50 mPa s, more preferably 13 to 45 mPa s. Even more preferably, it is 17 to 40 mPa ⁇ s. If the viscosity is too low, the emulsion composition tends to be less stable.
  • the viscosity of the 4% by mass aqueous solution of the modified PVA-based resin at 20° C. is preferably 5 to 50 mPa ⁇ s, more preferably 13 to 40 mPa ⁇ s. s, still more preferably 17 to 30 mPa ⁇ s. If the viscosity is too low, the emulsion composition tends to be less stable.
  • the 4% by mass aqueous solution viscosity is measured according to JIS K 6726 3.11.2.
  • the average degree of polymerization of the PVA-based resin is preferably 50 to 5,000, more preferably 150 to 4,000, still more preferably 300 to 3,000.
  • the average degree of polymerization can be determined according to the method for calculating the average degree of polymerization described in JIS K 6726.
  • each of the PVA-based resins can be used alone, and unmodified PVA-based resins can be used together, modified PVA-based resins can be used together, and unmodified PVA-based resins and modified PVA-based resins can be used together.
  • two or more different types having different average saponification degrees, viscosities, modified species, modified amounts, etc. can be used in combination.
  • the mass ratio of the content of the dispersant (C) to the total content of the components (A) and (B) [(C)/[(A)+(B)]] is not particularly limited, but is from 0.05 to 0.2 is preferred, more preferably 0.06 to 0.18, still more preferably 0.07 to 0.15, and particularly preferably 0.08 to 0.12. Outside this range, the stability of the emulsion composition tends to decrease.
  • the content of component (C) is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass, based on the total amount of the emulsion resin composition (or the total amount of the emulsion composition). Above, more preferably 1% by mass or more, particularly preferably 3% by mass or more. Also, it is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 12% by mass or less, and particularly preferably 10% by mass or less. Outside this range, the stability of the emulsion composition tends to decrease.
  • the dispersion medium is not particularly limited as long as it is a water-soluble component within the substance and concentration range that does not usually affect the stability of the emulsion composition, and any aqueous solution containing them may be used, such as water only, polysaccharides. Examples include an aqueous solution and an aqueous cellulose (CNF) solution, and if the amount is small, a water-soluble organic solvent may be used in combination.
  • Organic solvents include, for example, methanol, ethanol, and acetone. Among these, water is most preferable as the dispersion medium.
  • the content of component (D) is not particularly limited, but is preferably 25% by mass or more, more preferably 35% by mass or more, and even more preferably, based on the total amount of the emulsion resin composition (or the total amount of the emulsion composition). It is 40% by mass or more. Also, it is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less.
  • a dispersion medium is a combination of water and an organic solvent
  • the content of water relative to the total amount of the dispersion medium is preferably 60% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more. .
  • the mass ratio of the total content of components (A) and (B) to the content of component (D) [[(A) + (B)]/(D)] is not particularly limited, but is from 0.7 to It is preferably 1.3, more preferably 0.8 to 1.25, still more preferably 0.9 to 1.2.
  • An example of the emulsion resin composition according to the embodiment of the present invention contains, in addition to the above-described components, components that are commonly used in emulsion resin compositions as other components within a range that does not impair the effects of the present invention (for example, 10% by mass or less).
  • components include, but are not limited to, preservatives, antifungal agents, antibacterial agents, thermoplastic resins, various stabilizers, ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, antirust agents, curing agents, fillers, and the like.
  • Resin composition for emulsion and method for producing emulsion composition As a method for producing the resin composition for emulsion and the emulsion composition according to an example of the embodiment of the present invention, a production method known in the art such as a phase inversion emulsification method can be adopted. For example, (A) a step of melt-kneading an aliphatic polyester resin and (B) an additive, and (C) a dispersant and (D) a dispersion medium are added to the melt-kneaded composition. It is manufactured by a phase inversion emulsification process in which the
  • the melting point of the composition obtained by the step of melt-kneading (A) the aliphatic polyester resin and (B) the additive is not particularly limited, but for example, it is preferably 110° C. or less, more preferably 108° C. or less, and more preferably 108° C. or less. It is more preferably 105° C. or less.
  • the melting point is within the above range, the production of the emulsion composition tends to be facilitated in the phase inversion emulsification step of mixing with the dispersion medium, and the stability of the obtained emulsion composition tends to be high.
  • the lower limit of the melting point is not particularly limited, it is, for example, about 70°C.
  • the melt flow rate (MFR) of the composition obtained by the step of melt-kneading (A) an aliphatic polyester resin and (B) an additive is 8 g/10 min or more when measured at 190° C. and 2.16 kg. is preferred, 9 g/10 min or more is more preferred, and 10 g/10 min or more is even more preferred. Also, it is preferably 150 g/10 minutes or less, more preferably 100 g/10 minutes or less, and even more preferably 80 g/10 minutes or less.
  • MFR melt flow rate
  • the melt flow rate (MFR ) is preferably 10 g/10 minutes or more, more preferably 15 g/10 minutes or more, and still more preferably 20 g/10 minutes or more when measured at 190° C. and 2.16 kg. Also, it is preferably 150 g/10 minutes or less, more preferably 100 g/10 minutes or less, and still more preferably 80 g/10 minutes or less.
  • MFR melt flow rate
  • the melt flow rate (MFR ) is preferably 8 g/10 minutes or more, more preferably 9 g/10 minutes or more, and still more preferably 10 g/10 minutes or more when measured at 190° C. and 2.16 kg. Also, it is preferably 50 g/10 minutes or less, more preferably 45 g/10 minutes or less, even more preferably 42 g/10 minutes or less, and particularly preferably 42 g/10 minutes or less.
  • MFR melt flow rate
  • the method for producing an emulsion composition includes charging (A) an aliphatic polyester resin and (B) an additive into a kneader, and optionally A method of adding a solvent or the like, melt-kneading under heating conditions, adding (C) a dispersant such as a PVA-based resin, and (D) a dispersion medium such as water, and mixing and phase-inversion emulsifying these components.
  • the heating temperature is usually 40 to 250°C, preferably 60 to 200°C, more preferably 60 to 160°C, still more preferably 80 to 150°C.
  • the heating time is usually 10 to 1,800 seconds, preferably 10 to 600 seconds, more preferably 20 to 180 seconds.
  • kneader examples include extruders, homogenizers (high pressure), roll mills, kneaders, ink rolls, and Banbury mixers.
  • extruders homogenizers (high pressure), roll mills, kneaders, ink rolls, and Banbury mixers.
  • an extruder is preferable, and a multi-screw extruder having two or more screws such as a twin-screw extruder is particularly preferable.
  • Emulsion compositions can also be obtained. Specifically, pellets of a composition containing (A) an aliphatic polyester-based resin and (B) an additive are continuously supplied from the hopper of an extruder and melt-kneaded under heating conditions to obtain a PVA-based resin or the like.
  • Dispersant and (D) dispersion medium such as water are added from another supply port provided in the same extruder, kneaded and dispersed, phase inversion emulsified, and then continuously extruded from a die , an emulsion composition according to one embodiment of the present invention can be obtained.
  • the emulsion resin composition of the present embodiment obtained as described above is a water-based emulsion resin composition, and is preferably an emulsion composition obtained from a water-based emulsion resin composition.
  • An aqueous emulsion composition is one in which particulate matter is dispersed and emulsified in an aqueous solvent. Alternatively, it is an emulsion system in which an aqueous liquid such as an organic solvent is used as a dispersion medium (that is, a continuous phase).
  • the mixed composition of (A) the aliphatic polyester resin and (B) the additive is the dispersoid, which is dispersed in the aqueous solvent.
  • the emulsion composition of the present embodiment obtained as described above has excellent stability.
  • the stability of the emulsion composition can be evaluated, for example, by the method described in Examples below.
  • the sedimentation rate measured by the method described in Examples below is preferably 10% or less, more preferably 8% or less, even more preferably 6% or less, and particularly preferably 3% or less.
  • the dispersed particle size of the dispersoid in the emulsion composition according to one example of the embodiment of the present invention is 10 ⁇ m or less, preferably 5 ⁇ m or less, more preferably 2.5 ⁇ m or less, and even more preferably 2 ⁇ m or less. Also, the lower limit is usually about 0.01 ⁇ m.
  • the dispersed particle diameter is the median diameter (d50) corresponding to a cumulative particle diameter distribution value of 50% on a volume basis. ) can be measured.
  • the resin composition for emulsion according to one example of the embodiment of the present invention is excellent in biodegradability because it contains (A) an aliphatic polyester resin and (B) an additive. From the viewpoint of improvement, it is preferable to use (A) an aliphatic polyester resin, (B) an additive, and a component having biodegradability as a (C) dispersant. Among them, (C) PVA as a dispersant It is more preferable to use a system resin.
  • the emulsion resin composition according to an example of the embodiment of the present invention is not limited to the following, but is in the form of a molded article (film or the like) molded using the emulsion resin composition obtained by a known molding method.
  • the resin composition for emulsion according to one example of the embodiment of the present invention can be used as, for example, adhesives, adhesives, modifiers thereof, coating agents, heat sealing agents, paints, primers for paints, inks, binders, etc.
  • the resin composition for emulsion according to one example of the embodiment of the present invention is suitably used as a coating agent for an object to be coated (object to be coated) from the viewpoint of being excellent in heat-sealing properties, film-forming properties, and the like.
  • the heat-sealing property and film-forming property of the coating agent containing the emulsion resin composition can be evaluated, for example, by the methods described in Examples below.
  • the object to be coated with the emulsion resin composition according to one example of the embodiment of the present invention is not particularly limited, but for example, a paper substrate is preferable.
  • Pattern paper, release paper, inkjet paper, carbon paper, non-carbon paper, base paper for paper cups, greaseproof paper, manila ball, white ball, paper board such as liner, general fine paper, medium quality paper, printing paper such as gravure paper, etc. ⁇ Medium- and low-grade paper, newsprint, etc. can be mentioned.
  • a laminate comprising a layer made of a paper substrate and a layer made of an emulsion resin composition coated on the paper substrate is also suitable.
  • the object to be coated is preferably a plastic substrate
  • the plastic substrate include polyethylene terephthalate (PET) resin, polypropylene (PP) resin [biaxially oriented polypropylene (OPP), non-axially oriented polypropylene (CPP)], nylon resins, various biodegradable resins, polyethylene (PE) resins [low density polyethylene (LDPE), high density polyethylene (HDPE)], and the like.
  • PET polyethylene terephthalate
  • PP polypropylene
  • PPP polypropylene
  • CPP non-axially oriented polypropylene
  • nylon resins various biodegradable resins
  • PE polyethylene
  • PE polyethylene
  • LDPE low density polyethylene
  • HDPE high density polyethylene
  • a laminate comprising a layer made of a plastic substrate and a layer made of an emulsion resin composition coated on the plastic substrate is also suitable.
  • the coating method using the emulsion resin composition according to one example of the embodiment of the present invention is not particularly limited, but examples include roll coating, dip coating, bar coating, nozzle coating, die coating, and spraying.
  • a coating method, a spin coating method, a curtain coating method, a flow coating method, and the like can be mentioned.
  • KZW15TW-60MG twin-screw extruder
  • Example 1-2 Polybutylene succinate (a1-1) and cellulose acetate butyrate (b1-1) are continuously supplied from the hopper of a twin-screw extruder at a mass ratio of 90:10 (a1-1:b1-1), Melt-kneading was carried out in the same manner as in Example 1-1, except that a mixed composition having a melting point of 103° C. and an MFR (190° C., 2.16 kg) of 31 g/10 min was obtained. An emulsion composition was obtained. The dispersed particle size (median size) in the emulsion composition was 1.7 ⁇ m.
  • the emulsion performance of the emulsion compositions of Examples 1-1 and 1-2 was evaluated as described below. First, the sedimentation rate was evaluated in order to evaluate the stability of the emulsion composition. In addition, in order to evaluate the coating performance of the emulsion composition, evaluation of the film-forming property and evaluation of the heat-sealing property of the coating layer were performed. The results are shown in Table 1 below. As described above, in Comparative Example 1-1, no emulsion composition was obtained, so the evaluation described later was impossible.
  • Example 2-2 Polybutylene succinate adipate (a1-2) and mixed-group dibasic acid ester (b2-1) were mixed at a mass ratio of 85:15 (a1-2:b2-1) with a twin-screw extruder at 140°C.
  • a composition [melting point of the composition: 86 ° C., melt flow rate (190 ° C., 2.16 kg): 19 g / 10 minutes] was prepared by melt-kneading. 2 was obtained.
  • the dispersed particle size (median size) in the emulsion composition was 1.9 ⁇ m.
  • Example 2-3 Polybutylene succinate adipate (a1-2) and mixed-group dibasic acid ester (b2-1) were mixed at a mass ratio of 90:10 (a1-2:b2-1) with a twin-screw extruder at 140°C.
  • a composition [melting point of the composition: 86 ° C., melt flow rate (190 ° C., 2.16 kg): 13 g / 10 minutes] was prepared by melt-kneading. 2 was obtained.
  • the dispersed particle size (median size) in the emulsion composition was 2.2 ⁇ m.
  • the emulsion performance was evaluated as follows. First, the sedimentation rate was evaluated in order to evaluate the stability of the emulsion composition. In addition, in order to evaluate the coating performance of the emulsion composition, evaluation of the film-forming property and evaluation of the heat-sealing property of the coating layer were performed. The results are shown in Table 2 below.
  • Examples 1-1 and 1-2 containing (A) an emulsion composition containing an aliphatic polyester-based resin and (B) a cellulose acetate-based resin as an additive are emulsions It can be seen that a composition can be obtained and that the stability of the emulsion composition and the coating performance (film-forming property and heat-sealing property) are excellent.
  • Examples 2-1 to 2-3 containing (A) an emulsion composition containing an aliphatic polyester resin and further containing (B) an ester plasticizer as an additive were precipitated.
  • Comparative Example 2-1 which does not contain an ester plasticizer, has a high sedimentation rate and excellent stability of the emulsion composition compared to these Examples. It turns out that it is inferior to sex.
  • Examples 2-1 to 2-3 containing (A) an emulsion composition containing an aliphatic polyester resin and further containing (B) an ester plasticizer as an additive , While it is excellent in coating performance (film-forming property and heat-sealing property), Comparative Example 2-1, which does not contain an ester plasticizer, has coating performance (film-forming property) compared to such examples. It turns out to be inferior.
  • the resin composition for emulsion and the emulsion composition of the present invention are particularly useful as various coating agents, for example, coating agents for paper substrates, coating agents for plastic substrates, and the like.

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  • Life Sciences & Earth Sciences (AREA)
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Abstract

L'invention concerne une composition de résine en émulsion qui facilite la production d'une composition en émulsion, et permet d'obtenir une composition en émulsion qui présente une excellente stabilité, même lorsqu'elle contient une résine de polyester aliphatique.　La composition de résine en émulsion contient (A) une résine de polyester aliphatique, et (B) une résine d'acétate de cellulose, et un ou plusieurs types d'additifs choisis dans le groupe constitué de plastifiants de type ester.
PCT/JP2022/018470 2021-04-22 2022-04-21 Composition de résine en émulsion et agent de revêtement WO2022225024A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2624017A (en) * 2022-11-04 2024-05-08 Kemira Oyj Method of manufacturing an aqueous dispersion

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07258453A (ja) * 1994-02-09 1995-10-09 Novamont Spa 生分解性プラスチック材料製発泡製品とその製造方法
JP2001354841A (ja) * 2000-06-16 2001-12-25 Showa Highpolymer Co Ltd 生分解性ポリエステルの水系分散液
JP2004107413A (ja) * 2002-09-17 2004-04-08 Mitsui Chemicals Inc 可塑剤含有ポリ乳酸系樹脂水分散体
JP2004238579A (ja) * 2003-02-10 2004-08-26 Riken Vitamin Co Ltd 生分解性エマルジョン組成物及びその塗工物
JP2007302776A (ja) * 2006-05-11 2007-11-22 Tosoh Corp カード
US20130225761A1 (en) * 2011-04-29 2013-08-29 Metabolix, Inc Process for latex production by melt emulsification

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07258453A (ja) * 1994-02-09 1995-10-09 Novamont Spa 生分解性プラスチック材料製発泡製品とその製造方法
JP2001354841A (ja) * 2000-06-16 2001-12-25 Showa Highpolymer Co Ltd 生分解性ポリエステルの水系分散液
JP2004107413A (ja) * 2002-09-17 2004-04-08 Mitsui Chemicals Inc 可塑剤含有ポリ乳酸系樹脂水分散体
JP2004238579A (ja) * 2003-02-10 2004-08-26 Riken Vitamin Co Ltd 生分解性エマルジョン組成物及びその塗工物
JP2007302776A (ja) * 2006-05-11 2007-11-22 Tosoh Corp カード
US20130225761A1 (en) * 2011-04-29 2013-08-29 Metabolix, Inc Process for latex production by melt emulsification

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2624017A (en) * 2022-11-04 2024-05-08 Kemira Oyj Method of manufacturing an aqueous dispersion

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